VIN KHOA HC V CNG NGH VIT NAM

VIN KHOA HC VT LIU

TH ANH TH

CH TO V NGHIN CU CC TNH CHT CA CM BIN NHY HI CN TRN C S VT LIU OXIT PEROVSKIT

LUN N TIN S KHOA HC VT LIU

H NI - 2011

VIN KHOA HC V CNG NGH VIT NAM

VIN KHOA HC VT LIU

TH ANH TH

CH TO V NGHIN CU CC TNH CHT CA CM BIN NHY HI CN TRN C S VT LIU OXIT PEROVSKIT

Chuyn ngnh: Khoa hc Vt liu M s: 62.44.50.01

LUN N TIN S KHOA HC VT LIU

NGI HNG DN KHOA HC PGS. TS. Nguyn Ngc Ton

H NI - 2011

LI CM N Ti xin dnh nhng li cm n u tin v su sc nht gi ti PGS. TS. Nguyn Ngc Ton - ngi Thy trc tip hng dn ti, gip v to mi iu kin thun li nht cho ti hon thnh bn lun n. Ti cng xin cm n s gip ca GS. TSKH. Nguyn Xun Phc. Nhng ch dn, nhn xt ca Thy gip em rt nhiu trong qu trnh hon thnh bn lun n ny. Ti xin gi ti TS. Hong Cao Dng, NCS. Nguyn S Hiu, NCS. H Trng Giang, ThS. Phm Quang Ngn, ThS. Giang Hng Thi lng bit n su sc v s quan tm, ng vin ti cng nh cc kin ng gp, cc tho lun khoa hc trong qu trnh xy dng v thc hin cc th nghim khoa hc ca lun n. Ti xin by t lng bit n ca mnh ti TS. L Th Ct Tng, PGS. TS. Nguyn Xun Ngha, NCS. Hng Mnh, TS. Trn ng Thnh, nhng ngi rt nhit tnh cng ti thc hin cc php o c v th nghim phn tch. Ti xin chn thnh cm n Vin Khoa hc Vt liu, B Gio dc v o to, ti KC02.05, cc ti nghin cu c bn cp c s Vin Khoa hc Vt liu v cp Vin Khoa hc v Cng ngh Vit Nam to nhng iu kin thun li nht gip ti trong qu trnh thc hin lun n. Cui cng ti xin dnh tnh cm c bit ti B, M, Chng, con trai v nhng ngi bn ca ti. Nhng ngi lun mong mi, ng vin ti, gip ti thm ngh lc hon thnh bn lun n ny! H ni, thng 6 nm 2011 Tc gi

LI CAM OAN

Ti xin cam oan y l cng trnh nghin cu ca ring ti di s hng dn ca PGS.TS. Nguyn Ngc Ton. Hu ht cc s liu, kt qu nu trong lun n c trch dn li t cc bo co ti cc Hi ngh khoa hc, cc bi bo c ng trn tp ch ca ti v nhm nghin cu. Cc s liu, kt qu nghin cu l trung thc v cha c cng b trong bt k cng trnh no khc.

Tc gi

MC LC
Trang Li cm n Li cam oan Danh mc cc k hiu, cc ch vit tt Danh mc hnh nh v th Danh mc bng biu M u ...... Chng 1. Vt liu oxit perovskit v hiu ng xc tc .... 1.1. c im cu trc oxit perovskit . 1.1.1. Cu trc oxit perovskit .. 1.1.2. S pha tp v s khuyt thiu oxy . 1.1.3. S dch chuyn oxy v tnh dn ion ca oxit perovskit ......... 1.2. c trng hp ph ca oxit perovskit .. 1.2.1. Hp ph CO v NO ... 1.2.2. Hp ph oxy .. 1.3. Xc tc d th ... 1.3.1. Phn ng phn hy H2O2 .. 1.3.2. Phn ng oxy ha CO ... 1.3.3. Phn ng oxy ha cc hyrocacbon .... 1.3.4. Phn ng phn hy oxit nit ..... 1.3.5. S oxy ha etanol .. 1.4. 1.5 c trng nhy kh ca cc oxit perovskit .. Kt lun chng ....... i iv ix 1 5 5 5 7 9 11 11 12 13 13 14 17 18 19 20 21 23 23 23 26 29

Chng 2. Cm bin bn dn oxit kim loi ... 2.1. Cc phn ng kh-cht rn v c ch cm bin dn b mt . 2.1.1. Hp ph vt l v hp ph ha hc .. 2.1.2. Cc trng thi b mt.... 2.1.3. C ch nhy kh......

2.2. Cu trc v c trng cm bin kh. 2.2.1. Cu trc cm bin. 2.2.2. Cc c trng ca cm bin kh .. 2.3. Vt liu v cm bin nhy hi cn ...... 2.4. Kt lun chng ...... Chng 3. Cc k thut thc nghim ... 3.1. Cng ngh ch to vt liu ...... 3.2. Cc phng php nghin cu cu trc, vi cu trc ......... 3.2.1. Phng php phn tch nhit ... 3.2.2. Phng php phn tch cu trc bng nhiu x tia X .. 3.2.3. Kho st hnh thi hc b mt bng knh hin vi in t qut (SEM) 3.3. Cc phng php nghin cu tnh cht ... 3.3.1. Phng php TPD xc nh gii hp ph oxy . 3.3.2. Phng php xc nh din tch hp ph b mt BET .... 3.3.3. Phng php xc nh thnh phn oxy 3.3.4. Kho st c trng nhy hi cn ca cm bin .. 3.4. Kt lun chng ...... Chng 4. Ch to v nghin cu mt s tnh cht ca cc h vt liu LaBO3 v A(Fe,Co)O3 ng dng trong cm bin kh ... 4.1. Tng hp vt liu LaFeO3 v cc yu t nh hng ln kch thc ht 4.1.1. Tng hp vt liu v phn tch DTA 4.1.2. Cc yu t nh hng ln kch thc ht trong qu trnh tng hp 4.2. H vt liu LaBO3 (B l Fe, Co, Ni v Mn) .....
4.2.1. 4.2.2.

32 32 34 43 46 47 47 50 50 51 53 54 54 56 57 58 60 61 61 61 62 66 66 67 70 70 72 74

Cu trc v kch thc ht h mu LaBO3 (B= Fe, Co, Ni v Mn).. S gii hp oxy theo chu trnh nhit.......... Cu trc tinh th ca h vt liu ....... Hnh thi hc b mt ca mu bt LFC ....

4.3. H vt liu LaFe1-xCoxO3 (0,0 x 1,0) .....

4.3.1. 4.3.2.

4.4. H vt liu AFe0.6Co0.4O3 .....

4.4.1. 4.4.2.

Cu trc tinh th ... Hnh thi hc b mt ca h mu AFe0,6Co0,4O3 ......

74 74 75 76 76 77 78 78 79 80 81 82 82 86 87 88 90 90 93 93 94 94 94 96 96 97 98 98 98

4.5. Kt lun chng ....... Chng 5. Ch to v nghin cu cc c trng ca cm bin nhy hi cn

5.1.

Ch to cm bin ..
5.1.1. 5.1.2. 5.1.3. 5.1.4. 5.1.5. 5.1.6.

H in li .. gm .. Ch to h v qu trnh in li . Ch to l vi nhit . Ch to in cc cm bin ....... Ch to mng nhy kh . S ph thuc ca in tr cm bin vo nhit . Thi gian p v thi gian hi phc ca cm bin LaFeO3. chn lc ca cm bin .... n nh ca cm bin .. Kt qu o in tr ca cm bin theo nhit Thi gian p v thi gian hi phc ca cm bin ..

5.2.

H cm bin perovskit LaBO3 (B=Fe, Co, Mn v Ni) .....

5.2.1. 5.2.2. 5.2.3. 5.2.4.

5.3.

H cm bin perovskit LaFe1-xCoxO3 (0,0 x 1,0) ...

5.3.1. 5.3.2.

5.3.3. chn lc ca cm bin .... 5.3.4. n nh ca cm bin .. 5.4. H cm bin perovskit AFe0,6Co0,4O3 (A = La, Sm, Nd v Gd) .. 5.4.1. in tr ca cm bin ... 5.4.2. Thi gian p v thi gian hi phc ca cm bin AFC4..... 5.4.3. chn lc.... 5.4.4. n nh . 5.5. C ch dn in v c tnh nhy hi cn ca cc oxit perovskit . 5.5.1. Tnh cht dn ca cc oxit bn dn loi p 5.5.2. C ch hp ph b mt ......

5.5.3. S tham gia ca oxy mng v vai tr ca ion kim loi chuyn tip trong qu trnh xc tc etanol . 5.5.4. Vai tr ca cu trc, kch thc ht v cc nguyn t t him nn hot tnh xc tc etanol .... 5.6. Kt lun chng ....... Chng 6. Ch to thit b o hi cn 6.1. Nghin cu ch to thit b o nng cn trong hi th ... 6.1.1. Cc iu kin v yu cu kim nh my o nng cn .... 6.1.2. Thit k v ch to thit b o nng cn .. 6.2. Kim tra o lng thit b .... 6.3. o th nghim nng cn trong hi th mt s cng nhn Cng ty TNHH Ch bin thc phm ng .. 6.4. nh gi hot ng, vn hnh ca cc thit b . 6.5. Kt lun chng ....... Kt lun chung...... Cc cng trnh lin quan n lun n Ti liu tham kho ... Ph lc (Kt qu o th nghim thit b o nng cn trong hi th ca mt s cng nhn Cng ty TNHH Ch bin Thc phm ng ) 118 118 118 119 121 123 107 108 109 110 111 111 116 104

DANH MC CC K HIU, CC CH VIT TT

1. Cc ch vit tt ABO3 BAC BrAC BET DTA EEL EPR FET FTIR GC HS LCD LFC LFC1 LFC2 LFC3 LFC4 LFC5 LFC6 LFC8 LFO LS MIS MS O R Low Spin Metal Insulator Semiconductor Mass Spectroscopy Orthorhombic Rhombohedral Blood Alcohol Content Breath Alcohol Content Brunauer-Emmett-Teller Differential Thermal Analysis Electronic Energy Loss spectroscopy Electron Paramagnetic Resonance Field Effect Transitor Fourier Transform Infrared spectroscopy Gas Chromatography High Spin Liquid Crystal Display cng thc chung ca oxit perovskit nng cn trong mu nng cn trong hi th xc nh din tch b mt BET phn tch nhit vi sai ph tn hao nng lng in t cng hng t in t tranzito hiu ng trng ph hng ngoi bin i Fourier sc k kh spin cao mn hnh tinh th lng LaFe1-xCoxO3 LaFe0,9Co0,1O3 LaFe0,8Co0,2O3 LaFe0,7Co0,3O3 LaFe0,6Co0,4O3 LaFe0,5Co0,5O3 LaFe0,4Co0,6O3 LaFe0,2Co0,8O3 LaFeO3 spin thp it kim loi cch in bn dn ph khi i xng trc thoi i xng mt thoi

SAW SEM TGA TPD XRD

Surface Acoustic Wave Scanning Electron Microscopy Thermogravimetric Analysis Temperature Programmed Desorption spectroscopy X - ray Diffraction 2. Cc k hiu A, A, B a, b, c C CA d EG D Ea e G, h I K k L Ln O2-, O-, O2P ppm q R

sng m b mt knh hin vi in t qut phn tch nhit vi trng ph gii hp ph theo chu trnh nhit nhiu x tia X

v tr chim gi ca cc cation t him, kim loi kim th v kim loi chuyn tip trong cu trc perovskit ABO3 hng s mng tinh th nng axit xitric khong cch gia hai mt phng tinh th etylen glycol kch thc ht tinh th nng lng kch hot in t dn in l trng th ion ha, cng dng in h s chn lc hng s tc phn ng, hng s Boltzmann kch thc ht tinh th nguyn t t him cc dng oxy hp ph ion ha p sut kh, cng sut cm bin phn triu in tch in tr

r S SBET T t Toper tres trev VO, V V Go HPHY HCHEM ED EA

bn knh ion nhy cm bin din tch b mt BET nhit tuyt i tha s dung hn nhit lm vic cm bin thi gian p thi gian hi phc ca cm bin nt khuyt in p th tch mng tinh th nng khuyt thiu oxy bin thin nng lng Gibbs tiu chun nng lng lin kt hp ph vt l nng lng lin kt hp ph ha hc nng lng phn ly nng lng hot ha linh ng mt tm hp ph phn bao ph b mt, gc nhiu x i lc in t bc sng tia X bn rng ca vch nhiu x

DANH MC CC HNH NH V TH
Hnh 1.1. Cu trc perovskite (ABO3) lp phng l tng (a) v s sp xp cc bt din trong cu trc perovskite lp phng l tng (b). Hnh 1.2. Hnh 1.3. S bin dng ca cu trc perovskit khi gc lin kt B-O-B 180o. S di chuyn ca cc nt khuyt oxy trong perovskit (a) S to thnh ca mt nt khuyt oxy; (b) v tr nt khuyt b dch chuyn. Hnh 1.4. Hnh 1.5. S cu trc lin kt ca dinitrosyl, nitrit v nitrat. S hp ph v gii hp oxy trn b mt ca cc oxit LaBO3 (B = Cr, Mn, Fe, Co, Ni). Hnh 1.6. M hnh tng tc d th H2O2 trn mt (001) ca oxit perovskit (a); Cu hnh in t ca cc kim loi chuyn tip B (b). Hnh 1.7. Hot tnh xc tc CO ca h oxit perovskit LaBO3 (vi B = V, Cr, Mn, Fe, Co, Ni) 500 K vi (a) hn hp CO/O2 t l 2:1; (b) hn hp CO/O2 vi t l 1:1; vi ( ) tng ng V; ( ): Cr; ( ): Mn; ( ): Fe; ( ): Co v ( ): Ni. Hnh 1.8. Hot tnh xc tc propylen v isobuten ca h oxit perovskit LaBO3 (B = V, Cr, Mn, Fe, Co, Ni) 573 K. Hnh 2.1. M hnh Lennard-Jones cho hp ph vt l v hp ph ha hc; (a) hp ph vt l v (b) hp ph ha hc. Hnh 2.2. Hp ph ng nhit in hnh: I. II. III. Hnh 2.3. hp ph vt l, chuyn tip bt thun nghch, hp ph ha hc.

M hnh Madelung cho cht rn ion MX: l i lc in t v I l th ion ha.

Hnh 2.4.

Cc loi oxy hp ph c pht hin trn b mt SnO2 cc nhit khc nhau vi cc phn tch TPD, FTIR v EPR.

Hnh 2.5.

S hp ph ngho ca X l X- trn bn dn loi n: (a) vng bng, (b) sau hp ph v hp ph ca X l X+ trn bn dn loi p: (c) vng bng, (d) sau hp ph.

Hnh 2.6.

S to thnh hng ro th gia cc ht khi c s hp ph oxy trn b mt vt liu loi bn dn n.

Hnh 2.7.

Cu trc cm bin kiu khi gia nhit trc tip TGS 109 (a) v gia nhit gin tip TGS 813 (b) ca Hng Figaro (Nht Bn).

Hnh 2.8. Hnh 2.9.

Cm bin dng mng dy. nhy ca cm bin kh SnO2 cc nhit khc nhau vi cc kh chy: H2, CO, C2H8 v CH4; S ph thuc ca TM vo T50. Profin nng cc cht kh ngang qua chiu dy mng xp. Cc in cc c t trn nh, y hoc mt bn ca lp nhy kh. S: in cc mt bn, B: in cc y v U: in cc nh.

Hnh 2.10. Hnh 2.11.

Hnh 2.12.

S thm kh vi hot tnh khc nhau (cao, trung bnh v thp) ca thnh phn nhy kh, R: kh kh v RO: kh oxy ha.

Hnh 2.13.

(a) cc v tr in cc c s dng thit k cm bin; (b) cc cu hnh in cc ([i]: ci rng lc, [ii]: tip xc 4 im v [iii]: phng).

Hnh 2.14.

S cu trc vng nng lng cho (a) cm bin mng mng v (b) cm bin mng dy vi mch tng ng ca chng v p ng dng th.

Hnh 3.1. Hnh 3.2. Hnh 3.3.

S minh ha cc phn ng xy ra trong phng php Pechini. S qu trnh ch to vt liu ABO3. Gin m t nguyn l hot ng ca mt thit b phn tch nhit vi sai.

Hnh 3.4. Hnh 3.5. Hnh 3.6.

Hin tng nhiu x tia X t hai mt phng mng tinh th. S khi ca mt thit b nhiu x tia X. S nguyn l ca knh hin vi in t qut (SEM).

Hnh 3.7. Hnh 3.8. Hnh 3.9. Hnh 3.10. Hnh 3.11. Hnh 3.12. Hnh 4.1. Hnh 4.2. Hnh 4.3. Hnh 4.4. Hnh 4.5. Hnh 4.6.

S khi h o TPD. H o Micromeritics AutoChem II 2920. th BET in hnh. S ly tn hiu ca cm bin. S b tr th nghim h to hi cn 34 oC. H to hi cn. Hnh nh xerogen mu LaFeO3 thu c sau khi sy 15 gi 120oC. Gin DTA v TGA ca bt xerogen mu M2. Gin nhiu x tia X ca cc mu M1, M2 v M3. nh hng ca lng EG ln kch thc ht LaFeO3. nh SEM ca mu M2 (a) v M8 (b). Gin nhiu x tia X ca cc mu bt LaBO3 (B= Fe, Co, Ni v Mn). Ph TPD-O2 ca cc mu LaBO3; B: Mn, Fe, Co (a) v Ni (b). Hnh minh ha qu trnh hp ph v gii hp oxy trn b mt v cc qu trnh trao i oxy trong h vt liu ABO3.

Hnh 4.7. Hnh 4.8.

Hnh 4.9. Hnh 4.10

Gin nhiu x tia X ca mu LaFe1-xCoxO3- (0,0 x 1,0). S dch chuyn vch nhiu x 2=32,2o ca h mu theo hm lng coban: (a) Vi x = 0,0 - 0,4: rng vch thay i; (b) Vi x = 0,5 1,0: xut hin s tch i vch.

Hnh 4.11. Hnh 4.12. Hnh 4.13. Hnh 5.1. Hnh 5.2. Hnh 5.3. Hnh 5.4.

nh SEM ca cc mu LFC2 (bn tri), LFC4 (bn phi). Gin nhiu x tia X ca h AFe0,6Co0,4O3 (A=La, Nd, Sm, Gd). nh SEM ca mu GdFe0,6Co0,4O3. Mt ct ngang hai cu hnh cm bin. Bn thit k mt n in li cho cm bin. H in li. nh li tch hp mt n.

Hnh 5.5. Hnh 5.6.

nh l vi nhit c ch to bng phng php in li ln gm. S ph thuc th nui vo nhit l vi nhit; c trng cng sut ca l vi nhit.

Hnh 5.7. Hnh 5.8.

S n nh nhit cm bin theo thi gian. (a) - nh in cc cm bin ch to bng phng php in li; (b) nh mng nhy kh tch hp in cc, l vi nhit trn 2 mt.

Hnh 5.9. Hnh 5.10. Hnh 5.11.

Chiu dy mng nhy kh LaFeO3. Cm bin nhy hi cn c ch to hon chnh. S ph thuc vo nhit ca dn cm bin da trn vt liu LaBO3.

Hnh 5.12. Hnh 5.13.

S ph thuc vo tham s nhit (1000/T) ca hm ln(). Hnh minh ha c ch hp ph hi nc trn b mt cm bin LaFeO3.

Hnh 5.14.

nhy cm bin LaBO3 (B=Fe, Co, Mn v Ni) ph thuc vo nhit trong mi trng cha etanol 0,4 mg/l. S thay i nhy cm bin LFO. c trng hi p ca cm bin LFO ti 260 oC, nng cn 0,39 mg/l.

Hnh 5.15. Hnh 5.16.

Hnh 5.17.

S ph thuc nhit ca nhy cm bin LFO vi cc kh etanol, methanol, axeton v cacbonic nng 0,39 mg/l.

Hnh 5.18. Hnh 5.19.

chn lc ca cc cm bin LaFeO3 vi etanol, metanol, axeton. n nh thi gian ngn ca cm bin LFO (a) v n nh thi gian di trong mi trng hi cn 0,39 mg/l (b).

Hnh 5.20.

S ph thuc nhit ca dn cm bin LaFe1-xCoxO3 (0,1 x 0,4). S ph thuc nhit ca nhy cm bin LFC vi nng etanol 0,39 mg/l.

Hnh 5.21.

Hnh 5.22.

nhy ln nht (Smax) v nhit hot ng ph thuc hm lng coban (x). S thay i nhy cm bin LFC4 theo nng hi cn. c trng hi p ca cm bin LFC4 ti 228 oC. S ph thuc nhit ca nhy cm bin LFC4 vi cc kh etanol, methanol, axeton v cacbonic (0,39 mg/l).

Hnh 5.23. Hnh 5.24. Hnh 5.25.

Hnh 5.26. Hnh 5.27.

n nh ca cm bin LFC4. S ph thuc nhit ca dn cm bin da trn vt liu AFe0,6Co0,4O3 (A = La, Sm, Nd v Gd) trong mi trng khng kh m.

Hnh 5.28.

S ph thuc nhit ca nhy cm bin AFC4 vi nng etanol 0,39 mg/l.

Hnh 5.29. Hnh 5.30.

S thay i nhy cm bin AFC4 theo nng hi cn. nhy ca cc cm bin AFC4 vi etanol, methanol, axeton v cacbonic nng 0,39 mg/l ti 228 v 245 oC.

Hnh 5.31.

n nh thi gian di trong mi trng hi cn 0,39 mg/l: (a) LaFC4; (b) GdFC4; (c) NdFC4; (d) SmFC4.

Hnh 5.32. Hnh 5.33. Hnh 5.34. Hnh 6.1. Hnh 6.2. Hnh 6.3.

S minh ha c ch oxy ha etanol ca cc vt liu LaBO3. S ph thuc ca hm ln(Rg/Ra) vo tham s ln(Cetanol). Cu hnh spin trong khi bt din BO5 trn b mt vt liu LaBO3. S khi thit b o nng kh. S nguyn l phn tng t (analog). nh my o Alco-I cm tay ghp ni vi my in mini.

DANH MC BNG BIU

Bng 2.1. Bng 2.2. Bng 4.1. Bng 4.2. Mt s thit b o hi cn c thng mi ha trn th trng: Tng kt cc vt liu nhy hi cn nh hng ca lng etanol ln kch thc ht LaFeO3 Hng s mng v kch thc ht tinh th trung bnh ca h mu LaBO3 (B= Fe, Co, Ni v Mn) Bng 4.3. Bng 4.4. Bng 4.5. Bng 4.6. Bng 5.1. Nhit v lng oxy gii hp Kch thc ht v cc thng s mng ca h mu LaFe1-xCoxO3 Kt qu phn tch thnh phn oxy. Hng s mng, kch thc ht ca cc mu Thi gian p (tres) v thi gian hi phc (trev) ca cc cm bin AFC4 (A=La, Gd, Nd v Sm) Bng 6.1. Cc thng s k thut ca thit b o nng cn

MU
Ngy nay, cc cm bin kh c ng dng rng ri trong rt nhiu cc lnh vc khc nhau nh: kim sot mi trng sng v mi trng cng nghip nhm m bo sc khe v an ton lao ng; iu khin t l khng kh - nhin liu trong cc ng c t trong nhm nng cao hiu sut ca phn ng chy v tit kim nhin liu; iu khin mi trng trn my bay, tu v tr; pht hin hng cm ti cc ca khu v sn bay Do , i hi cc cm bin phi c nhy cao, chn lc tt v hot ng n nh. Thnh phn hn hp kh cng c th c o mt cch chnh xc bng cc thit b phn tch nh sc k kh, khi ph, ph hng ngoi bin i Fourier hoc bng cch phi hp cc thit b ny. Cc thit b ny thng rt t tin, kh vn hnh, cng knh v khng th vn hnh ngoi mi trng. Trong cc trng hp nh vy, cm bin kh hoc thit b o da trn cm bin kh l s la chn ph hp. Nhiu dng cm bin c pht trin pht hin cc cht ha hc trong pha kh. Chng bao gm thit b quang da trn hin tng thay i mu sc hoc pht hunh quang, thit b sng m b mt, cc thit b in ha, ha in tr/bn dn, diod kim loi - in mi - bn dn, tranzito hiu ng trng v mt s dng khc. Tuy nhin, cc cm bin kiu in tr c bit hp dn do a dng v vt liu nhy kh v cc phng php ch to, gi thnh r, phm vi ng dng rng v em li nhiu tim nng ng dng trong vic ch to cm bin a h. Cm bin kh cho php xc nh thng tin v mi trng kh, da trn lp nhy kh v phn chuyn tn hiu in. Vic pht hin kh c da trn s thay i mi trng kh dn n thay i cc tnh cht lp nhy kh v c chuyn thnh tn hiu in. Lp nhy kh c ti u ha bng vic la chn vt liu, phn chuyn tn hiu in c ti u ha bng vic la chn cng ngh thch hp. Trong s cc cm bin kh, cc cm bin da trn cc vt liu bn dn oxit kim loi rt quan trng do s a dng v vt liu nhy kh v phng php ch to. Bn cnh nhng u im nh thi gian sng di, tin cy cao, c bn tt vi cc kh n mn, gi thnh thp th cm bin nhy kh bn dn oxit kim loi li th hin cc nhc im nh chn lc thp, b nh hng bi m mi trng, d

b gi ha Do vy, cc gii php thng c cc nh nghin cu la chn l tm quy trnh ch to vt liu n nh, gim kch thc ht xung c nano mt nhm lm tng nhy kh; la chn vt liu thch hp cho chn lc cao vi tng loi kh. Cc vt liu nhy kh c nghin cu v ng dng rng ri l SnO2, TiO2, In2O3, WO3 tng chn lc ca cm bin da trn cc vt liu ny, cc nh nghin cu pha tp vt liu ny vi cc kim loi c hot tnh xc tc cao nh Pt, Pd, Au hay trn ln vi cc oxit kim loi khc. Mt khc, trong s cc vt liu bn dn oxit kim loi, cc vt liu perovskit ABO3 thu ht c nhiu s quan tm c bit hn c bi s a dng v tnh cht cng nh c ch xc tc ca chng. Hn na, hot tnh xc tc ca cc h vt liu ny c th thay i c v ph thuc vo s thay th tng phn bi cc nguyn t kim loi khc nhau vo cc v tr A hoc/v v tr B trong cu trc. Hn th na, cc oxit perovskit cn cho bn nhit cao, cu trc n nh nn c th ci thin c tin cy v tui th ca cm bin. Cho n nay, cc vt liu oxit bn dn kim loi v cc oxit perovskit ABO3 s dng ch to cm bin nhy kh c th c tng hp bng nhiu phng php ha hc khc nhau nh: phng php ng kt ta, phng php sol-gel, phng php thy phn nhit, phng php vi nh tng, phng php phn hy dng siu m, phng php phn hy dng laze, phng php lng ng ha hc t pha hi v phng php thy phn nhit cc tin hp cht. Phng php sol-gel c s dng rng ri hn c bi cc sn phm thu c c ng th tt, kch thc ht nh (c nano mt), din tch b mt ln (vi chc m2/g) thch hp vi ng dng cm bin kh. Trong cng ngh ch to cm bin, lp nhy kh thng c ch to di dng mng mng hoc mng dy. Mng mng c tc p ng kh nhanh hn nhng in tr ca cm bin li khng n nh bi s khuch tn kh kh khn do cu trc ca mng. Trong mng dy, kh i qua mt phn chiu dy ca mng, tc p ng b hn ch bi chiu dy. Mng dy c din tch b mt hiu dng i vi s hp ph kh ln, nhy ca cm bin t l nghch vi kch thc ht. Trong

thc t, mc d cc cm bin mng dy c cng sut tiu th ln hn, nhng cng ngh ch to n gin, d thc hin ti phng th nghim, chi ph thp, tui th cao hn, c nhy cao hn, bn hn. Ngoi ra, k thut ch to mng dy cn c kh nng sn xut v t ng ha cao hn, thi gian cn thit t nguyn mu n sn phm rt ngn. Do , cc cm bin mng dy thu ht c s quan tm nghin cu ca nhiu nh khoa hc v nhanh chng c pht trin thnh cc sn phm thng mi. Trong iu kin phng th nghim Vit nam, chng ti la chn cng ngh mng dy nghin cu v ch to cm bin. Vit Nam, hng nghin cu v vt liu nhy kh cng c nhiu phng th nghim quan tm t nhiu nm. Tuy nhin cc nghin cu v vt liu (phn ln l cc bn dn oxit kim loi n nh SnO2, TiO2) cm bin nhy kh mi ch dng cc nghin cu c bn, o to v ch to th nghim cm bin v thit b bo ngng (Trng i hc Bch khoa H ni). Bn cnh , s lm dng ru, bia ca ngi lao ng v ngi iu khin cc phng tin giao thng gy ra nhiu tai nn ng tic, gy thit hi v ngi v ca. Do vn t ra i vi cc nh qun l v cc nh chc trch l phi kim sot hm lng cn trong hi th ca ngi lao ng trong gi lm vic v ngi iu khin phng tin giao thng trn ng. V nhng l do nu trn, mc ch ca lun n ny l: Ti u ha cng ngh ch to vt liu oxit perovskit da trn phng php sol gel to phc. Tng hp cc vt liu oxit perovskit LaBO3 (B=Fe, Co, Ni v Mn), AFe1xCoxO3

(vi 0,0x1,0) (A=La, Gd, Nd v Sm) c cu trc nano mt ng

dng ch to cm bin nhy hi cn. La chn vt liu ph hp cho cm bin nhy hi cn. La chn phng n thit k ch to cm bin v o c cc c trng nhy hi cn Ch to th nghim thit b o hi cn c kh nng s dng ngoi hin trng.

vi ti: Nghin cu ch to v cc tnh cht ca cm bin nhy hi cn trn c s vt liu oxit perovskit. Cu trc ca lun n gm: L do chn ti c trnh by trong phn m u. Chng mt gii thiu v vt liu oxit perovskit - cu trc v cc tnh cht lin quan n hot tnh xc tc ca chng. Tng quan v cm bin da trn c s bn dn oxit kim loi v cc vt liu ng dng cho cm bin nhy hi cn c trnh by trong chng hai. Chng ba trnh by tm tt cc k thut thc nghim c s dng nghin cu trong lun n. Cc kt qu nghin cu ca lun n c trnh by trong ba chng cui. Trong chng bn cp n cc kt qu nghin cu ch to v mt s tnh cht cc h vt liu oxit perovskit ng dng trong cm bin kh, chng nm trnh by cc kt qu nghin cu ch to v cc c trng ca cm bin nhy hi cn trn nn oxit perovskit v chng su l cc kt qu v ng dng vt liu, cm bin nhy hi cn trong thit b o hi cn c ch to th nghim. Phn kt lun chung tm tt li cc kt qu t c ca lun n. Cui cng l ti liu tham kho v danh mc cc cng trnh cng b trn cc tp ch, tham d hi ngh khoa hc trong v ngoi nc lin quan n lun n.

CHNG1 VTLIUOXITPEROVSKITVHIUNGXCTC
Cc cht xc tc s dng trong cng nghip ha cht hin i phn ln u da trn cc oxit kim loi phc hp. Trong , cc oxit phc hp kiu perovskit ABO3 l ni bt hn c. S a dng v tnh cht ca cc oxit ny c c trng bi 90% cc nguyn t kim loi trong bng h thng tun hon cc nguyn t ha hc tn ti trong t nhin dng cu trc oxit kiu perovskit v kh nng tng hp cc oxit perovskit phc hp bi vic thay th tng phn cc cation v tr A v B bng cc nguyn t nguyn t khc. S thay th tng phn ny dn n s a dng trong tnh cht ca cc oxit h perovskit [108]. Trong chng ny, chng ti s cp n mi tng quan gia cu trc ha hc ca cc oxit perovskit ABO3 vi hiu ng xc tc d th v ha hc b mt ca vt liu. 1.1. c im cu trc oxit perovskit 1.1.1. Cu trc oxit perovskit Cu trc perovskit l tng ABO3 l lp phng vi nhm khng gian Pm 3 m c m t trn hnh 1.1a. Trong cu trc ny, mng n v c trng cho cu trc l mt hnh lp phng c cc hng s mng a = b = c v cc gc = = = 90o). V tr tm nh ca hnh lp phng l v tr ca ion A, thng c gi l v (b)
Hnh 1.1: Cu trc perovskit (ABO3) lp phng

( )

V tr A V tr B V tr Oxy

(a)

tr A, tm ca su mt hnh lp l tng (a), v s sp xp cc bt din trong cu trc perovskite lp phng l tng (b). phng l v tr ca ion phi tr, thng l v tr ca ion oxy v tm ca hnh lp phng l v tr ca ion B, thng c gi l v tr B. iu c ngha l xung quanh ion B c su ion oxy v

quanh ion A c mi hai ion oxy phi tr. Nh vy cu trc perovskit l mt siu cu trc vi mt khung kiu ReO3 c xy dng bi s kt hp cation A vo trong cc bt din BO6. c trng tinh th quan trng nht ca cc hp cht c cu trc ny l s tn ti cc bt din BO6 ni tip trong mng n v vi su ion phi tr (thng l ion O2-) ti nh ca bt din v mt ion dng B ti tm ca bt din. Cch m t ny cho chng ta thy gc lin kt B-O-B, = 180o v di lin kt B-O gia cc ion dng B v ion phi tr bng nhau. iu ny cho php chng ta hnh dung mt cch tng minh hn khi c s bin dng ca cu trc perovskit khi h tinh th khng cn l lp phng, di lin kt B-O theo cc trc s khng bng nhau v gc lin kt BO-B s khc 180o (hnh 1.2). Trong cu trc l tng, khong cch B-O l a/2 (a l hng s mng ca mng lp phng) trong khi khong cch A-O l a/2 v mi lin h gia cc bn knh ion l: rA+rO = 2(rB+rO). Tuy nhin, ngi ta cng thy rng cu trc lp phng ca cc hp cht ABO3 vn c duy tr ngay c khi phng trnh trn khng c tha mn. Khi o lch khi cu trc l tng, tha s dung hn (t) p dng nhit phng c nh ngha bi phng trnh [25]: t = (rA+rO)/2(rB+rO) (1.1)
Hnh 1.2. S bin dng ca cu trc perovskit khi gc lin kt B-O-B180o

Mc d i vi cu trc perovskit l tng, t = 1 nhng kiu cu trc ny vn tn ti cc gi tr t thp hn (0,75 < t < 1,00). Cu trc lp phng l tng ny xut hin trong mt s trng hp gi tr t rt gn 1 v cc nhit cao. Trong a s trng hp xut hin s mo mng tinh th. S lch khi cu trc l tng dn n cc h tinh th c i xng thp hn nh orthorhombic (trc thoi), rhombohedral (mt thoi), tetragonal (t gic), monoclinic (n t hay mt nghing) v triclinic (tam

t hay ba nghing). Cu trc mo mng c th tn ti nhit phng nhng n c th chuyn sang cu trc lp phng khi nhit cao. S chuyn pha cu trc ny c th xut hin theo nhiu bc qua cc pha mo trung gian [31, 46]. 1.1.2. S pha tp v s khuyt thiu oxy Vic thay th mt phn cc cation v tr A v B bng mt nguyn t th ba l mt k thut c bn thay i cu trc ca cc hp cht perovskit, nhm khm ph ra cc tnh cht mi. Tnh khng hp thc d oxy trong cc oxit perovskit thng khng ph bin do vic gp oxy vo mng tinh th nh oxy ngoi nt v mt nhit ng hc l khng thun li. Hn na cu trc ABO3 gm mt mng AO3 xp cht vi cc cation B trong cc bt din BO6. Do s c cc nt khuyt cc v tr cation [90, 101, 102]. Van Roosmalen v cc cng s [117] kho st mu LaMnO3+ bng phng php nhiu x ntron, nhiu x in t cho thy khng c oxy ngoi nt v xut hin nt khuyt cation v tr La v Mn vi lng bng nhau. Nhiu cng trnh nghin cu khc cho thy cc nt khuyt v tr cation thng chim u th v tr nguyn t t him (v tr A). Cc nt khuyt v tr B trong cc oxit perovskit khng ph bin do cation B c in tch ln v kch thc nh nn cc nt khuyt v tr B l khng thch hp v nhit ng hc, cation A ln hn, v tr phi tr 12 d b thiu ht tng phn [26, 45, 118]. Hn na, dy BO3 trong cu trc perovskit to nn mt mng li ba chiu bn vng. Mt th d tiu biu l s thay th Sr cho La trong La1-xSrxCoO3-y c thc hin mt cch d dng [45]. Th nht l cc ion dng La3+ v Sr2+ c bn knh ion gn bng nhau (rLa3+ = 0,136 nm, rSr2+ = 0,118 nm [45]), do s thay th v tr s hu nh khng gy ra s mo mng. Th hai, s phn b v tr ca cc ion m O2- quanh La3+ hoc Sr2+ l tng ng nhau, cho php s thay th gia La3+ v Sr2+ trong mng. Th ba, s thay th Sr2+ cho La3+ s to ra s b in tch cc b, nhng cc ht ti cc b loi p c cn bng bi s bin i mt phn Co3+ thnh Co2+. Cui cng, s mt mt in tch cc b do s th ch La3+ bi Sr2+ c cn bng bng cch to ra s khuyt thiu oxy cng nh s bin i Co3+ thnh Co4+. Cng thc cu to ha hc ca La1-xSrxCoO3-y l [74]:

La1-x3+Srx2+Co1-x+2y3+Cox-2y4+O3-y2-VyO

(i vi y x/2)

(1.2)

y VyO biu din nt khuyt oxy. Cng thc ny cho chng ta thy dn in ca vt liu l mt hm ph thuc vo nng thay th x. Nu khng c s khuyt thiu oxy (y = 0), trng thi ion ca La1-xSrxCoO3 l: La1-x3+Srx2+Co1-x3+Cox4+O32(1.3)

S thay th gia La v Sr trong mng c th xy ra l do s tn ti ng thi cc ha tr khc nhau ca Co v do s to thnh cc khuyt thiu oxy. xc nh gii hn lng khuyt thiu oxy, chng ta c th xt lp (AO3-y)(4-2y)-. duy tr khung c s ca ABO3-y, lng khuyt thiu ion m ln nht l ymax = 1. Thc vy, khi xem xt s sp xp cc lp ion dng B v s c mt ca cc ion pha tp, biu thc (1.2) cho thy lng khuyt thiu ln nht l x - 2ymax = 0 hay ymax = x/2. Thay vo biu thc (1.2) thu c: La1-x3+Srx2+Co3+O3-x/22-Vx/2O (1.4)

Trong biu thc ny khng c mt Co4+, khi vt liu s mt chc nng ca n. Hn na, hm lng nt khuyt ln nht c php l bng mt na hm lng pha tp, tr khi Co3+ c chuyn thnh Co2+. Nu s thay th La bi Sr l c trt t v hm lng tp cht Sr trong n v khng phi mt s nguyn, chng ta hy vng s c mt siu cu trc, c th c xc nh bng k thut nhiu x in t. Phn tch trn c da trn gi thit rng s khuyt thiu oxy tha mn iu kin y nh hn hoc bng x/2. Do s c s chuyn i ho tr t Co3+ n Co4+. Trong trng hp s khuyt thiu oxy khng cn bng in tch, v vy hm lng oxy c th c duy tr vi ba nguyn t trn mt n v cng thc v cu trc t c s n nh nht. Mt khc, nu s khuyt thiu ion m l ln, c th dn n s chuyn Co3+ thnh Co2+: La1-x3+Srx2+Co1-2y+x3+Co2y-x2+O3-y2-VyO (i vi x/2 y 1) (1.5)

Nu cht pha tp c mt vi nng x, s khuyt thiu oxy s tn ti cn bng in tch. Nhng hm lng v tr khuyt cn phi nh hn mt (y 1)

m bo s n nh ca cu trc. Trn thc t, cc php o ph EEL phn gii cao ca Co2+, Co3+ v Co4+ c th xc nh c s khuyt thiu oxy. 1.1.3. S dch chuyn oxy v tnh dn ion ca oxit perovskit Cc hp cht vi cu trc perovskit hoc cu trc tng t thng c s dng nh cc vt liu dn oxy, chng hn nh LaMnO3 v trong lnh vc pin nhin liu nh Fe1-xSrxCoO3 [45, 114]. i vi cc vt liu ny, kch thc, linh ng cao ca cc ion dng v tr A v B cng nh s pha tp cc ion dng ph hp c th lm cho oxy khuch tn d dng trong tinh th. Vi cc lp (AO3)4- trong cu trc perovskit, kch thc ca cc ion dng A c th xem nh l tng ng vi cc ion m oxy, nh Ba2+ (0,135 nm), Pb2+ (0,119 nm), Sr2+ (0,118 nm) v Ca2+ (0,100 nm); O2- (0,144 nm). Khi , s di chuyn ca oxy s b hn ch. cc ion m oxy khuch tn d dng hn, cch tt nht l to ra cc nt khuyt oxy. D nhin l vic tng cng nng nt khuyt oxy c th t c khi vt liu c x l nhit. Nhng nhit thng, s thay th ca cc ion dng ha tr 3 (th d nh La3+) bng cc ion dng ho tr 2 nh Sr2+ v Ca2+, cng c th to thnh cc nt khuyt oxy.

Cation B

Cation A

Nt khuyt O

Hnh 1.3. S di chuyn ca cc nt khuyt oxy trong perovskit: (a) S to thnh ca mt nt khuyt oxy; (b) v tr nt khuyt b dch chuyn [45, 114].

Trong cc lp (LaO3)3-, cc ion m oxy c xp st nhau bao quanh ion dng A. Vi vic thiu i mt ion m oxy (do s to thnh ca mt nt khuyt) s

10

gy ra mt tng tc Coulomb mnh gia cc ion dng A (hnh 1.3). Lc y ny lm khong cch gia hai ion dng A lin k ln hn, v cc ion dng A ht cc ion m oxy xung quanh chuyn ng vo v tr nt khuyt oxy. Qu trnh ny tng ng vi s chuyn ng ca cc nt khuyt oxy theo chiu ngc li. S di chuyn lin tc ca cc ion m ny l nguyn nhn gy ra tnh dn ion ca vt liu. Tnh dn ion ny tng ng vi s dch chuyn ca cc nt khuyt oxy. Cng vi cc c tnh cu trc c bit v kh nng khuch tn oxy, lm cho cc vt liu ny nm trong s cc ng vin thch hp nht cho cc ng dng trong pin nhin liu, xc tc oxy ho, v cm bin nhy kh. Mt khc, Ishihara v cc ng nghip [42] nghin cu thy rng LaGaO3 c pha tp bi cc cation kim loi chuyn tip lm tng tnh dn ca ion oxy cng nh t l thm oxy ca mu. c bit, trong h La0,8Sr0,2Ga1-xNixO3, t l thm oxy tng vi s tng ca nng Ni v t gi tr ln nht ti x bng 0,25 mi nhit . H Sr0,4La0,6Fe0,8Co0,2O3 c xem nh l mt vt liu dn ion y ha hn trong k thut mng bn thm tch oxy [42]. Bn knh ca cc cation A v B trong cu trc perovskit ABO3 c vai tr quan trng i vi tnh dn ion ca vt liu. Khi tnh ton mi tng quan gia nng lng hnh thnh nt khuyt v bn knh ca cc cation A v B, Cherry v cc ng nghip [13] ch ra rng, nng lng hnh thnh nt khuyt nh hn nng lng ca cc ion A v cho gi tr ti u khi bn knh nt khuyt c gi tr bng 0,095 nm. Nng lng hnh thnh nt khuyt gim vi s tng kch thc cation B v cho gi tr cc tiu ti 0,075 nm. l gii cc kt qu ny, tha s dung hn (t) cng c kho st [64]. Cc tnh ton cho thy rng cc perovskit vi t 0,81 cho nng lng hnh thnh nt khuyt thp hn v do vy chng s khuch tn nhanh hn, iu ny em li nhiu ha hn trong nghin cu xc tc v pin nhin liu vng lm vic c nhit thp. Nhng pht hin ny c th c l gii bi hiu ng hi phc mng. Cc oxy linh ng tin gn li nh, chng phi i qua tm ca khi tam gic c to bi cc cation. Cc tnh ton cng cho thy rng cc tng tc vng chng ln gim bi s hi phc ca cc cation ny. Gi tr t t cc tiu tng ng vi

11

trng thi cn bng hi phc ca cc cation A v B ti nt mng. Ngha l, vic phn b hi phc gia cc cation ng vai tr quan trng vng nng lng thp ca cc nt khuyt thiu oxy. iu ny c khng nh trong cc h vt liu oxit LaBO3 khi pha tp thm cc cation c ha tr thp nh Sr, Ca ... s lm tng hiu ng xc tc v dn ion ca vt liu [60, 62, 97]. 1.2. c trng hp ph ca oxit perovskit c ci nhn tng qut v c trng hp ph ca vt liu perovskit, bn cht v cu trc ca cc tm hp ph trn b mt oxit perovskit cng nh vai tr ca cc tm ny trong cc phn ng xc tc lun c kho st. Cc qu trnh ng hc hp ph v s gii hp ca cc tm b mt cng cn c xem xt. 1.2.1. Hp ph CO v NO S hp ph CO ln h vt liu LaBO3 (B = kim loi chuyn tip) c nghin cu vi nhiu cng trnh c cng b. Cc kt qu ch ra rng, kh nng hp ph CO ph thuc mnh vo cu hnh in t ca cc cation B v t gi tr ln nht khi cation kim loi chuyn tip B l Fe3+ [107]. Lng hp ph CO tng theo nhit hp ph t 298 K n 773 K. Qu trnh hp ph trn h vt liu ny l nhanh. ng hc phn ng c biu din theo phng trnh Elorich [85]. Cc kt qu kho st s hp ph ca cp CO2-CO trn h LaCrO3 ch ra rng, CO2 v CO hp ph ln cng mt loi tm trn b mt [107]. Khi c s tham gia ca O2, phn ng hp ph O2 s din ra trc sau mi n phn ng hp ph CO. Cc kh O2 v CO hp ph ln cc tm b mt khc nhau. Tng tc CO vi oxy b mt v cc ion kim loi cng c cp [21, 84, 85, 107, 111]. Kh nng hp ph kh NO trn h LaBO3 (B = kim loi chuyn tip) cng c kho st. Cc kt qu cho thy s hp ph kh NO t gi tr ln nht ng vi h cha Mn v Co [107]. Lng NO hp ph khng ph thuc vo nhit trong h LaFeO3 v LaNiO3. i vi cc h LaCrO3 v LaMnO3, hp ph thay i theo nhit l nh (di 20%) [78, 83, 84, 107].

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Quang ph hng ngoi ca NO trn LaMnO3 ch ra cc nh hp th c trng cho lin kt gia NO vi b mt mu di dng dinitrosyl, nitrit v nitrat. Pht hin ny cho thy rng tng tc phn t NO hoc thng qua ion Mn3 + to dng dinitrosyl hoc thng qua ion O2- to thnh nitrit v nitrat [131]. Cc dng cu trc dinitrosyl, nitrit v nitrat to thnh c minh ha trong hnh 1.4.

dinitrosyl

nitrit

nitrat

Hnh 1.4. S cu trc lin kt ca dinitrosyl, nitrit v nitrat

1.2.2. Hp ph oxy Qu trnh hp ph oxy trn oxit perovskit c tp trung nghin cu ch yu do cc hp cht ny c th dng lm cht xc tc cho qu trnh oxy ha-kh. Kremenic v cc ng nghip [51] bo co s hp ph oxy trn LaBO3 (B l Cr, Mn, Fe, Co, Ni). Cc tc gi ch ra cc i hp ph ng vi Mn v Co. iu ny trng hp vi cc kt qu nghin cu ca Iwamoto v cc ng nghip trong cc oxit kim loi chuyn tip M2O3 [44]. S hp ph v gii hp oxy trn b mt cc oxit perovskit LaBO3 c minh ha trn hnh 1.5 [68]. Cc kt qu kho st s hp ph oxy theo chu trnh cho thy rng, cc nh TPD oxy thu c trn h La1-xSrxCoO3 l kh phc
Hnh 1.5. S hp ph v gii hp oxy trn b mt ca cc oxit LaBO3 (B = Cr, Mn, Fe, Co, Ni) [54]

tp. Yamazoe v cc ng nghip [130] ch ra rng, trn h vt liu La1-xSrxCoO3 xut hin hai nh gii hp oxy, vi nh nhit thp (kiu ) c gn cho oxy

13

hp ph, nh nhit cao (kiu ) cao c gn cho oxy mng tinh th. S thay i nh kiu theo t phn thay th x c th c gii thch do mc khng hp thc v mt sai hng mng ca cc perovskit ny ph thuc vo gi tr x [20, 68, 74, 87, 100, 130]. Mt khc, Yokoi v cc ng nghip [132] cng ch ra rng, lng oxy gii hp v nhit nh gii hp oxy- gim khi s in t vng 3d ca cc kim loi chuyn tip tng ln [133]. Bc lin kt B-O s gim khi s in t vng 3d ca cc kim loi chuyn tip tng. Ngha l, nhit gii hp oxy ph thuc vo tng tc gia oxy hp ph vi cc ion kim loi chuyn tip. Nhn chung, s hp ph oxy trn b mt l mt qu trnh phc tp. Trong cc nghin cu gn y Au v cc ng nghip [7] ch ra rng, s hp ph oxy b chi phi cc qu trnh ng hc hp ph ha hc v mi tng quan n s to thnh cc dng oxy tch in m (O2 1.3. Xc tc d th 1.3.1. Phn ng phn hy H2O2 Phn ng phn hy H2O2 thng c quan st thy trn cc xc tc d th. Phn ng ny c nhiu tc gi la chn trong vic nghin cu qu trnh ng hc v xc nh tc phn ng. Mi lin h gia cu trc b mt ca oxit perovskit vi cc tnh cht in xc tc trong phn ng phn hy H2O2 cng c cp n [10]. Theo Wolfram v cng s [123], cc ion B trn b mt phi tr BO5 v trong khi c phi tr l BO6. Do tnh i xng b mt thp hn trong khi nn cc mc nng lng ca cc in t 3d s b tch thnh cc mc (eg, t2g). Cc mc eg ca BO6 c phn chia thnh cc mc dx2+y2 v dz2 vi mc sau nm di mc u tin trn b mt, v cc mc t2g phn chia thnh cc mc suy bin bc hai dxz, dyz v mc suy bin bc mt dxy (xem hnh 1.6b). Theo m hnh ny, cc orbital dz2 s b chim gi bi mt in t tng ng vi cc kim loi chuyn tip c cu hnh spin cao (Co, Ni). Cc orbital dz vi s c mt ca cc in t cha ghp i trong cc perovskit ABO3 c th ng mt vai tr nh cc tm hot ng cho phn ng xc 2O-).

14

tc d th H2O2 trn b mt, cho php t c tc phn ng cao do xu hng chim gi mc phn lin kt * ca lin kt Bz-OH. Mt khc, cc nghin cu phn ng phn hy H2O2 ca h vt liu LaFexNi1xO3

[123] cng ch ra rng, cc phn ng xc tc d th c s chuyn in t trn

cc oxit perovskit vi cc tm hot ng thng l cc ion kim loi chuyn tip vi cc orbital d b chim gi mt phn. Hng s tc phn ng t l tuyn tnh vi nng lng ha hc v c biu din theo biu thc di y: log(A) = mFa + c (1.6)

y A l tham s hm m c trng cho tc phn ng; Fa: nng lng hot ha ca cc tm hot ng; m l khi lng cht b xc tc; c = log(kiso) (vi kiso l tc phn ng d th phn hy H2O2 trong iu kin ng nhit. S phn b v mt ca ca cc tm hot ng b mt ny ph thuc vo thnh phn cht xc tc v cng ngh ch to vt liu.

Hnh 1.6. M hnh tng tc d th H2O2 trn mt (001) ca oxit perovskit [123].

1.3.2. Phn ng oxy ha CO Phn ng oxy ha CO c xem nh mt phn ng th nghim cho vic nghin cu mi tng quan gia hot tnh xc tc CO vi cc sai hng mng tinh th, cu hnh in t ca ion chuyn tip B3+ v tnh cht b mt ca perovskit. Trong h vt liu LnBO3, cc ion Ln3+ khng tham gia qu trnh xc tc. Cc ion

15

B3+ tham gia chnh v quyt nh hot tnh xc tc ca vt liu. c bit trong cu trc cc ion B3+ c nh x vi khong cch gia ion ny n ion khc xp x 0,4 nm s cho hot tnh xc tc vi kh CO v O2 l tt nht [109]. Trn c s d liu ng hc v quang ph, Tascon v cc ng nghip [107] xut mt c ch phn ng n gin cho qu trnh oxy ha CO trn h LaCoO3 c biu din theo phng trnh phn ng di y: O2 (kh) O2-(hp ph) CO(kh) CO(hp ph) + 2O-(hp ph) CO3 2-(hp ph) 2O-2(hp ph) CO32-( hp ph) (chm) CO2 (kh) + O 2-(hp ph) (1.7) (1.8) (1.9) (1.10)

CO(hp ph)

CO2 (hp ph) + O 2-(hp ph)

y, phng trnh phn ng (1.10) c xem nh phng trnh xc nh tc phn ng. Cc phn t O2 trong khng kh c hp ph ln v tr ca cc ion Co2+ di dng O2-, sau phn ly thnh cc nguyn t O- hp ph cng tm (Co2+). Mt khc, phn t CO s hp ph ln cc ion chim gi trn b mt mu to trng thi khng n nh. Cc phn t ny s tng tc vi cc nguyn t O- to cu trc cacbonat sau phn hy thnh kh CO2. Mt khc, hot tnh xc tc ca phn ng c trnh by trn hnh 1.7 theo mc chim gi cc mc d ca ion chuyn tip B3+. Cc bt din ca ion B3+ chia cc orbital d thnh hai mc: mc thp hn (t2g) gm cc orbital m chng b y t hn bi cc in tch m (O2-) so vi cc orbital mc cao hn (eg). Nhn thy rng hot tnh xc tc cc i t c c hai trng hp chim gi ca cc mc eg t hn 1 in t, cc mc t2g s c in y mt na hoc in y hon ton (xem hnh 1.7). Nhn chung hot tnh xc tc ph thuc nhiu vo bn cht ca kim loi chuyn tip v tr B hn l bn cht ca kim loi t him v tr A v: ACoO3 ~ AMnO3 > ANiO3 > AFeO3 >> ACrO3 [109]. Hn na, s oxy ha CO ca cc oxit perovskit ph thuc nhiu vo tnh hp thc ca chng. S bin i trng thi oxy ha ca ion B3+ thng qua vic thay th mt phn ion A3+ bi mt ion khc c trng thi oxy ha thp hn 3, lm thay i

16

ha tr ca ion B dn n thay i nng anion hay cation. S thay i ny nh hng mnh n tnh oxy ha kh ca B v tnh linh ng ca oxy trong cc oxit perovskit. Phng php ny c s dng rng ri trong vic kho st vai tr chim gi cc orbital 3d trong cc hp cht oxit perovskit. i vi h vt liu (La,A)CoO3, Hnh 1.7. Hot tnh xc tc CO ca h oxit perovskit LaBO3 (vi B = V, Cr, Mn, Fe, Co, Ni) 500 K vi (a) vo v tr A dn n lm trong hn hp CO/O2 t l 2:1; (b) hn hp CO/O2 vi t l 1:1; vi ( ) tng ng V; ( ): Cr; ( ) Mn; ( ) Fe; ( ) Co; v ( ): Ni [26]. tng tc oxy ha CO, Co2+ khi a cc ion Ce4+ trong khi c mt ca cc ion Co4+ bi vic a Sr2+ vo v tr A li lm gim tc . iu ny cho thy rng phn t CO c lin kt vi ion coban trn b mt vt liu to thnh dng phc carbonyl. C th, cc nguyn t cacbon ca nhm CO ny s kt cp vi orbital trng ca ion coban to thnh lin kt cng vi vic cho cc in t t2g ca ion Co3+ vo orbital phn lin kt ca CO. Cn ch rng vic to lin kt ca CO l ti u khi c hai qu trnh l c th thc hin c. Mi tng quan gia tc phn ng vi s chim gi ca cc orbital 3d ch ra rng, tc phn ng bin i theo p sut ring phn ca CO [28]. Bng phng php xc nh linh ng ca oxy v phn ng trao i oxy ng v, Nitadori v cc ng nghip [74] ch ra rng, oxy tham gia qu trnh xc tc c chia lm ba loi khc nhau c trng bi linh ng v ph thuc vo v tr ca chng trong cht rn bao gm: oxy b mt O-; oxy bin ht O-2 v oxy khi O2-. Voorhoeve v cng s [26] ch ra rng cc gi tr nng lng hot ha cho s xut hin ca cc ion

17

phn ng oxy ha CO i vi cc h perovskit (La,A)CoO3 (A = Ce, Sr) bin i khng ng k. 1.3.3. Phn ng oxy ha cc hyrocacbon Qu trnh oxy ha cc

hyrocacbon ca cc oxit perovskit thu ht nhiu s nhiu s quan tm ca cc nh khoa hc trn th gii. in hnh cho hng nghin cu ny l cc nhm tc gi Nakamura [68], Nitadori v cc ng nghip [74]. Trong th nghim kho st hot tnh xc tc ca h La1xSrxMnO3

cho s oxy ha propan, cc

tc gi ch ra rng hot tnh xc tc ph thuc vo tnh kh ca mu. Lng oxy hp ph ph thuc thun nghch vi tc cn bng ng v ca oxy. Cc tham s c trng cho qu trnh oxy ha xc tc hyrocacbon ph thuc vo hm
Hnh 1.8. Hot tnh xc tc oxy ha propylen v isobuten ca h oxit perovskit LaBO3 (B = V, Cr, Mn, Fe, Co, Ni) 573 K [51].

lng oxy b mt mu. Ngha l hot tnh xc tc ca mu c kim sot bi c trng khng hp thc ca thnh phn b mt mu. Trong nghin cu qu trnh t chy propylen v isobuten 573 K trn h vt liu LaBO3 (B = V, Cr, Mn, Fe, Co, Ni), Kremenic v cc ng nghip [51] ch ra rng, tc t chy isobuten cao hn so vi propylene (hnh 1.8). Trong c hai trng hp u quan st thy hai cc i LaMnO3 v LaCoO3. Kt qu ny ph hp vi c ch hp ph oxy trn b mt v ph hp vi m hnh orbital chim gi ca cc in t d trong dy oxit perovskit. Arai v cc ng nghip [4,63] ch ra rng, cc manganit, cobanit, ferrit v La1-xSrxBO3 (vi B l cc kim loi chuyn tip) c hot tnh xc tc cao tng ng

18

vi hot tnh xc tc ca Pt/Al2O3. c trng th v ca cc perovskit ny l kh nng bin i kch thc n v bng vic thay th cc ion A bng cc ion c ha tr thp hn hoc cao hn lm thay i lin kt B-O trong cu trc ABO3. Hn na, vic th tng phn cc cation v tr A c th nh hng n hot tnh xc tc ca mu do s bn ha ca cc trng thi oxy ha khng ng nht ca cc cation B v to ra cc sai hng trong cu trc tinh th. Cc sai hng ny khng ch nh hng trc tip n hot tnh xc tc m cn nh hng n linh ng ca oxy mng tinh th do tnh khng hp thc c to bi s th v tr cation A trong mu [108]. Trong cc nghin cu gn y trn h La1-xAxBO3 (B l cc kim loi chuyn tip) ca Ferri v Forri [20] cng cho thy rng, vic th v tr A bng cc cation ha tr hai (A = Sr, Ca) hay cc cation ha tr bn (A = Ce) s lm gim hoc tng hot tnh xc tc phn ng t chy CH4 tng ng [20]. Vic th cc cation ha tr 2 s lm cho cc trng thi oxy ha ca Co cao hn. Nng Co4+ tng vi s tng hm lng thay th ca cc cation ha tr hai (Sr2+). Tuy nhin, do cc cation Co4+ khng bn nn qu trnh gii phng oxy c th xy ra dn n s to thnh cc nt khuyt oxy. Mt khc vic th v tr A bng cc cation Ce4+ s kh mt phn Co3+ thnh Co2+, do vy s to ra mt lng ln cc tm hot ng c kh nng hp ph oxy t pha kh. 1.3.4. Phn ng phn hy oxit nit S phn hy N2O thnh N2 l mt trong cc phn ng m hnh tt nht nh gi hot tnh xc tc ca cc vt liu xc tc d th h oxit perovskit. Phng trnh phn ng ha hc phn hy N2O c din ra theo cc giai on sau [14]: N2O(kh) N2O(hp ph) + e N2O (hp ph) N2O(kh) + O (hp ph) 2O (hp ph)
-

N2O(hp ph) N2O

(hp ph)

(1.11) (1.12) (1.13) (1.14) (1.15)

N2 (kh) + O (hp ph) N2(kh) + O2 (kh) + e O2 (kh) + 2e -

19

Theo phng trnh phn ng (1.15), tc phn hy b c ch bi oxy v s gii hp oxy. Ngha l, tc phn ng phn hy ph thuc vo hng s mng tinh th trong h vt liu perovskit do di lin kt v nng lng lin kt lm thay i lin kt B-O(hp ph). Cc kho st thc nghim trn h La0,8Sr0,2BO3- (B = Cr, Fe, Mn, Co, Y) c thc hin bi Gunasekaran v cc ng nghip [36] cho thy, h La0,8Sr0,2CoO3 cho chuyn ha cc i n 90 % nhit 873 K. Hot tnh phn hy N2O ca h ny tng ng vi cht xc tc Pt/Al2O3 nhit trn 773 K. Cc nghin cu c trng ca phn ng oxy ha kh v qu trnh gii hp ca h vt liu ny cng c cp. Cc tc gi cng ch ra rng, hiu ng hp ph oxy v qu trnh gii hp oxy s lm c ch s chuyn ha N2O v km hm tc phn ng tng cng ph hp vi c ch phn ng trong cc phng trnh trn. a s cc kt qu nghin cu phn ng phn hy NO trn h perovskit u c din gii bi s tham gia ca NO trong qu trnh hp ph ha hc v qu trnh phn ly NO. Cc phng trnh phn ng ca cc qu trnh ny c biu din di dng sau [26]: B- B + NO + NO + 2e 2N(hp ph) vi B- B + N2 N2O (kh) (1.16) (1.17) (1.18) (1.19)

OL2- + N(hp ph) N2 (kh)

N(hp ph) + NO(hp ph)

l nt khuyt oxy v OL l oxy mng tinh th. Cc phng trnh trn cho

thy, s phn hy NO bao gm s phn ly NO thnh nit v oxy trn b mt cht xc tc v nit gii hp ngay thnh dng kh N2 trong khi oxy li b gi li trn b mt cht xc tc. iu ny cho thy, cc cht xc tc khng ch hp ph v phn ly NO m cn c kh nng to iu kin gii hp oxy. Nhiu oxit perovskit c hot tnh xc tc phn hy NO nh: cc maganit, cobanit, ferit, YBa2Cu3O7-, La2CuO4, BaRuxB1-xO3 [37, 112, 113]. 1.3.5. S oxy ha etanol S oxy ha etanol c pht hin thy trn cc h perovskit LaCo1-xNixO3 v LaCo1-xFexO3 [26]. S ph thuc ca hot tnh xc tc vo nng coban (Co)

20

trong cc hp cht LaCo1-xNixO3 l khng ln. Tri ngc hon ton vi s bin i v tnh dn in ca h vt liu ny [92], trong cc hp cht thay th st, khi hm lng thay th st t gi tr 0,01 (x = 0,01), vt liu s c hot tnh xc tc cao nht. Hot tnh xc tc v dn t l vi nhau v nh hm ph thuc vo nng thay th (x) trong h LaCo1-xFexO3. iu ny cho thy vai tr ca cc ion n l c nh hng mnh n hot tnh xc tc ca vt liu. Mt khc, cc trng thi spin thp l nguyn nhn ch yu lm gim nng lng hot ha trong phn ng trao i oxy. Vi h perovskit LaCo1-xNixO3, c ion Co3+ v Ni3+ u c th tn ti trng thi spin thp, mc d cc ion Co3+ c thay th lm thay i cc tnh cht in trong khi nhng khng lm nh hng n hot tnh xc tc. Trong h LaCo1xFexO3,

cc ion Fe3+ ch tn ti trng thi spin cao. Khi hm lng thay th st (x)

tng ln s lm gim nng cc ion spin thp ko theo s thay i hot tnh xc tc. Cc ion trng thi spin cao y hot ng nh cc tm hp ph etanol trong khi cc ion trng thi spin thp c vai tr vn chuyn cc ion oxy b mt ti phn t ru [109]. 1.4. c trng nhy kh ca cc oxit perovskit Vic pht trin cm bin kh pha rn vi chn lc v tin cy cao l rt quan trng trong cc ng dng cng nghip [40, 41]. Mt s oxit ABO3 em li nhiu ha hn trong vic s dng lm cm bin kh bi bn nhit v bn ha hc cao. Do chc nng nhy kh ca cc oxit bn dn da trn c ch ca s thay i in tr ph thuc vo qu trnh hp ph kh nn cc thng s vt l khc ca h vt liu oxit perovskit nh hng n dn in cn c kho st. Trong cc kt qu nghin cu gn y cho thy, khi cc kh kh nh CO, CH3OH hp ph trn b mt oxit LnBO3 loi p (B = Mn, Cr, Co) s lm gim dn in ca mu [40]. Hin tng ny c th c biu din bng cc phng trnh phn ng sau: CO(kh) + O 2-(hp ph) CH3OH (kh) + 3O 2-(hp ph) CO2 (hp ph) + 2 e(1.20) (1.21)

CO2 (hp ph) + 2H2O(hp ph) + 6 e -

21

Theo cc phng trnh trn ta nhn thy rng, mt in t c gii phng do qu trnh hp ph ha hc cht kh trn b mt s lm gim dn l trng bi s tng tc vi in t t do ny. Cc phng trnh ny c th c xem nh cc phng trnh phn ng xc tc trn b mt oxit perovskit. Hn na, vic ng dng cc cm bin kh b hn ch bi bn ca cc pha perovskit trong mi trng kh kh v nhit cao. bn ca mt dy cc oxit perovskit LaBO3 (B = V, Cr, Mn, Fe, Co, Ni) c Nakamura v cc ng nghip [68] nghin cu nhit 1273 K v trong mi trng kh kh CO/H2. Th t bn c biu din nh sau: LaCrO3 > LaVO3 > LaFeO3 > LaMnO3 > LaCoO3 > LaNiO3. Khi kho st kh nng pht hin etanol trong hi th ca h vt liu (A,A)BO3 (A: t him; A: kim loi kim th; B: kim loi chuyn tip), Obayashi v cc ng nghip [77] ch ra rng, khi c mt hi cn, dn in ca cc vt liu ny thay i rt ln. Hot tnh xc tc trong phn ng oxy ha metanol ca h vt liu ACrO3 v AFeO3 cho thy l rt cao v b nh hng bi cc ion kim loi chuyn tip v cc ion t him. Rao v cc ng nghip [91] xut rng, cc c trng xc tc ca cc cobanit lin quan mt thit n cc trng thi spin c bit l cc trng thi spin cao Co3+. ng ch rng hot tnh xc tc ca cc cobanit t him ny ln nht l SmCoO3 tng ng vi t h Co spin cao trn Co spin thp l ln nht. Bn cnh vic thay th mt phn kim loi kim th trong h A1-xAxBO3 s to ra l trng linh ng. nhy kh ca mu khng nh hng ng k nhng su ca tm bt l trng trong cc oxit perovskit ny c ci thin. Nu cc ion A v A l c nh, khi cc ion B ng vai tr xc nh nhy kh ca vt liu. iu ny c kim chng trong h Sm0,5Sr0,5MO3, nhy kh ca Sm0,5Sr0,5FeO3 ln hn Sm0,5Sr0,5CoO3. Nu hot tnh xc tc c so snh bng thi gian p th c hai t s ny ph thuc mnh vo c trng b mt ca vt liu [5]. 1.5. Kt lun chng Tnh xc tc ca cc oxit perovskit ch yu da vo bn cht ca cc ion v cc trng thi ha tr ca chng. Bn cht ca nguyn t A (t him) nh hng ln

22

bn ca cc oxit perovskit nhng t nh hng ln hot tnh xc tc ca chng. iu ny tri ngc vi trng hp nguyn t B. Tuy nhin, khi pha tp mt phn nguyn t A bi nguyn t khc s to ra s bin i cu trc, to ra cc nt khuyt oxy v lm thay i trng thi ha tr ca kim loi chuyn tip lm thay i hot tnh xc tc ca vt liu. Hot tnh xc tc ca vt liu ph thuc vo nhiu yu t nh sai hng cu trc, linh ng ca oxy trong mng tinh th perovskit; cu hnh in t ca cation kim loi chuyn tip, nh hng ln nng lng lin kt kim loi-oxy; ha tr ca cation B nh hng ln tnh oxy ha kh, c ngha l d dng thay i trng thi oxy ha cation v gii phng nhanh oxy; mc thay th v tr A hoc B nh hng ln s pha long v bn ca cc tm hot ng v din tch b mt nh hng ln hot tnh xc tc.

23

CHNG 2 CM BIN BN DN OXIT KIM LOI Vt liu c s dng rng ri nht trong cm bin bn dn l cc oxit kim loi. S khc bit gia vt liu ny vi cc bn dn khc c th hin qua qu trnh phn ng ha hc bt thun nghch to thnh cc oxit bn vng khi t ngoi khng kh nhit cao, cc oxit kim loi duy tr n nh trong khi tng tc vi oxy b mt ca chng. Cc phn ng din ra trn b mt s ko theo s trao i in t v dn n s thay i in tr ca vt liu. Cc phn ng ha hc ny c thc hin bi qu trnh xc tc ca cht kh hp ph ln cc trng thi sai hng b mt dn n s bin i trng thi b mt cm bin. Qu trnh xc tc ny khng ch din ra trn lp b mt vt liu m cn c th din ra trong lng vt liu vi khong cch khuch tn so vi b mt vt liu c vi m hoc ngn hn. Do vy, nhit lm vic ca loi cm bin ny l phi thp cho php qu trnh hp ph b mt din ra v lm chm qu trnh cn bng sai hng khi. Mt khc nhit lm vic ca cm bin ny cng phi cao m bo phn ng xc tc v trao i in tch gia lp b mt v trong khi. Cc kt qu thc nghim ch ra rng nhit lm vic ca loi cm bin ny thng nm trong khong t 200 n 500 oC. Nhit lm vic ca loi cm bin ny ph thuc rt nhiu vo bn cht vt liu v mc ch s dng ca cm bin. Trong chng ny tc gi s tp trung ch yu vo dng cm bin bn dn oxit kim loi kiu in tr, cc nguyn tc c bn, phn ng cht kh-cht rn, thit k cm bin v cc c trng c bn ca cm bin. 2.1. Cc phn ng kh-cht rn v c ch cm bin dn b mt 2.1.1. Hp ph vt l v hp ph ha hc Cc nguyn t hoc cc phn t trong pha kh c th b ht v gi li trn b mt theo hai cch: (a) hp ph vt l v (b) hp ph ha hc. Trong m hnh Lennard-Jones, nng lng ca mt h bao gm cht hp ph v cht b hp ph c biu din di dng hm ph thuc vo khong cch gia cht hp ph v cht b hp ph v c ch ra trn hnh 2.1 [66].

24

Khi phn t cht b hp ph qu xa, nng lng ca h xem nh bng khng. Khi phn t tin li gn b mt (ng cong a), n c th phn cc v cm ng vi lng cc tng ng trong lp b mt, dn n tng tc lng cc/lng cc van der Waals vi nng lng lin kt HPHY tng ng. Nng lng ny thng c gi tr nh hn 0,2 eV (5 kcal/mol). Nu phn t b hp ph dch chuyn tip n gn b mt, khi s sinh ra lc y gia nguyn t b mt v phn t b hp ph. Do vy, phn t hp ph vt l
Hnh 2.1. M hnh Lennard-Jones cho hp ph vt l v hp ph ha hc; (a) hp ph vt l v (b) hp ph ha hc [1].

s nh x vng chc ti trng thi nng lng cc tiu (rp) vi mt khong cch ng k so vi b mt. Do khng xt n s ng gp ca nng lng hot ha trong qu trnh ny, tc hp ph vt l tr nn khng ph thuc vo nhit . Tuy nhin s gii hp cc phn t i hi mt nng lng HPHY. Do vy tc hp ph vt l c th c vit [57]:
dPHY / dt = k ads P 0 k des exp( H PHY / RT )

(2.1)

y o, , P v k tng ng l mt cc tm hp ph b mt, mt cc tm c bao ph bi cc cht b hp ph, p sut kh v hng s tc phn ng. Do s hng th hai ca phng trnh (2.1) ph thuc vo nhit , nn s hp ph vt l chim u th ch yu nhit thp v khng ng k nhit cao. trng thi dng, phng trnh 2.1 c a v phng trnh ng nhit Langmuir:
= P /[P + (k des / k ads ) exp( H PHY / RT )]

(2.2)

Nu p sut rt thp, phng trnh (2.2) biu din di dng nh lut Henry:
(k ads / k des ) exp(H PHY / RT )P

(2.3)

25

y l phn bao ph (phn b mt b che ph bi cht b hp ph) tr nn t l trc tip vi p sut kh. Mt khc, mt phn t c th phn ly thnh cc nguyn t khi cung cp cho n mt nng lng phn ly ln (ED). Khi mt nguyn t tin gn b mt (ng cong b), n s tng tc mnh vi b mt hp ph thng qua s trao i in tch gia nguyn t v b mt hnh thnh lin kt ha hc b mt ti khong cch rc. Cht b hp ph c th tham gia vo lin kt ha hc, hoc b ht ti v tr tm axit Lewis (trng thi acceptor cation khng b chim gi) cho in t, hoc ti tm baz Lewis (trng thi donor anion b chim gi) bt gi cc in t hnh thnh lin kt tnh in. Trong cc trng hp ny, nhit hp ph ha hc (HCHEM) thng ln hn 1 eV ( 23 kcal/mol), i khi gn bng nhit to thnh ca hp cht. Tuy nhin, s hp ph ha hc trc tip ca cc phn t dng nh t c kh nng xy ra do nng lng ED ln. Trn thc t, nng lng hp ph hot ha EA thng qua qu trnh hp ph ha hc v vt l nh hn nhiu. Tc hp ph ha hc t pha kh phn t c th c biu din [57]:
dCHEM / dt = k ads P 0 exp( E A / RT ) k des exp[ (H CHEM + E A ) / RT ]

(2.4)

Ti trng thi dng, bao ph hp ph ha hc c vit di dng:

= / 0 = k ads / k des exp[H CHEM / RT ]

(2.5)

Do , c hai qu trnh hp ph ha hc v gii hp u cn c cung cp nng lng v chng thng din ra vng nhit cao hn so vi hp ph vt l. V mt thc nghim, nng lng hot ha (EA) tng vi s tng ca bao ph ti nhit nht nh. S ph thuc ny c biu din mt cch nh tnh trn hnh 2.1. Do tnh d th ca b mt, cc cht b hp ph in y t cc v tr c nng lng thp nht n v tr c nng lng cao nht (HCHEM cao nht). Do HCHEM gim vi s tng ca bao ph. Theo m hnh Lennard-Jones, ng cong (b) s dch ln khi qu trnh hp ph ha hc din ra, ngha l khi HCHEM gim s lm tng EA vi bao ph trong khi ng cong (a) vn gi khng b nh hng [15, 124].

26

ng cong hp ph ng p in hnh ( bao ph l hm ca nhit vi p sut kh khng i) c minh ha bi ng chm ( ) trong hnh 2.2. nhit thp (vng I), s hp ph c c trng bi qu trnh hp ph vt l c s ng gp ca nng lng hot ha (ng cong (a) hnh 2.1) tng ng vi phng trnh (2.3); ti vng nhit cao (vng III), s hp ph c c trng bi qu trnh hp ph ha hc (ng cong (b) hnh 2.1) v tun theo
Hnh 2.2. Hp ph ng nhit in hnh: (I) hp ph vt l, (II) chuyn tip bt thun nghch, (III) hp ph ha hc [15].

phng trnh (2.5). Trong vng nhit trung bnh, s chuyn tip t hp ph vt l sang hp ph ha hc xut hin khi cn bng hp ph vt l t c d dng, nhng hp ph ha hc gim mt phn cn bng bao ph (vng II). S gim hp ph ha hc c th dn n t s tng dn ca EA. Trong vng nhit ny, vi mt b mt sch, gi tr ca EA ban u thp qu trnh hp ph ha hc xy ra rt nhanh. Khi b mt c bao ph, EA tng ln dn n tc hp ph gim. V cui cng, tc hp ph gim dn v khng. Nu tng nhit cho ti khi nng lng nhit vt qua ro hot ha EA dn n bao ph tng ln. Khi tc gii hp (s hng th 2 trong phng trnh (2.4)) gim dn so vi tc hp ph cho n cn bng bao ph trong vng III t c. Do vy, s hp ph trong vng trung gian i khi c gi l hp ph ha hc bt thun nghch. Mt khc, trong vng III, tc gii hp tr nn cn bng vi tc hp ph theo ng cong (b) hnh 2.1 [15]. 2.1.2. Cc trng thi b mt Trn b mt ca cc cht rn, tnh tun hon b gin on. Do vy, tn ti cc v tr nguyn t khng c bo ha v phi tr so vi bn trong khi vt liu.

27

Nhng gin on ny hot ng nh mt tp cho (donor) hoc mt tp nhn (acceptor). iu ny c hiu d dng bi m hnh Madelung cho tinh th ion nh c ch ra trong hnh 2.3. Theo m hnh Madelung [57], i lc in t ca nguyn t m in X xa v cng (R ) tr nn ln ln dn dn khi n b di chuyn ti v tr thng thng trong tinh th ion MX do th tnh in dng ca cc ion M+ xung quanh trong tinh th. Mt cch tng t, nguyn t kim loi M c
Hnh 2.3. M hnh Madelung cho cht rn ion MX: l i lc in t v I l th ion ha [1]

th ion ha I cao (nng lng bt in t ra khi mt nguyn t kim loi) R , n gim dn v tr mng tinh th ca n c bao quanh bi cc ion X-. Bn trong mng tinh th, mc nng lng trng cho in t trn mt nguyn t X tr nn thp hn mc in y trn mt nguyn t M, lm cho cc in t ri khi M v to thnh ion X-. Cc mc nng lng khng b chim gi ca cc ion M+ tr thnh vng dn khi v cc mc nng lng b chim gi ca cc ion X- to thnh vng ha tr khi. T m hnh n gin ny cc mc nng lng in t cc v tr trn b mt khc vi trong khi, to ra cc trng thi b mt ni ti. Orbital khng b chim gi trn cation hot ng nh mt trng thi b mt ging acceptor (tm axit Lewis) v orbital b chim gi trn anion nh trng thi donor (tm baz Lewis) [15]. Shockley cng nh ngha mt trng thi b mt ni ti, cn c gi l trng thi Shockley cho mt vt liu ng ha tr, cc nguyn t b mt to thnh cc lin kt u a [15]. Cc nguyn t bn ngoi hp ph ln mt b mt c th by in t t khi hoc bm in t vo khi cht nn to thnh trng thi nng lng nh x b mt (trng thi b mt t bn ngoi). Th d, hp ph oxy ln mt tinh th ion c th xut hin dng nguyn t hoc phn t. Trong tinh th ion, nng lng in t ca

28

oxy b hp ph tr nn thp hn mc Fermi, v chuyn in t t khi ti oxy b hp ph bi cc qu trnh sau: O2 + e- = O2-(hp ph) O + e- = O-(hp ph) (2.6) (2.7)
Hnh 2.4. Cc loi oxy hp ph c pht hin trn b mt SnO2 cc nhit khc nhau vi cc phn tch TPD, FTIR v EPR [53, 128, 98].

Cc phn t tch in ny lin kt vi b mt qua lc ht tnh in, i khi cn c gi l hp ph

ion ha, mt dng ca hp ph ha hc. Do s chim gi ca in t trong cc trng thi b mt cng phi tun theo thng k Fermi, nng tng ng ca O2-, O- trn O2 v O c vit nh sau: [O2-]/[O2] = exp[-(EO2- - EF)/kT] [O-]/[O] = exp[-(EO- - EF)/kT] (2.8) (2.9)

y EO2- v EO- ln lt l cc mc nng lng b mt cho cc phn t v nguyn t oxy. Thm na cc phn t oxy c th phn ly thnh cc nguyn t trn b mt ca oxit bi phn ng ha hc sau: O2 = 2O c biu din nh trong (2.8) [12]: [O2-]/[O2] = [O2]1/2exp[-(EO2- - EO- - 1/2Go(15))/kT] (2.11) (2.10)

T cc phng trnh (2.8)-(2.10), nng tng ng ca O2- v O- c th

y Go(15) l bin thin nng lng Gibbs tiu chun cho phn ng (2.10). Do Go(15) c gi tr dng ln nn nng ca O- tng vi s tng ca nhit nhng li gim vi s tng ca p sut oxy ring phn. S c mt ca cc cht ny trn SnO2 c pht hin bng TPD, FTIR v EPR, di 150 oC ch yu l phn t O2-, v trn nhit ny ch yu l nguyn t O- nh c ch ra trong hnh 2.4 [53]. Mt khc, trong trng hp ZnO v Bi2Mo3O12 [12], O2- th hin n nh ln n trn 175 v 250 oC.

29

Khi c mt cc trng thi b mt ni ti hoc do bn ngoi, cc in t di chuyn do c sai khc gia cc mc nng lng cc trng thi b mt v mc Fermi ca khi. Th d, hp ph oxy b mt cc oxit kim loi d0 v d10 nh SnO2 (110), ZnO (101-0) v TiO2 (110) dn n mt s chuyn in t t do t vng dn sang oxy hp ph. Nng khng ng k ca cc trng thi vng cm b mt hnh hc l tng ca chng lm cho chng tr nn c ch cho cm bin dn [15]. Trng thi b mt c mc nng lng thp hn mc Fermi trong khi s by cc in t t vng dn to thnh lp ngho di b mt i vi bn dn loi n v t vng ha tr to thnh mt lp tch ly i vi bn dn loi p. Th d, lp ngho c to
Hnh 2.5. S hp ph ngho ca X l Xhp ph ion ha ca oxy to thnh trn bn dn loi n: (a) vng bng (b) sau hp ph v hp ph ca X l X+ trn bn dn loi o hoc l O2 (< 150 C) hoc l O (> p: (c) vng bng (d) sau hp ph

thnh b mt SnO2 (loi n) bi s

150oC). Lp tch ly c pht trin khi oxy hp ph by in t t vng ha tr ca oxit niken (loi p) to thnh O-. Trng hp u c gi l hp ph ngho do ngun in t trong vng dn b hn ch v trng hp sau c gi l hp ph tch ly do c nhiu in t trong vng ha tr. V l do ny, cc oxit loi p l cc cht xc tc tt hn cc oxit loi n. Khi mc nng lng ca trng thi b mt cao hn mc Fermi, in t s c bm t b mt n cht nn, vo vng dn i vi oxit loi n v vng ha tr i vi oxit loi p to thnh mt lp tch ly hay mt lp ngho tng ng (xem hnh 2.5). 2.1.3. C ch nhy kh Cm bin oxit kim loi kiu in tr thng c h s khuch i in tr trn 100 ln khi t trong mi trng kh kh nh H2, CH4, etanol, CO v C3H8. C ch hp ph oxy trn b mt cm bin c biu din theo phng trnh sau:

30

Hp ph vt l: O2 (kh) O2 (hp ph) Hp ph ha hc (bc kh th nht): O2 (hp ph) + e- O2-(hp ph) S phn ly ca oxy (bc kh th hai): O2-(hp ph) + e- 2 O-(hp ph) O-(hp ph) + e- O2-(hp ph) O2-(hp ph) O2-(tinh th) Qu trnh hp ph ha hc lm thay i in tr b mt ca vt liu (hnh 2.6). Trong mi trng c kh kh (nh CO), chng s tng tc vi cc ion oxy trn b mt, gii phng in t tr li v lm tng dn ca vt liu (i vi bn dn loi n):
COgas + O-ads CO2 + e(2.15)

(2.12) (2.13)

(2.14)

Ngc li, khi c kh oxy ha nh NO2 s lm gim dn ca vt liu (i vi bn dn loi n) theo phng trnh sau: NO2 (kh) + e- NO2-(hp ph) NO2-(hp ph) NO(kh) + O-(hp ph) Tip xc gia cc ht n tinh th vi vng in tch khng gian bao quanh b mt ca mi ht, pha trong ht v ti ch tip xc gia cc ht c minh ha trn hnh 2.6. Vng in tch khng gian, l vng ngho cc ht ti in, c in tr ln hn in tr ca khi. Do , phn ln in tr ca mu do tip xc gia cc ht to ra. S hp ph oxy ly cc in t t vng b mt, cc in t dn vt qua vng in mi ny bng c ch nhy mc gia cc nguyn t ln cn. S di chuyn cc in t t ht ny sang ht khc i hi phi c s kch thch cc in t vt qua ro th ca b mt ht. dn ca cm bin kh trn c s vt liu gm c biu din nh sau:
= 0 exp ( -qS / kT )

(2.16)

(2.17)

31

dn ca cm bin t l vi mt h s, exp(-qS/kt), v 0 l hng s ph thuc vo vt liu, mt tip xc, lc nh in, v linh ng. Gi tr ca qS s tm c bng cch gii phng trnh Poisson [15]. Trong trng hp hp ph oxy, oxy s ht cc in t t khi v gy ra s m rng vng ngho in tch gn b mt trong cc bn dn loi n. Tuy nhin, s hp ph oxy b gii hn do hin tng un cong vng. S hp ph ha hc khng th tip tc xy ra nu mc Fermi ca
Hnh 2.6. S to thnh hng ro th gia cc ht khi c s hp ph oxy trn b mt vt liu loi bn dn n.

khi tng ng vi nng lng ca cc trng thi b mt m trn c in t. S lng nguyn t b hp ph ho hc trn mt n v din tch b mt l:
N g = x0 nq ( x )

(2.18)

Vi x0: dy vng in tch khng gian; nq(x): s in t trn mt n v th tch. S gim lp in tch khng gian v s di chuyn cc in t t bn trong oxit n b mt to ra bi kh c hp ph trn, c th nh gi c t phng trnh Poisson mt chiu i vi bn dn cha cc tp cht donor v acceptor trn mt n v th tch [15]:
d 2 E ( x ) qn q ( x ) x = = E m 1 2 x0 S dx

(2.19)

y E(x) v s tng ng l in trng v hng s in mi ca bn dn. Hng ro nng lng qb v chiu dy vng in tch khng gian x0 c biu din nh sau:
q b =
2 qx0 nq ( x0 )

2 S

2 S b x0 = qnq ( x0 )

1/ 2

(2.20)

32

Do :
2 s nq ( x0 ) b Ng = q
1/ 2

(2.21)

nq(x0) l nng tp cht b ion ha hon ton. Hng ro Schottky qb m t s chnh lch nng lng gia b mt v khi bn dn. Trong qu trnh trao i in tch t do, cc in t phi vt qua ro nng lng ny. Hin tng hp ph oxy trn b mt xy ra tng t i vi bn dn loi p, tuy nhin khi cc phn t oxy ly in t t vng b mt s sinh ra cc l trng trong vng b mt, lm gim rng vng ngho ca b mt. Khi , cao ro th gia b mt v khi vt liu s gim, lm tng dn ca vt liu so vi khi cha hp ph kh. Ngha l, in tr ca bn dn loi p gim. Khi b mt cm bin tip xc vi kh kh, cc ion oxy c hp ph trn b mt s phn ng vi kh ny v gii phng in t. Cc in t ny s ti hp vi l trng trong khi, m rng vng ngho, tng cao ro th. Khi , dn ca vt liu nhy gim, ngha l in tr ca cm bin li tng. chnh l c ch thay i tnh cht in ca bn dn loi p khi c lm vt liu cm bin. 2.2. Cu trc v c trng cm bin kh 2.2.1. Cu trc cm bin Cm bin oxit kim loi c th c ch to dng khi, mng mng, mng dy v bao gm cc vt liu tinh th kch thc nano n ht ln, bng vic s dng nhiu k thut nh: (1) phng php thiu kt thng thng cho dng khi; (2) k thut in li cho kiu mng dy v (3) k thut lng ng chn khng cho kiu mng mng. Mt vi vt liu mang li nhiu ha hn bi tnh lp li trong ch to, mt vi vt liu cho chi ph gi thnh thp, cn mt vi vt liu khc li em li kh nng pht hin kh nhanh a) Kiu khi Nhiu cm bin thng mi c ch to bng phng php thiu kt gm thng thng c kiu hnh ch nht (model TGS 109 - hng Figaro - Nht Bn)

33

hoc ng hnh tr (model TGS 813 ca Figaro - Nht Bn) (xem hnh 2.8). Cc cm bin ny c gia nhit bng phng php trc tip hoc gin tip bng dy hp kim Ir-Pd hoc Cr, m bo nhit hot ng trong vng t 300 n 450 oC. Mc d vy, cc kiu cm bin ny c thit k kh phc tp v in nng tiu th ln (> 500 mW), nhng b li n cho n nh tt nn c s dng rng ri trong cc thit b pht hin r r kh c v kh chy.

Hnh 2.7. Cu trc cm bin kiu khi gia nhit trc tip TGS 109 (a) v gia nhit gin tip TGS 813 (b) ca Hng Figaro (Nht Bn).

b) Kiu mng dy Cc cm bin kiu mng dy c ch to bng phng php in li (xem hnh 2.8). Kch thc cm bin c th rt xung khong 1x1 mm. Nng lng tiu th ca cm bin thp hn 200 mW. Vt liu in li c ch to bng cch trn mu bt (th d
Hnh 2.8. Cm bin dng mng dy.

SnO2) vi cht ph gia, cht chng keo t nh propadyol hoc terpineol v cht kt dnh hu c nh etyl silicat v cht xc tc kim loi qu. Hn hp ny c in ln c tch hp in cc Au hoc Pt. L vi nhit ca cm bin c thit k mt sau . c) Kiu mng mng Cc cm bin ny hin nay khng c s dng rng ri nh kiu mng dy v kiu cu trc khi. Tuy nhin, do kh nng tch hp thit b v n nh cao hn, cc cm bin ny em li nhiu tim nng ng dng trong tng lai. Nng

34

lng tiu th ca cm bin loi ny di 150 mW. Cm bin c th c ch to bng cch s dng cc k thut lng ng pha hi vt l hoc ha hc, phn x, quay ph vt liu sol-gel trn cc Si, Al2O3 (hoc saphia) [17, 80, 98]. 2.2.2. Cc c trng ca cm bin kh Mt cm bin kh bao gm 2 phn: lp nhy kh v phn chuyn tn hiu cm bin thnh tn hiu in. Lp nhy kh c ti u bng vic la chn vt liu cn b phn chuyn tn hiu li quyt nh bi k thut ph hp. Cc vt liu s dng cho vic thit k v ch to cm bin kh phi p ng c tiu chun 3S l: nhy (Sensitivity), chn lc (Selectivity) v n nh (Stability). i vi mt s loi cm bin kh, tnh thch hp v k thut (Suitability) cng c a vo tiu chun thit k v c gi l 4S. a) nhy nhy ca cm bin c nh ngha l h s gia in tr ca lp nhy kh trong mi trng cha kh vi in tr trong khng kh, S = Rgas/Rair (hoc S = (Rgas-Rair)/Rair). Ngha l, nhy ca mt cm bin kh bn dn l mt hm ph thuc vo bao ph b mt trng thi dng ca cht b hp ph oxy tng ng vi n trong khng kh. bao ph b mt cng thp, nhy cng cao. nhy cc i ca mt cm bin c cu trc xp ph thuc vo cht kh cn c pht hin bi cc yu t sau: S ph thuc vo nhit ca trng thi cn bng bao ph ca cht b hp ph oxy trong khng kh (tc hp ph oxy); Hnh 2.9. nhy ca cm bin kh SnO2 cc nhit
khc nhau vi cc kh chy:H2, CO, C2H8 v CH4.

35

S ph thuc vo nhit ca trng thi cn bng v hng s thi gian trong phn ng xc tc gia cht hp ph v kh nghin cu. thm ca oxy v kh nghin cu qua mi trng xp ( khuch tn ca kh). nhit thp, trng thi cn bng bao ph ca cht b hp ph oxy trong khng kh l cao, tc phn ng xc tc ca cht kh cn c pht hin vi oxy b mt l thp n mc nhy l khng ng k. Mt khc, nhit cao, tc di chuyn ca cht b hp ph oxy tr nn cao do phn ng xc tc mnh, cn bng bao ph ca oxy trong khng kh l thp nn nhy vn thp. cc nhit trung bnh, nhy cc i ca cm bin SnO2 ng vi cc kh kh khc nhau c minh ha trn hnh 2.9. Hn na, do s tiu th oxy lin quan n s chuyn ha ca kh nghin cu cc nhit thp hn vi vic tng hot tnh xc tc, dn n ti nhit (TM), nhy t gi tr cc i. nhy cc i ny t l nghch vi hot tnh xc tc, ngha l hot tnh xc tc cng cao th cc i nhy cng thp (TM). Bc ca hot tnh xc tc c th c nh gi bng nhit (T50) ti chuyn ha kh nghin cu thnh cc cht oxy ha t 50% khi qua mt mng cht xc tc. T50 cng nh th hot tnh xc tc cng cao. Do vy, TM ph thuc tuyn tnh vo T50 o c t nhiu hot tnh xc tc Hnh 2.11. Profin nng cc cht kh ngang ca vt liu nhy kh. Mi lin h ny qua chiu dy mng xp. Cc in cc c c minh ha trn hnh 2.10 [129].
t trn nh, y hoc mt bn ca lp nhy kh. S: in cc mt bn, B: in cc y v U: in cc nh [16].

Hnh 2.10. S ph thuc ca TM vo T50

[129].

36

Trong mi trng xp, khuch tn hiu dng ca cht kh (D) c th thp hn ng k so vi khuch tn ca n trong mi trng, DO ( y, D = 10-2 10-3DO). Thm na, kh b tiu th trong sut qu trnh khuch tn qua lp xp dy mt tc kCi, n c xc nh lng thm qua ca kh nghin cu v pha b mt hot ng. S bin thin nng kh qua mng xp dy s nh hng ln nhy (hnh 2.11). V c bn, nng ca cc cht kh ring phn trong mng c th thu c t vic gii phng trnh khuch tn tng qut sau [16, 67]:
Ci 2C = Di' 2 i kCi t x

(2.22)

y k l hng s tc cho phn ng tiu th kh trn b mt ca vt liu nhy kh. trng thi dng (Ci / t = 0), phng trnh (2.22) c th c gii di cc iu kin bin sau: Ci = CiO x = h v dCi/dx = 0 x = 0

Nu dn ca vt liu nhy kh c mt mi quan h vi nng kh theo

= 0 + 1Ci, vi 0 v l cc hng s v dn c o gia cc in cc

c t trn cc mt (S), dn tng ca cm bin mng dy c th thu c bng cch ly tch phn cc phn dn song song (hw/l)dx:
hw 0 = 0 + 1 ( Ci ) l
cosh ( x / h ) kh 2 / D ' 1/2 ( i) 1 x d 1/2 0 cosh kh2 / D' h ( i)

(2.23)

y l v w tng ng l di gia cc in cc v chiu dy ca lp nhy kh. Phng trnh (2.23) c th c n gin ha:
=
hw h* w 0 + 1 ( Ci0 ) l l

(2.24)

Vi:

cosh ( x / h ) kh 2 / D ' 1/ 2 ( i) h x d = 1/ 2 h 0 2 ' h cosh ( kh / Di )

* 1

nh hng ca chiu dy mng ln nhy i vi mt thnh phn kh cho hoc mt hot tnh xc tc ca vt liu cho c th c nh gi t phng trnh 2.24. Da vo chiu dy mng, ngi ta c th phn chia thnh hai trng hp: (1) i vi mng rt dy (h >> h*), (hw/l)o v nhy bng khng.

37

(2)

i vi mt mng c chiu dy tng ng vi h*, (hw/l)[o + 1(CiO)]; nhy t ti u. Trong trng hp in cc y

(B), dn c xc nh hoc l qua ng (1) hoc l ng (2), cho knh in tr thp hn. iu ny ph thuc vo khong cch ca khe in cc v chiu dy ca mng nhy kh. i vi mt khe hp, nhy ph thuc vo tng tc ca kh vi vt liu nhy kh c trong khe gia cc in cc. i vi mt cm bin khe rng, ng (1) cnh tranh vi ng (2) nn hot tnh v chiu dy mng ng thi nh hng n nhy.
Hnh 2.12. S thm kh vi hot tnh khc nhau ca thnh phn nhy kh [35], R: kh kh v RO: kh oxy ha

Tm li, nu mt thnh phn nhy kh c hot tnh cao (h* 0), kh nghin cu b oxy ha gn nh hon ton vng pha ngoi v ch lng vt cht kh c th t n vng trong cng ti cc in cc c nh x dn n nhy rt thp. Mt khc nu thnh phn nhy kh c hot tnh trung bnh (h h*), mt lng ng k cht kh c th thm vo vng trong cng cho nhy cao hn. Ngc li, cm bin c hot tnh khng ng k th hin nhy thp do tiu th cht b hp ph oxy thp vng trong cng thay v hu nh kh thm vo hon ton. Trong trng hp ny, nhy thp dn n t gi tr hm m thp trong khng hot ng. S ph thuc ca thm kh vo hot tnh ca thnh phn nhy kh c minh ha trong hnh 2.12 cho cu trc in cc y. Hot tnh xc tc ci thin nhy, thi gian p i vi kh no , mt lng nh kim loi qu c thm vo vt liu cm bin dng phn tn ht mn kch thc nm. Kim loi qu c s dng lm cht xc tc trong trng hp ny thng l: Pd,

38

Ag, Rh, Ir v Pt, cc gm lm xc tc nh V2O5, Re2O7, CuO v NiO. Cc cht xc tc ny rt hiu qu bi chng tc ng mnh ln s bin i h s din tch b mt ring trn gam vt liu cng nh nng cao cc sai hng b mt. Mt khc, nhy ca cm bin cng ph thuc vo cng ngh pha tp kim loi qu [127]. Cht xc tc ng cc vai tr sau: Th nht: lm tng nng oxy hp ph trn b mt O- hoc O2- (hiu ng ha hc). Th hai: ghim nng lng Fermi ca cc trng thi b mt (hiu ng in t) Vai tr th nht c th t c qua c ch trn bi cc phn t oxy b phn ly thnh nguyn t trn cht xc tc, chng trn ra trn [65]. Oxy trn ra di chuyn v tc ng ln phn tip xc gia cc ht lm nh hng n in tr cm bin nh phng trnh = o exp(-eVS/kT). V hiu ng in t, t phng trnh EF = ES + kT ln
f ( y f/(1-f) l t 1 f

s cc trng thi b chim gi vi cc trng thi khng b chim gi), s ghim nng lng Fermi xut hin khi cc trng thi b mt lin kt vi cht xc tc c mt nng vt qu 1012/cm3. S phn tn cht xc tc dng ht mn ghim nng lng Fermi ca bn dn nng lng Fermi ca cht xc tc, bin i vi s hp ph cc cht kh theo biu thc sau: = - Ns / 0 (2.25)

y , Ns, v 0 tng ng l m men lng cc ca cc cht hp ph, tng mt cc tm hp ph, phn bao ph v hng s in mi ca khng gian t do. Do , s thay i cng thot ca cht xc tc bi s hp ph s lm thay i cu trc vng nng lng ti lp tip xc gia cc bin ht dn n thay i in tr ca cht gm oxit kim loi. S ph thuc ny c biu din di dng biu thc sau:

= 0 exp[- (ECS-EF)/kT]
Fermi ca cht xc tc.

(2.29)

y ECS v EF tng ng l nng lng vng dn b mt ca cht bn dn v mc

39

Khi nng oxy hp ph trn b mt cht xc tc tng, mc Fermi ca cht xc tc v ca bn dn tip xc vi cht xc tc tng ng b gim. iu ny dn n s tng ro b mt cc tip xc gia cc ht ging nh ro cao t c khi oxy c hp ph vi nng cao trn cht bn dn. Ni cch khc, s hp ph oxy trn cht xc tc lm di chuyn in t t cht xc tc, n ln lt ly in t ra khi cht nn bn dn to ra lp ngho in t bn di. Do trong SnO2 rng lp khng gian in tch tip xc cht xc tc/oxit l khong 100 nm cho nng nt khuyt oxy trong khi in hnh c 1016/cm3, cht xc tc phi c phn tn n mc m khong cch trung bnh gia cc cht xc tc tr nn t hn khong 50 nm cho s bao ph hon ton lp in tch khng gian b mt. Ag v Pd l cc cht xc tc in hnh ca kiu ny, chng to nn cc oxit bn Ag2O, PdO nhit thp trong mi trng oxy ho v chng d dng b kh v kim loi khi c mt kh chy [30, 127]. Morrison [65, 48] nh gi thay i nng lng Fermi ca xc tc MoO3 trn TiO2, khi c xung kh kh (propylen), MoO3 b kh, lm chuyn mc nng lng Fermi t 0,83 n 0,34 eV. b) Thi gian p Thi gian hi phc Thi gian p l thi gian cn thit gi tr li ra ca cm bin n nh khi cc iu kin o thay i t ngt t trng thi ny sang trng thi khc. Thi gian p l khong thi gian gia 10 v 90 % gi tr n nh. Trong cm bin kh, gi tr ny ph thuc ch yu vo ng hc ca phn ng ha hc. Thi gian p ph thuc vo tc hp ph/gii hp v ph thuc vo kh nng phn ng ca tng kh ring (tng nhit tng thi gian p). Thi gian hi phc c nh ngha l thi gian cn thit vt liu tr v trng thi ban u khi ngt kch thch kh (hp ph li oxy nhanh, khng ph thuc vo kh cn o). c) chn lc Thc t l s hp ph v phn ng xc tc ca cc kh trn b mt cm bin dn n cm bin c th nhy vi nhiu kh khc nhau, dn n khi nim nhy

40

xin. Cc nh nghin cu c gng rt nhiu lm gim nhy xin ny. Cc cch tip cn ph bin cho vic ci thin chn lc l [35]: (i) La chn mt cu hnh in cc thch hp v chiu dy lp nhy kh c kh nng cn tr cc kh khc; (ii) Thm vo cht xc tc thch hp v/hoc cht pha tp lm dch cc i nhy v pha kh nghin cu; (iii) La chn nhit hot ng ti u kh c chn hot ng nht. Cc tip cn khc bao gm [35]:

Pht trin cc oxit kim loi mi so vi cc oxit truyn thng nh ZnO, SnO2, TiO2; S dng tng tr (bin i tn s) thay v o in tr mt chiu dc; S dng mng lc hoc cm bin nhiu lp cho vic hp ph hoc phn ng chn lc. S dng dy cc cm bin nhy tng phn chung vi phn nhn bit v phn tch a cu t. Php o nhy v chn lc c th ph thuc vo cu trc hnh hc ca in cc nh l: v tr in cc v khong cch khe in cc tng ng vi chiu dy lp nhy. Cc in cc c th c t trn nh, y hoc bn cnh lp nhy kh nh c minh ha trong hnh 2.13a v cu hnh c chn l phng, hoc ci rng lc hoc mi d (hnh 2.13b). Trong s chng, cu hnh cu hnh phng ci rng lc hoc 2 mi d song song c s dng ph bin nht trong thc nghim. Nhn chung, khi cc in cc c t trn nh hoc bn cnh, t c nhy cao hn in cc trn y do tnh hiu lc ca phn ng xc tc b mt ca cc cht kh. Tuy nhin, cc in cc t y li c li cho chn lc. Th d, cc in cc y vi khe nh cho php mt kh km hot ng c pht hin trong s c mt ca mt kh hot ng cao khc do nh hng kh hot ng cao b ui trong khi khuch tn qua lp nhy trong khi kh km hot ng hn li khng b nh hng. Mt khc, nu in cc y c khe ln so vi chiu dy ca cm bin th cc kh hot ng mnh c th c pht hin c trong s c mt ca kh km hot ng khc do knh dn c to thnh qua vng b mt m n b nh hng nht bi kh hot ng. Komori [50] pht hin c mtan khi c mt cc kh hot ng

41

hn nh hydro, CO v etanol bng vic s dng mt lp nhy kh dy hn su phn ng cho cc kh hot ng hn (h* 0) nhng li nh hn cho mtan (h* h). Mt trong cc cch chc chn v hiu qu nht m bo chn lc ca cm bin kh bn dn l s dng cc b lc vt l hoc ha xc tc trn nh lp nhy kh. Cc b lc ny cho kh nghin cu thm qua d dng nhng li ngn cn cc kh cn tr n lp nhy kh bng nguyn l vt l hoc ha hc [22]. N c bit hiu qu cho chn lc hyro do mng dy hot ng nh mt ry phn t ngn cn tt c cc kh khc ngoi tr hyro c ng knh phn t nh nht t n thnh phn nhy kh. B lc ha hc c th cho cm bin nhng cc kh khc li b ui i bng cc phn ng ha xc tc trong b lc. Mt b lc cu trc xp Ga2O3 c lng ng bng cch in li ln mng mng Ga2O3 c th loi b nhy xin vi etanol chn lc pht hin metan trong s c mt ca etanol, ngc li lp lc Nb2O5 [79] trn SnO2 li kh nhy xin vi hyrocacbon nh propan chn lc pht hin etanol. Thm na, chn lc cng ph thuc vo vt liu v phng php ch to in cc [96]. d) n nh Ngc li vi chn lc v nhy, vn v n nh t c cp trong cc ti liu. iu ny khng c ngha l n nh t nh hng ln tnh hu ch ca cm bin kh. ng hn l n nh l vn thng c ch n giai on ch th v sn xut. n nh rt kh gii quyt ch yu do thiu php kh nghin cu xuyn qua ti b mt s dng thit k cm bin; (b) cc cu
hnh in cc ([i]: ci rng lc, [ii]: tip xc 4 im v [iii]: phng)
Hnh 2.13. (a) cc v tr in cc c

42

hiu bit chnh xc cc qu trnh vt l v ho hc bn di. Cc vn n nh c th lin quan n cc thc t sau: (1) cm bin dn b mt lun b lm bn b mt do nhit hot ng ca n kh thp t 100 n 450 oC; (2) mt cm bin da trn oxit bao gm mt khi c thiu kt cha hon ton trong cc tip xc gia cc ht khng ging nhau; v (3) nhng thay i c th xut hin t s khc nhau v h s gin n nhit v/hoc cc phn ng tip xc in cc kim loi/vt liu gm. Nhn chung, tip xc kim loi/vt liu gm ch ra mt x s khng ohmic do s khc nhau v cng thot ca vt liu gm v kim loi. Th d, mt ro kiu Schottky c to thnh tip xc Pt/SnO2 [19]. Do vy, khi p ng in c o cho cu trc kim sot tip xc vi mt in cc Pt trn cm bin SnO2 thiu kt vi mt chiu dy h > h*, c trng tip xc ng mt vai tr ch yu trong p ng I-V cho mt s ph thuc dng in hoc in tr ph thuc th hiu dch nh c ch ra trong hnh 2.14a. Tuy nhin, n c gim bt trong cu trc mng dy xp, n c ni nhau thnh dy vi mt s ln cc tip xc Schottky ht vi ht vi in tr tng ng c minh ho trong hnh 2.14b. Khi nim n nh lin quan n cc vn c chuyn ha theo thi gian. Cc chuyn ha ny c pht hin bi tnh khng n nh ca ng nn v bi bi s bin i nhy ca vt liu. Cc chuyn ha ny c th c iu kin mi trng, thay i trng thi b mt ca cm bin hoc tnh khng n nh ca b mt ny, hoc t bn ngoi lp
Hnh 2.14. S cu trc vng nng lng cho (a) cm bin mng mng v (b) cm bin mng dy vi mch tng ng ca nhiu ngun gc nh s bin i ca cc chng v p ng dng - th [79].

43

nhy nh hot ha bi th p vo v thay i nhit hot ng do bin i vic t nng. Ngi ta xc nh c hai kiu chuyn ha: chuyn ha thi gian ngn ( chnh xc) v chuyn ha thi gian trung bnh/di. Cc chuyn ha sau (trung bnh v di) ch ra s gi ha ca lp nhy. 2.3. Vt liu v cm bin nhy hi cn Alcohol hay cn gi l etanol (hi cn), thng c trong bia, ru, cc sn phm qu trnh ln men hoa qu v trong mi trng cng nghip ch bin thc phm. Do vy cm bin v thit b o hi cn c pht trin nhm o nng cn trong hi th ca ngi iu khin phng tin giao thng, kim tra cht lng thc phm, iu khin qu trnh ln men hoa qu... iu gii thch ti sao nhiu nhm tc gi trn th gii tp trung nghin cu nhm pht trin cm bin v thit b o c nhy v chn lc cao vi hi cn [125]. C nhiu phng php xc nh nng hi cn trong hi th. Cc phng php nh ph khi, sc k kh cho kt qu rt chnh xc nhng khng th o ngay ti hin trng. Ta phi dng dng c ly mu kh th v mang v phn tch ti phng th nghim. Ta c th xc nh nng hi cn gin tip qua vic phn tch nng cn trong mu hoc trong nc tiu ngi cn kim tra. Tuy nhin vic kim tra nng cn trong mu hay trong nc tiu phc tp v cch thc ly mu cng nh cc thit b phn tch. Cch thc c bn v ph bin nht hin nay l xc nh nng cn trong hi th bng cc thit b o cm tay. Cc cm bin nhy hi cn c nghin cu ch to trong phng th nghim cng nh c thng mi ha trn th trng hin nay ch yu l cm bin in ha v cm bin da trn oxit kim loi dng rn. Cc cm bin hot ng theo nguyn tc in ha c u im l c chnh xc cao, chn lc tt, tuy nhin n i hi cng sut hot ng ln, nhy khng cao v thi gian p ng di. Trong khi cc cm bin da trn oxit kim loi bn dn li c nhy cao (t nng vi ppm n vi chc phn trm), p ng nhanh, d ch to, kch thc gn nh, bn cao v tiu th t nng lng. Tuy nhin, loi cm bin ny cng c mt s

44

nhc im cn khc phc l chn lc km v ph thuc mnh vo cc iu kin mi trng nhit , m. Mt khc, hin tng gi ha v hin tng u c xc tc cng lm nh hng bt li n bn, chnh xc ca cm bin. Tnh chn lc ca cm bin c th thay i c bng cch la chn vt liu cm bin ph hp v s dng cc cht xc tc, mng lc kh. Cc cm bin loi ny rt ph hp vi cc loi my o. Bng 2.1. Mt s thit b o hi cn c thng mi ha trn th trng: K hiu Hng thit b sn xut
Lion Lion alcolmet (Anh) er SD400

c trng thit b
Cm bin in ha (fuel cell); Khong o: 0,00 - 2,00 mg/l BrAC hay 0 - 400 mg% BAC; Thi gian p: 30 giy; Thi gian hi phc: 60 giy; chnh xc: 0,01 mg/l BrAC hay 2 mg%BAC; Ngun 5 pin AA; Lu tr hn 500 kt qu o. Kt hp c cm bin hng ngoi v cm bin in ha; Khong o: 0 0,500 g/210 l Ngun: AC 110 - 240 V; DC: 12 V C h tr cng RS 232 v USB. Cm bin in ha; Khong o: 0 - 5,5BAC; Sai s: vng 0 - 1: 0,05 tuyt i; vng 1 - 2: 5% gi tr o; lch chun: 0,008; vng nhit : - 5on + 50oC, C th o 1600 ln, C th lu gi 999 ln o vi thi gian, ngy, thng. Cm bin in ha; Khong o: 0,000 - 0,600 BAC; Thi gian p: 10 giy; Thi gian hi phc: 30 giy; chnh xc: 0,005 BAC Lu gi 5000 kt qu o.

nh thit b

Alcotest 9510

Drger (c)

Alcoqua nt 6020

Envitec (c)

Phoenix 6.0

Hng Lifeloc

Vt liu c dng ph bin nht trong ch to cm bin kh l oxit thic SnO2. SnO2 c nhiu tnh cht c trng v ring bit, lm cho vt liu ny c ch cho nhiu ng dng. Mng mng a tinh th v gm SnO2 c s dng trong ch to in tr nh mng SnO2 dn in trong sut c bit nh l in cc lm

45

b phn gia nhit trong sut trong ch to tranzito, lm lp ph trong sut gim tnh in v b phn khc trong thit b in m ti yu cu c dn in v truyn qua cao. Oxit thic SnO2 c u im nh phn ng mnh vi cc kh kh ti nhit tng i thp do c kh nng hp ph oxy trn b mt nh tnh khng hp thc ca vt liu. Ngoi ra, oxit ny cn c gi thnh r so vi cc vt liu khc. Hin nay, c rt nhiu nhng nghin cu nhm ci tin nhy, kh nng chn lc v n nh ca cm bin da trn loi oxit ny, bng cch thm vo mt lng nh cc cht xc tc ph hp. Ngoi oxit thic, cn c nhiu oxit khc cng c dng trong cc cm bin nhy hi cn nh: In2O3 [126], WO3 [52]... v cc hn hp oxit nh: Fe2O3 - SnO2 [33, 38], WO3-TiO2 [34]... (Bng 2.2). Bng 2.2. Tng kt cc vt liu nhy hi cn [23] Vt liu SnO2 In2O3 SnO2 2%CeO2/SnO2 W/TiO2 xTiO2-(1-x)WO3 CdO-Fe2O3 Fe2O3(0.9)-SnO2(0.1) SnO2.Nb2O5 BaSnO3 xSnO2+(1-x)-Fe2O3 LaNiO3 Pr0.5Sr0.5CoO3 Pr0.25Sr0.75FeO3 La1.4Sr0.6NiO4 LaFe0.8Co0.2O3 LaFeO3 Nhit hot ng (oC) 260 323 - 473 350 300 350 160 350 220 200 290 225 250 300 270 250 250 Nng hi cn 0 500 (ppm) 100 500 (ppm) (RH = 30-50%) 0 4000 (ppm) 100 1000 (ppm) 0 1000 (ppm) 0-1000 (ppm) 0 1000 (ppm) 0 20 (mg/l) 0 800 (ppm) 0 2 (mg/l) 0 2 (mg/l) 0 2 (mg/l Thi Ti liu gian p tham kho ng (s) [28] 16 [59] [86] [88] 300 [27] 1200 15 [34] 23 [56] [33] 180 [122] [106] [105] [115] 12 [76] [76] [76] [29]

46

Nh vy vt liu ch to cm bin nhy hi cn rt a dng, t cc oxit n nh SnO2, In2O3, WO3, hn hp hai oxit nh CeO2 v SnO2, n oxit phc hp nh cc oxit perovskit. Cho n nay, cc nh khoa hc vn n lc tm kim nhng vt liu mi nhm ci thin hot ng ca cm bin [69, 71, 70]. Vt liu oxit perovskit ABO3 nhanh chng c ch ti nh hot tnh xc tc mnh. Hot tnh xc tc ny c th thay i c bng cch thay th tng phn bi cc nguyn t kim loi khc vo cc v tr A hoc (v) v tr B. Ngoi ra cc oxit perovskit cn c bn nhit, bn ha hc cao v cu trc n nh nn c th ci thin c tin cy v tui th ca cm bin [61]. Cc thit b o hi cn trn th trng u cha s dng oxit perovskit lm vt liu cm bin. Do vy chng ti mun tm hiu, nghin cu ch to v pht trin cm bin nhy hi cn trn c s vt liu ABO3, t c th ch to cc dng thit b o nng cn phc v trc tip cho cc ng dng Vit nam. 2.4. Kt lun chng Do nhng vn c cp trn, vic nghin cu cm bin kh da trn cc oxit kim loi ngy cng pht trin vi cc xu hng nghin cu ni bt: (i) tng cng nghin cu c bn trong nhng nm gn y hiu bit tt hn v c ch nhy kh; (ii) cc k thut tng hp cc vt liu mi v ch to thit b; (iii) pht trin cc cm bin c chng hn hoc cc ng dng tp trung hn. c im cui cng c th gip cho vic y mnh pht trin hn na cc cm bin c chng s dng trong nhiu mi trng.

47

CHNG 3 CC K THUT THC NGHIM 3.1. Cng ngh ch to vt liu Trong nghin cu vt liu, yu cu u tin v quan trng l ch to thnh cng mu nghin cu. Cho n nay c rt nhiu phng php ch to mu oxit a kim loi nh phn ng pha rn, ng kt ta, sol-gel, precursor-hp cht Phng php phn ng pha rn c u im l n gin v mt ha hc nhng li c nhiu hn ch nh sn phm thu c c ng nht v tinh khit ha hc khng cao, kch thc ht ln, s phn b kch thc ht rng, b mt ring nh, kh thc hin khi trong h phn ng c cht d bay hi. Sn phm c ch to t phng php ng kt ta c tnh ng nht cao, tinh khit ha hc v b mt ring ln. Tuy nhin phng php ny li kh thc hin do vic la chn iu kin cc ion kim loi kt ta ng thi l kh khn v phc tp. Phng php precursor-hp cht da vo vic a cc ion kim loi vo cng mt tin cht nn hn ch ca phng php ny l thnh phn ca cc oxit a kim loi phi trng vi thnh phn ca precursorhp cht v ch p dng d iu ch mt s vt liu c thnh phn t lng. Mi phng php c nhng u im v hn ch ring. Do vy, ty theo mc ch s dng vt liu m la chn phng php ch to cho ph hp. Trong cc phng php , phng php sol-gel cho sn phm c kt tinh, ng th tt, kch thc ht nh (c nano mt) v din tch b mt ln (10 - 40 m2/g) ch yu do cc cht phn ng c ha trn mc phn t nn h thp nhit thiu kt (700 - 900 K), rt thch hp cho cc ng dng trong cc lnh vc xc tc, cm bin kh... Trong cc loi oxit kim loi, oxit perovskit dng bt c kch thc ht nano mt c chng ti la chn nghin cu nhm ng dng cho ch to cm bin kh. Trong phng php sol-gel, ta c th d dng kim sot thnh phn hp cht, dung dch t c tnh ng th v kim sot nng m khng cn s dng thit b t tin. Cc phng php sol-gel thng c s dng l: sol-gel thy phn mui; sol-gel thy phn ancoxit v sol-gel to phc. Phng php sol-gel thy phn

48

mui hay ancoxit kim loi da trn cc phn ng thy phn v ngng t cc mui/ancoxit to thnh cc ht hyroxit hoc oxit kch thc nano mt. Nhn chung cc ancoxit kim loi thng c s dng lm vt liu ban u cho cng ngh sol-gel nhng mt s ancoxit rt kh x l do rt nhy vi m. Thm na khi ch to cc vt liu a cu t, tc thy phn v ngng t cc mui/ancoxit khc nhau nn khng d kim sot[49, 73]. S dng cc mui kim loi d dng x l hn so vi cc ancoxit kim loi, chuyn ha chng sang dng oxit d dng bi phng php phn hy nhit, cng c th thc hin bng nhiu dung mi hu c to phc vi kim loi v r tin. Ni cch khc, cng ngh sol-gel vi cc mui kim loi c th thc hin c bi s to thnh phc cht vng cng gia ion kim loi vi phi t hu c. Phng php sol-gel to phc khng nhy vi s c mt ca nc (tr mt vi ngoi l); khng i hi mi trng kh tr v thm ch khng cn kim sot cn thn thi gian v iu kin qu trnh to gel m vn c th t c tnh ng th. l s t hp ca cc yu t gii thch cho kh nng s dng rng ri ca phng php sol-gel to phc trong vic tng hp cc vt liu st in, siu dn, st t, CMR, quang xc tc, pin nhin liu, in cc, xc tc v cc oxit phc hp khc. Nhiu nh khoa hc nghin cu s to thnh phc kim loi - phi t hu c ch to cc gm v cc mng mng oxit kim loi bi cng ngh sol-gel bng vic s dng vt liu ban u l cc mui kim loi nh cc nitrat [47, 75, 89]; cc clorua [39, 72] v cc axetat [8, 94]. Phng php Pechini l mt phng php ni ting trong vic ch to mu oxit kim loi, tin cht polyme c ch to t cc mui kim loi, etylen glycol v axit xitric bng vic x l nhit nhit thp [9, 95, 104]. Phng php ny cho php cc cation kim loi c trn ln quy m phn t v vic to vng cng cc ion kim loi trong dung dch axit xitric to iu kin thun li cho qu trnh to ra sn phm oxit phc hp cui cng. Hn na, qu trnh ny cho nhiu thun li trong vic ch to vt liu nh gi thnh thp, thnh phn ng nht, tinh khit cao v nhit x l thp. Phng php ny c p dng ch to

49

cc mng mng, ng dng cho vt liu dn in [11, 55], vt liu st in [103], vt liu quang hc [54], cht in ly [1] v.v Ngun gc ca phng php sol-gel to phc c t bng pht minh ca Pechini [82] khi ch to cc t in dng mng mng bng vic s dng cc axit hu c a chc c kh nng to vng cng vi ion kim loi trong cc phc bn v mt diol- cht cha 2 nhm chc ru. Cc diol hot ng nh mt dung mi trong bc to phc v sau tham gia vo phn ng polyeste ha vi axit hyro cacboxylic nh axit xitric, tactaric v glycolic to nn mng polyme ba chiu vi cc phc cha kim loi c trn ln mc nguyn t. Khi so snh vi a s cc axit, axit xitric (C3H7(OH)(COOH)3) c s dng rng ri nht trong phng php sol-gel to phc do n c n nh cao. Cc phc kim loi vi phi t xitric in hnh c xu hng n nh do s kt hp mnh ca ion xitric vi cc cation kim loi bao gm 2 nhm cacboxyl v mt nhm hyroxyl nh trong hnh 3.1. axit xitric
O HO C H C H C O C OH HO H C H OH H C H HO M1 HO H C C H C O O C O H C H H C H O H C H H C H H H O O C H O C C O C OH O M3 H H O H C C C O H C H C C H O M2 H C H O O C O O C O H C H OH M1, M2, M3

etylen glycol

ion kim loi

H C H HO O O O C C

Hnh 3.1. S minh ha cc phn ng xy ra trong phng php Pechini.

Vic thm etylen glycol (HOC2H4OH) dn n s to thnh este hu c. Phn ng ngng t xut hin vi s to thnh mt phn t nc (to thnh t cc

50

ion hyroxit ca axit cacboxylic v cc proton t ru). Phn ng ngng t v polyme ha c tng cng bi x l nhit. Hnh 3.2 gii thiu cc bc ch yu ca phng php sol-gel to phc trong ch to vt liu oxit perovskit. Cc mui kim loi thch hp c a vo etylen glycol (EG), lng d dung dch axit xitric (CA) c thm vo
Hnh 3.2. S qu trnh ch to vt liu ABO3.

to thnh phc kim loi-xitrat. Sau nhit c tng ln n 80 oC y mnh s to thnh polyeste do phn ng gia axit xitric t do (d) v etylen glycol. Mng li polyme ca gel c oxy ha dn n xerogen, x l nhit 450 - 600
o

C phn hy cc cht hu c, thiu kt v thu c bt mu oxit. 3.2. Cc phng php nghin cu cu trc, vi cu trc

3.2.1. Phng php phn tch nhit Da trn cc hiu ng thu c khi gia nhit vt liu, phng php phn tch nhit c dng xc nh nhit chuyn pha, ht khi lng, nng lng chuyn pha, s thay i v kch thc, ng sut, tnh cht n hi ca vt liu v.v... Cc phng php phn tch nhit thng c kt hp vi cc phng php phn tch cu trc khc nh nhiu x tia X v nh hin vi in t iu chnh v ti u ha qu trnh ch to vt liu, gii thch c ch ca qu trnh hnh thnh cc pha trong vt liu ... C hai k thut phn tch nhit thng gp l phn tch nhit vi sai (DTA) v phn tch nhit vi trng (TGA). K thut phn tch nhit vi sai (DTA) Bn cht ca k thut ny l da trn s thay i nng lng nhit trong qu trnh hp th nhit t bn ngoi ca mu nghin cu khi xy ra cc qu trnh bin

51

i bn trong vt liu. Vi cc chuyn pha loi I thng gp, mi trng thi chuyn pha ca mu s tng ng vi s bin thin nng lng nhit ti cc vng nhit khc nhau, l kt qu ca qu trnh gii phng hoc thu nng lng nhit ca mu. Nhit ca mu c o nh mt hm ca nhit mu chun (khng thay i vi nhit ) so snh. Mi trng thi chuyn pha ca mu o s l
Hnh 3.3. Gin m t nguyn l hot ng ca mt thit b phn tch nhit vi sai.

kt qu ca qu trnh gii phng hoc thu nhit bi mu. Vi phn nhit (T) i vi nhit iu khin T m ti ton b h thay i s cho php phn tch nhit chuyn pha v xc nh y l qu trnh chuyn pha ta nhit hay thu nhit. T th phn tch nhit vi sai DTA c th xc nh nhit chuyn pha v thnh phn nh lng ca mu. K thut phn tch nhit vi trng (TGA) K thut ny da trn s thay i khi lng ca mu nghin cu khi xy ra cc qu trnh t gy hoc hnh thnh cc lin kt vt l, ha hc ti mt nhit xc nh, t thu c cc d liu lin quan n nhit ng hc v ng nng ca cc phn ng ha hc, c ch phn ng, cc phn ng trung gian v phn ng cui cng. Hai php phn tch nhit ny thng c o kt hp trong cng mt thit b. Cc mu trong lun n c o trn thit b o Shimazu TA-50 t ti Vin Ha hc, Vin Khoa hc v Cng ngh Vit Nam. 3.2.2. Phng php phn tch cu trc bng nhiu x tia X Nhiu x tia X l thit b dng nghin cu, xc nh pha cu trc tinh th ca vt liu. N l mt trong nhng cng c quan trng nht c s dng trong nghin cu ha hc cht rn v khoa hc vt liu. Nguyn l hot ng ca n da

52

trn hin tng nhiu x tia X. Khi chiu chm tia X vo vt liu kt tinh, n s b phn x bi cc mt phng tinh th. H mt phng tinh th (hkl) no c gi tr d (khong cch gia hai mt phng ln cn c cng ch s) tha mn iu kin phn x Bragg: n = 2d.sin() s cho mt cc i nhiu x ti v tr gc
= arcsin(n / 2d ) tng ng

trn gin nhiu x. i vi mi loi vt liu kt tinh, gin nhiu x tia X l duy nht v c c trng bi mt b vch nhiu x. Phn tch gin nhiu x, ta c th thu c cc thng tin nh tnh, nh lng v cc pha tinh th c trong vt liu v xc nh chnh xc hng s mng tinh th, phn bit vt liu kt tinh vi vt liu v nh hnh. T gin nhiu x tia X ngi ta c th xc nh c kch thc ht trung bnh t cng thc gn Hnh 3.5. S khi ca mt thit b nhiu x tia X. ng Scherrer:
L= Trong , 0.9 .cos (3.1)
Hnh 3.4. Hin tng nhiu x tia X t hai mt phng mng tinh th.

L: Kch thc ht, n v: , : Bc sng tia X, y = 1,5406 , : bn rng ca vch nhiu x, n v: rad, : Gc nhiu x.

53

Cc php o gin nhiu x tia X ca h mu c thc hin trn h nhiu x k SIEMENS D5000 ti Vin Khoa hc Vt liu - Vin Khoa hc v Cng ngh Vit Nam. Cc iu kin ghi gin nhiu x tia X l: - Ch o: /2, - Tc quay mu quanh trc vung gc vi mt phng mu: 30 vng/pht, - ng pht tia X: loi ng c anode bng Cu, hiu in th 35 kV, cng dng in 30 mA, - ng m: ng m bn dn Si (Li) vi ca s in t t 8,04 0,3 keV tng ng vi nng lng ca bc x CuK c bc sng = 1,5406 (vi nng lng ny, bc x CuK c lc b hon ton ngay t u), - Gc 2 c qut t 10o n 82o, - Mot bc vi bc o: 0,02o. Cc s liu nhiu x tia X c ghi nhn bng my tnh vi chng trnh iu khin l DIFFRAC-AT lm vic trong mi trng DOS.

3.2.3. Kho st hnh thi hc b mt bng knh hin vi in t qut (SEM)

Knh hin vi in t qut (SEM) l thit b s dng nghin cu hnh thi hc b mt ca mu. y l thit b dng chp nh vi cu trc b mt vi phng i ln gp nhiu ln so vi knh hin vi quang hc vi nguyn tc hot ng nh sau. Chm tia in t c nng lng cao - c gi l chm tia in t s cp c to ra v iu khin chm tia Hnh 3.6. S nguyn l ca knh hin vi in t
qut (SEM).

ny qut trn mt din tch rt nh ca b mt mu. Sau , cc tn hiu c pht ra do tng tc ca in t s cp vi mu - c gi l cc tn hiu th cp c

54

ghi nhn v phn tch. Cc tn hiu ny bao gm: in t th cp (1), chm in t tn x ngc (2), in t tn x khng n hi (3), in t tn x n hi (4), in t hp th (5), in t Auger (6) v tia X (7). Cc tn hiu (1, 2, 5, 6, 7) c s dng trong knh hin vi in t qut. Cn c vo cc thng tin thu c bi ng m t cc tn hiu trn, ngi ta c th dng li hnh thi b mt ca mu mt cch chnh xc. Trong lun n, cc mu c chp bng thit b knh hin vi in t qut pht x trng HITACHI S-4800 t ti Phng th nghim trng im trc thuc Vin Khoa hc Vt liu. Thit b ny c phng i cao nht c th t n 200.000 ln, phn gii c th t c 2 nm th hiu 1 kV.

3.3. Cc phng php nghin cu tnh cht 3.3.1. Phng php TPD xc nh gii hp ph oxy
Phng php xc nh gii hp ph theo chu trnh nhit (TPD) dng quan st s hp ph phn t trn b mt mu khi nhit b mt tng. Khi cc phn t n tip xc vi b mt, chng b hp ph trn bng cch to ra lin kt ha hc vi b mt do c hin tng cc tiu ha nng lng. Nng lng lin
Hnh 3.7. S khi h o TPD
T(t) = T0 + .t Bung chn khng Tinh th Ph k khi lng H iu khin v my vi tnh

kt thay i theo s ng gp ca cht ht v b mt. Nu b mt mu c t nng ti mt im, nng lng nhit c chuyn sang cho cc phn t c hp ph to ra s hp ph n. Nhit m ti xy ra s hp ph gi l nhit hp ph. Do TPD th hin thng tin v nng lng lin kt. Cng ca tn hiu hp ph I(T) t l vi tc m ti nng phn t hp ph ca b mt (-dN/dt) gim c biu din nh sau:

55

I(T) -

-E des dN N x = exp a dT RT

(3.2)

Trong : x l bc hp ph ng hc (c th bng 0, 1 hoc 2); l h s gc ca s ph thuc thi gian ca nhit kho st; Eades l nng lng hot ha ca gii hp. Ph TPD th hin cng thay i khi lng ca mu theo thi gian hoc nhit [10]. Nu c nhiu hn mt trng thi lin kt ca phn t hp ph vi b mt mu th ta s c cc nh hp ph rt phc tp trong ph TPD. Din tch nh hp ph t l vi s
Hnh 3.8. H o Micromeritics AutoChem II 2920

lng phn t hp ph. V tr ca nh hp ph lin quan ti entanpy hp ph ngha l cng lin kt ca phn t hp ph vi b mt mu. o TPD, ngi ta dng mt ph k khi lng di iu kin chn khng cao, nhit ca mu o c tng tuyn tnh theo thi gian bng mt chng trnh t ng. Kt qu o c t ng ghi bng mt chng trnh my tnh. Trong lun n ny, chng ti s dng oxy nghin cu gii hp theo chu trnh nhit, tc tng nhit : 10
o

C/pht, lu lng kh oxy (10% th tch

trong He): 25,17 ml/pht (iu kin nhit p sut tiu chun). Cc mu c o trn h Micromeritics AutoChem II 2920 t ti B mn Ha du, Trng i hc Bch khoa H Ni.
Hnh 3.9. th BET in hnh.

56

3.3.2. Phng php xc nh din tch hp ph b mt BET

L thuyt BET l l thuyt v s hp ph vt l ca cc phn t kh trn b mt cht rn. Nm 1938, ln u tin Stephen Brunauer, Paul Hugh Emmett v Edward Teller a ra l thuyt BET, BET l ba ch ci u tin trong tn ca ba nh khoa hc ny. L thuyt BET l s m rng ca l thuyt Langmuir, v s hp ph phn t n lp, xt s hp ph a lp da trn cc gi thit sau: (a) s hp ph vt l cc phn t kh trn cht rn trong v s cc lp; (b) khng c tng tc gia cc lp hp ph; (c) l thuyt Langmuir c th p dng ng cho mi lp ring l. Phng trnh BET c a ra t cc gi thit trn:
1 c 1 P = v[(P0 / P ) 1] v m c P0 1 + v c m

(3.3)

Trong , P v P0 l p sut cn bng v p sut bo ha ca cc cht b hp ph ti nhit hp ph, v l lng kh c hp ph (chng hn xt trong mt n v th tch), v vm l lng kh c hp ph ca mt lp, c l hng s BET, c biu din bi phng trnh sau:
E EL c = exp 1 RT

(3.4)

Trong E1 l nhit lng hp ph bi lp th nht, v EL l nhit lng hp ph bi lp th hai hoc cc lp su pha trong v bng nhit lng ha lng. Phng trnh (3.2) ng vi trng hp hp ph ng nhit, c th c biu din bng mt th ng thng vi trc tung l 1/v[(P0/P)-1] v trc honh l = P/P0 theo cc kt qu thc nghim. th ny c gi l th BET (hnh 3.9). Phng trnh ny c mi lin h tuyn tnh vi 0,05 < P/P0 < 0,35. Gi tr dc A v v tr th ct trc tung (l) c dng xc nh lng kh c hp ph bi mt lp, vm, v hng s BET, c, theo phng trnh:
vm = 1 A+ I

(3.5)

57

c = 1+

A I

(3.6)

Phng php BET c s dng rng ri trong cc nghin cu b mt tnh din tch b mt ca vt rn thng qua s hp ph ca cc phn t kh. Din tch b mt tng cng Stotal v din tch b mt ring S c xc nh qua phng trnh sau:
S BET ,total =

(v m Ns )
V

(3.7) (3.8)

S BET =

S total a

Trong ,

N: S Avogadro; s: Thit din ca phn kh c hp ph; V: Th tch mol kh c hp ph; a: Khi lng mu cht rn.

3.3.3. Phng php xc nh thnh phn oxy

Ngoi cc nghin cu bng nhiu x ntron, xc nh t lng oxy trong cc oxit perovskit, chng ta c th s dng cc phng php phn tch ha hc khc nh chun s dng dung dch chun l kali icrmat hoc phng php chun iod. Cc phng php ny u thng qua cc phn ng oxy ha - kh khc nhau, cho php xc nh t lng oxy trong hp cht cn phn tch. y chng ti s dng phng php icrmat. Trc tin cc oxit c ha tan trong dung dch axit. Sau dng dung dch Fe2+ kh ha cc cation kim loi ha tr cao hn, dung dch K2Cr2O7 c dng chun lng Fe2+ d. T mi lin h gia nng v th tch dung dch Fe2+, dung dch K2Cr2O7, khi lng mu ban u chng ta rt ra c t lng oxy. Cc phn ng oxy ha kh xy ra nh sau: Fe2+ + B4+ Fe3+ + B3+ Fe2+ + C3+ Fe3+ + C2+ 6Fe2+ + (Cr2O7)2- + 14H+ 6Fe3+ + 2Cr3+ + 7H2O (3.8)

58

u im: Phng php n gin, s dng ha cht r tin, chnh xc tng i cao. Nhc im: Cc mu khng ha tan hoc tan t trong dung dch axit th khng p dng phng php ny c. c bit vi cc oxit cha Cu(I) v Pb(IV) thng cho kt qu khng lp li do trong mi trng rt axit chng to thnh cc phc bn dn n kt qu b sai lch.

3.3.4. Kho st c trng nhy hi cn ca cm bin a) S mch kho st c trng ca cm bin

Cc php o c trng nhy kh ca cm bin c thc hin ti Phng Cm bin v Thit b o kh, Vin Khoa hc Vt liu. Cc cm bin c mc theo s nh hnh 3.10. Tn hiu ly ra c ghi nhn lin tc tng giy bng ng h vn nng Keithley model DMM 2700 ghp ni vi my tnh. in tr ca cm bin c xc nh theo biu thc: RS = (VC - VRL) RL/VRL (3.9)
Hnh 3.10. S ly tn hiu ca cm bin Vi VC: th cp cho cm bin; RL: in tr ti; VRL: st th trn in tr ti; RH: in tr l vi nhit;VH: in th l vi nhit; VS: st th trn cm bin.

b). H to hi cn
H to hi cn bao gm cc bnh cu cha dung dch etanol c t trong b iu nhit, c nh 34 oC. Mi quan h gia nng pha lng v pha hi tun theo cc nh lut Henry v cng thc Dubowski [18].

59

Hnh 3.11. S b tr th nghim h to hi cn 34 oC

CH2O l nng etanol trong dung dch nc. Khi khng kh c sc qua dung dch etanol c nng CH2O, nng ca etanol trong khng kh, Cair c cho bi cng thc Dubowski: Cair = 0,04145 x 10-3CH2O x exp (0,06583 x t) y t l nhit o bng oC. i vi t = 34 oC, Cair = 0,38866 x 10-3CH2O. S khi v nh h to hi cn c minh ha trn hnh 3.11. v 3.12. (3.10)

b) H o c trng nhy hi cn ca cm bin

Cc php o c c trng nhy kh ca cm bin c thc hin ti Phng Cm bin v Thit b o kh, Vin Khoa hc Vt liu trn h o t ch to. H o ny s dng hai lu lng k in
Hnh 3.12. H to hi cn.

t (c khong chia tng ng t 0 - 50 ml/pht v 0 - 500 ml/pht) cng vi hai lu lng k c hc c khong chia t 0 - 1000 ml/pht. Cc cm bin c mc theo

60

s nh hnh 3.10. Tn hiu ly ra c o ghi nhn lin tc tng giy bng ng h vn nng Keithley model DMM - 2700 ghp ni vi my tnh.

3.4. Kt lun chng

Trn y chng ti trnh by mt cch tng quan cc phng php tng hp vt liu, cc k thut phn tch vi cu trc v phng php kho st cc tnh cht c bn ca cc h vt liu oxit perovskit ng dng ch to cm bin kh. Cc phng php v h o ring dng trong kho st c tnh nhy kh ca vt liu v chun cm bin nhy hi cn cng c cp trong chng ny. Cc kt qu tng hp v kho st tnh cht ca h vt liu oxit perovskit nhy hi cn c trnh by trong cc chng tip theo.

61

CHNG 4 CH TO V NGHIN CU MT S TNH CHT CA CC H VT LIU LaBO3 V A(Fe,Co)O3 NG DNG TRONG CM BIN KH
Trong chng ny chng ti s tho lun v vic s dng phng php solgel to phc s dng axit xitric v etylen glycol l cc tc nhn chnh trong tng hp vt liu oxit perovskit nhm ng dng trong ch to cm bin v thit b o hi cn. C s ca phng php ny l phn ng este ha gia glycol v axit cacboxylic a chc. pht trin lin tc mch polyme, s tn ti ca t nht hai nhm chc trong cng mt monome l rt quan trng. Trong giai on u, dung dch cung cp mi trng cn thit ngn cn s phn tch cation, sau mng li polyme tng i bn s by cc cation v duy tr ng th ban u ca dung dch. Qu trnh polyme ha hon thnh v lng dung mi d c lm bay hi, mng li polyme ca gel c oxy ha to xerogen, thiu kt v thu c bt mu oxit.

4.1. Tng hp vt liu LaFeO3 v cc yu t nh hng ln kch thc ht 4.1.1. Tng hp vt liu v phn tch DTA
Cc mui La(NO3)3 v Fe(NO3)3 vi t l thnh phn theo hp thc c ha tan trong nc ct, sau thm cht to phc axit xitric - CA v cht to polyme (etylen glycol EG). Hn hp dung dch c trn u v n nh nhit ti nhit 60 oC. pH ca mi trng c iu chnh trong khong 6 n 7 bng dung dch NH4OH long. Nhit c nng ln 80 oC y mnh s to thnh polyeste do phn ng gia axit xitric d v
Hnh 4.1. Hnh nh xerogen mu LaFeO3 thu c sau khi sy 15 gi 120 oC.

etylen glycol trong hn hp dung dch. Sau 6 gi, ta thu c gel hu c c mu nu sm. Hn hp gel ny c sy kh nhit 120 oC, sau 15 gi thu c

62

xerogen. Nung phn hy cc tin cht hu c v cc nitrat nhit 450 oC trong thi gian 2 gi. Hn hp bt mn ny c thiu kt 600 oC trong 4 gi. Bt LaFeO3 thu c c mu nu vng. Hnh nh xerogen mu LaFeO3 thu c sau khi sy 15 gi 120 oC c minh ha trn hnh 4.1 cho thy xp cao. Kt qu phn tch DTA ca xerogen c trnh by trn hnh 4.2. ng cong DTA ca xerogen cc mu u cho thy tt c cc mu u c qu trnh ta nhit lin tc trong khong nhit rng (khong t 50 n

Hnh 4.2. Gin DTA v TGA ca bt xerogen mu M2.

500 oC). Qu trnh ta nhit xy ra trong vng nhit thp (di 300 oC) l do s phn hy ca gc xitrat, s phn hy ny xy ra mnh nht 234 oC. S ta nhit tip tc xy ra nhit cao hn cho n 500 oC, trong khong nhit ny xy ra cc qu trnh phn hy ca gc nitrat vi cc i 372 oC. T trn 500 oC tr i, bt u qu trnh thu nhit, c th l do bt u s kt tinh hnh thnh pha perovskit. Trn gin TGA (xem hnh 4.2) cho thy s mt mt khi lng ch yu xy ra trong hai vng nhit t 150 n 250 oC v t 250 n 450 oC, tng ng vi s phn hy ca cc gc xitrat v nitrat. nhit trn 500 oC, khi lng mu gim hn 70 %, trn khong nhit cao hn, khi lng mu hu nh khng thay i, mu bt u chuyn sang qu trnh kt tinh to pha. Chng ti la chn nhit 600 oC tt c cc mu.

4.1.2. Cc yu t nh hng ln kch thc ht trong qu trnh tng hp a). nh hng ca cht to phc
Trong phng php sol-gel to phc, axit xitric (C3H7(OH)(COOH)3) c s dng rng ri nht do n c n nh cao. Axit xitric l mt axit hu c a chc tng i mnh. Cc phc kim loi vi phi t xitric c xu hng n nh do

63

s kt hp mnh ca ion xitric vi cc cation kim loi bao gm hai nhm cacboxyl v mt nhm hyroxyl. Cc mu c la chn kho st vi cc t phn mol c th bao gm: La:Fe:CA l 1:1:3 (M1), 1:1:4 (M2) v 1:1:5 (M3). Cc mu ny c tng hp trong mi trng vi t phn mol CA/EG = 4:6 v theo cc quy trnh tng hp nh c trnh by phn trn. Cc kt qu phn tch gin nhiu x tia X ca cc mu M1, M2 v M3 c trnh by trn hnh 4.3. Nhn thy rng, nhit 600
o

C cc mu u n pha, c cu

trc trc thoi (cc nh nhiu x tng ng vi th JCPDS s 371493) v khng c s khc bit nhau nhiu. Cc kt qu xc nh Hnh 4.3. Gin nhiu x tia X ca cc mu M1, kch thc ht cho cc mu bng
M2 v M3

cng thc gn ng Scherrer ch ra rng, mu M2 cho kch thc ht nh nht (19 nm), cc mu M1 v M3 c kch thc ht ln lt l 22 v 26 nm. Kt qu thu c cho thy mu c t l mol La:Fe:CA = 1:1:4, t l CA/EG = 4:6 kh ph hp vi cc s liu c cng b trc y [89]. Do vy, t l mol La:Fe:CA = 1:1:4 s c lm chun trong cc kho st s nh hng ca cht to polyme ln kch thc ht mu.

b). nh hng ca cht to polyme

Cht to polyme c chng ti s dng trong kho st s nh hng ln kch thc ht y l etylen glycol. Phn ng polyeste ha vi axit hyro cacboxylic nh axit xitric to nn mng polyme ba chiu vi cc phc cha kim loi c trn ln quy m nguyn t. Cn bng ca phn ng este ha c dch chuyn v pha polyeste bng cch tng nng cht phn ng hoc ly i sn phm khi mi trng phn ng. L do s dng lng d EG lin quan n s cn thit loi b nc khi mi trng phn ng. Trong hi bay ra cha EG s

64

c loi b dn khi phn ng. im si ca EG l thp nht trong s cc diol, bi vy vic la chn EG lm monome l iu thun li nht. Chng ti gi t l mol ion kim loi: axit xitric cc mu l 1:4 nhng lng etylen glycol khc nhau. K hiu mu M4, M2, M5 v M6 vi t l mol CA:EG ln lt l: 3:7; 4:6; 5:5 v 6:4. Cc mu u c ch to vi quy trnh nh nhau. Kt qu phn tch nhiu x tia X cho thy cc mu c cu trc n
Hnh 4.4. nh hng ca lng EG ln kch thc ht LaFeO3.

pha. Kch thc ht ca cc mu M4, M2, M5 v M6 c gi tr tng ng l 23, 19, 26 v 29 nm. S nh hng ca thnh phn to polyme ln kch thc ht c biu din trn hnh 4.4. Nhn thy rng, vi t l mol CA:EG = 4:6 cho kch thc ht LaFeO3 nh nht (19 nm).

c). nh hng ca lng cht phn tn

Thng thng, trong qu trnh tng hp vt liu bng phng php sol gel, cht phn tn ch c xt n vi vai tr tng ng u ca mu. Vi mc ch tm kim cng ngh ch to vt liu c kch thc ht ti u, nn s nh hng ca cht phn tn ln kch thc ht cng c kho st. Cc mu c s dng y c t l mol La:Fe:CA l 1:1:4 v t l CA/EG bng 4:6. S khc bit gia cc mu l lng cht phn tn tham gia trong qu trnh tng hp. T l th tch cht phn tn - etanol c s dng y l: 0, 50, 75 v 100%. Tng ng vi cc mu c k hiu l M2, M7, M8 v M9. Cc kt qu nh gi kch thc ht ca cc mu kho st thng qua gin nhiu x tia X c trnh by trong bng 4.1. Nhn thy rng, mu M8 cho kch thc ht nh nht bng 11 nm. Cht phn tn (etanol) khng ch lm tng ng u ca mu, m cn nh hng mnh ln kch thc trung bnh ca mu. Nguyn nhn ca s nh hng

65

ny c th l do sc cng b mt ca etanol (22,75 dyne/cm 20 oC [75]) l nh hn nhiu so vi nc (72,75 dyne/cm 20 oC), nn chng lm gim lc hp dn gia cc ht keo v ngn cn s to m gia cc ht. Do , trong qu trnh tng hp cn khng ch lng cht phn tn ch ti u m bo kch thc ht thu c l nh nht. Vi cht phn tn l etanol, cc kho st cho thy khi t l th tch etanol 75% thu c bt LaFeO3 c kch thc ht nh nht. Bn cnh cc kt qu xc nh din tch b mt ring mu vi kch thc ht khc nhau ch ra rng, cc mu c kch thc ht ln nht (19 nm) cho SBET l 21 m2/g v nh nht (11 nm) cho SBET l 38 m2/g. Mt khc, cc kt qu kho st v hnh thi hc qua nh SEM ca cc mu M2 v M8 c trnh by trn hnh 4.5 cho thy mu M8 c ng u hn mu M2. iu cho ta nhn xt rng, vic thm cht phn tn etanol khng ch nh hng mnh ln kch thc ht m cn lm tng ng u ca mu.

Bng 4.1. nh hng ca lng etanol ln kch thc ht LaFeO3

M2 M7 50 13 M8 75 11 37,48 M9 100 18 -

% th tch etanol Kch thc ht (nm) SBET (m /g)

2

0 19 21,25

(a)

(b)

Hnh 4.5. nh SEM ca mu M2 (a) v M8 (b).

Tm li, vi t l mol La:Fe:CA = 1:1:4; CA/EG = 4:6 v lng cht phn tn etanol 75% th tch cho mu bt LaFeO3 c kch thc ht nh v ng u

66

nht. Cc mu thu c (mu M8) hon ton c th p ng c mc ch s dng lm vt liu cho ch to cm bin nhy kh.

4.2. H vt liu LaBO3 (B l Fe, Co, Ni v Mn)

Oxit kim loi bn dn l nhng vt liu c ha hn nhiu hn trong cm bin ha hc pha rn, bi cm bin da trn cc vt liu ny c nhiu u im nh kch thc nh, chi ph thp, tiu th in nng thp v tnh tng thch cao vi cc vi mch in t. Mt s cht oxit kim bn dn nh SnO2 [121], TiO2-WO3 [73], CdO-Fe2O3 [49], Fe2O3-SnO2 [89], SnO2-Nb2O5 [75]... c s dng ch to cc cm bin etanol. Cc oxit perovskit cng c cp n trong cc nghin cu cm bin kh. Khi nghin cu h vt liu (Ln,A)BO3 (Ln = t him, A = kim loi kim th, B = kim loi chuyn tip), Obayashi v cc ng nghip [77] thy rng, khi c mt etanol, dn in ca cc oxit thay i ng k. y l th d u tin ca vic ng dng oxit perovskit trong cm bin kh.

4.2.1. Cu trc v kch thc ht h mu LaBO3 (B= Fe, Co, Ni v Mn)

Cc mu bt h LaBO3 (B = Fe, Co, Ni v Mn) c ch to theo cng ch cng ngh nh trnh by phn 4.1. Sau khi ch to, cc mu bt c phn tch nhiu x tia X. Gin nhiu x tia X ca cc mu LaBO3 c trnh by trn hnh 4.6. Cc oxit LaCoO3 v LaNiO3 c cu trc tinh th h mt thoi (cc nh nhiu x tng ng vi th JCPDS s 25-1060 v 341028); oxit LaFeO3 c cu trc tinh th h trc thoi (cc nh nhiu x tng ng vi th JCPDS s 37-1493) v oxit LaMnO3 c cu trc tinh th h lc gic (cc nh nhiu x tng ng vi th JCPDS s 32-484). Kch thc ht trung bnh v
Hnh 4.6. Gin nhiu x tia X ca cc mu bt LaBO3 (B= Fe, Co, Ni v Mn).

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hng s mng c tnh ton bng cc phn mm WINFIT v FULLPROF, cc kt qu c trnh by trong bng 4.2.

Bng 4.2. Hng s mng v kch thc ht tinh th trung bnh ca h mu LaBO3 (B= Fe, Co, Ni v Mn) Oxit a () b () c () D (nm)
LaFeO3 LaMnO3 LaCoO3 LaNiO3 5,557 5,505 5,443 5,425 7,837 5,505 5,443 5,425 5,548 13,545 13,099 13,140 12,0 15,1 13,6 13,1

4.2.2. S gii hp oxy theo chu trnh nhit

Cc kt qu kho st s gii hp O2 theo chu trnh nhit ca cc mu LaBO3 c trnh by trn hnh 4.7. Nhit v lng oxy gii hp ra c trnh by trong bng 4.3. C th thy rng, trn gin gii hp TPD-O2 ca cc mu nghin cu u th hin r ba nh gii hp oxy ngoi tr LaMnO3. Cc kt qu gii hp di 500 oC thu c kh ph hp vi cc tc gi c cng b trc y [3].

Hnh 4.7. Ph TPD-O2 ca cc mu LaBO3 vi B: Mn, Fe, Co (a), v B: Ni (b).

Cc dng oxy tng ng vi cc bc gii hp y c c trng cho s hp ph ha hc ca oxy trn b mt cht rn v s tham gia ca oxy khi. Gin minh ha cho c ch hp ph v gii hp oxy c minh ha trn hnh 4.8. Khi

68

nhit tng ln trng thi oxy hp ph trn b mt perovskit xy ra theo cc bc phn ng c minh ha di y [3].

Bc th nht (1): S hp ph oxy c th l kt qu ca s tng tc gia cc tm

hot ng b mt vi cc phn t oxy trong pha kh (1):

O-(B mt) B(B mt)(n-1)+ B(B mt)n+ + O2 (pha kh)

O-(hp ph) B(B mt)n+

O-(B mt) B(B mt)n+

(4.1)

y, B l cc kim loi chuyn tip, n c gi tr bng 3 hoc 4 v vt liu c biu din di dng:
O-(hp ph) B(B mt)n+ Hoc O-(B mt) B(B mt)n+ O2-(hp ph) B(B mt)n+ B(B mt)n+

k hiu cho

nt khuyt anion. Phn ng trao i gia oxy hp ph vi oxy trong lin kt b mt

(Ohp ph O)2-(B mt)

+ O2

B(B mt)n+

B(B mt)n+

(4.2)

S trao i oxy c th c hnh thnh t s chia ct lin kt O-O ca cc phn t b hp ph hnh thnh ba cu t ba nguyn t oxy ring phn (O3)2- (c to bi gia oxy b mt trong lin kt B3+O vi phn t oxy hp ph). Tuy nhin, trong mt s trng hp bc trao i ny khng din ra trong mt s hp cht cacbonat [3].
Hnh 4.8. Hnh minh ha qu trnh hp ph v gii hp oxy trn b mt v cc qu trnh trao i oxy trong h vt liu ABO3.

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Trn hnh 4.7 ch ra rng nh gii hp u tin (1) c nhit nh di 440oC v nh th hai (2) c nhit nh 490 oC. Phng trnh phn ng c trng cho qu trnh gii hp oxy- hai nh ny c biu din theo phng trnh sau - bc th hai (2):

O2-(hp ph)

O-(hp ph)

B(B mt)n+ B(B mt)n+

B(B mt)(n-1)+ B(B mt)n+ +

O2 (kh)

(4.3)

Phn ng (4.2) c trng cho bc gii hp oxy-1. Qu trnh gii hp do s kh mt s ion Bn+ thnh ion B(n-1)+ c din ra vng nhit cao hn c m t bi phng trnh 4.3. Cc oxy mng sau gii hp c th c ti sinh sau khi b phn ly ti v tr tm hot ng ban u hoc khuch tn trc tip vo khi (3) hoc t b mt vo bin ht theo bc th t. Cc qu trnh khuch tn ny din ra song song vi nhau - t b mt vo khi v t bin ht vo khi tng ng vi nh gii hp th 3 quan st c vng nhit trn 500 oC c c trng cho s gii hp ca oxy mng tinh th ra khi b mt oxy-. Phng trnh phn ng cho cc bc ny c minh ha di y: Qu trnh trao i oxy gia b mt v khi (3):
O2-(hp ph) O2-(mng) O2-(mng) O2-(hp ph) B(Khi)n+ B(Khi)n+

B(BM)n+

B(BM)n+

B(Khi)n+

B(Khi)n+

B(BM)n+

B(BM)n+

Qu trnh trao i gia b mt v bin ht (4):

O2-(hp ph) O2-(mng) O2-(mng) B(BM)n+ B(BM)n+ B(BH)n+ O2-(hp ph)

B(BM)n+

B(BM)n+

B(BH)n+

B(BH)n+

B(BH)n+

Qu trnh trao i gia bin ht v khi (3):

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O2-(hp ph)

O2-(mng)

O2-(hp ph) B(BH)n+ B(BH)n+ B(Khi)n+

O2-(mng)

B(BH)n+

B(BH)n+

B(Khi)n+

B(Khi)n+

B(Khi)n+

T kt qu thc nghim c trnh by trong bng 4.3 nhn thy rng, nhit gii hp oxy- t cc oxit LaBO3 (B = Mn, Fe, Co v Ni) c xu hng gim vi s tng ln ca s in t 3d ca kim loi chuyn tip. Bc lin kt B-O s gim khi s in t vng 3d ca cc kim loi chuyn tip tng. Ngha l, nhit gii hp oxy ph thuc vo tng tc gia oxy hp ph vi cc ion kim loi chuyn tip.

Bng 4.3. Nhit v lng oxy gii hp Lng oxy gii hp (mmol/g) ( ): Tgii hp (oC) Oxit 2 1 LaMnO3 0,13 (441) 0,35 (493) LaFeO3 0,40 (422) 0,76 (479) 0,19 (539) 0,07 (375) 0,45 (490) 0,09 (541) LaCoO3 0,04 (283) 0,11 (449) 0,01 (542) LaNiO3 4.3. H vt liu LaFe1-xCoxO3 (0,0 x 1,0)
Cc hp cht LaFeO3 v LaCoO3 l cc bn dn loi p. Khi t trong mi trng kh oxy ha hay kh kh, s hp ph cc phn t kh ca mi trng ln b mt vt liu lm tng hay gim dn in ca chng. Kh nng nhy kh ca vt liu ph thuc rt mnh vo nhit hot ng ca cm bin. nhy ca vt liu cng thay i i vi cc loi kh khc nhau. Ti mi nhit , nhy ca vt liu cn thay i theo nng kh trong mi trng. Trong phm vi ca lun n ny, h vt liu LaFe1-xCoxO3 (0,0 x 1,0) s c ch to theo cng mt ch cng ngh. Thnh phn pha tinh th ca mu c kim tra bng phng php nhiu x tia X mu bt vi bc x Cu K (1,5406 ), thc hin trn h nhiu x k Siemens D5000. H vt liu c ch to di cng mt iu kin bao gm cc mu: LaFeO3 (LFO), LaFe0,9Co0,1O3 (LFC1), LaFe0,8Co0,2O3 (LFC2), LaFe0,7Co0,3O3 (LFC3), LaFe0,6Co0,4O3 (LFC4), LaFe0,5Co0,5O3 (LFC5), LaFe0,4Co0,6O3 (LFC6), LaFe0,2Co0,8O3 (LFC8), LaCoO3 (LCO).

4.3.1. Cu trc tinh th ca h vt liu

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Gin nhiu x tia X ca cc mu cho thy cc mu hon ton n pha. Cc mu vi hm lng Coban thay th x t 0,0 n 0,4 c cu trc trc thoi (O), cn cc mu vi x nm trong khong t 0,6 n 1,0 c cu trc mt thoi (R). S chuyn cu trc ca h khi hm lng coban tng c th hin r trn gin nhiu x tia X, cc vch nhiu x chnh ca cc mu c nng thay th (x) nm trong khong t 0,0 n 0,4 l cc vch n (hnh 4.9), trong khi cc vch v tr tng ng ca cc mu c x bng 0,6 n 1,0 li l cc vch tch i (hnh 4.9).

Hnh 4.9. Gin nhiu x tia X ca mu LaFe1-xCoxO3- (0,0 x 1,0).

Hnh 4.10. S dch chuyn vch nhiu x v tr 2 = 32,2 o ca h mu theo hm lng coban: (a) Vi x = 0,0 - 0,4: rng vch thay i; (b) Vi x = 0,5 - 1,0: xut hin s tch i vch.

Quan st trn gin nhiu x, cho thy khi hm lng coban thay th tng ln, cc nh c xu hng dch chuyn v pha gc 2 ln (xem hnh 4.10), ngha l y s c s gim kch thc c s. Kch thc ht trung bnh v hng s mng c tnh ton bng cc phn mm WINFIT v FULLPROF, kt qu c th hin

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trong bng 4.4. T bng 4.4, ta cng nhn thy vi cu trc trc thoi, khi hm lng coban tng th th tch c s gim, iu ny cng xy ra tng t vi cu trc mt thoi. iu ny c th c gii thch l do bn knh ca ion Co3+ (0,61 ) nh hn bn knh ion ca Fe3+ (0,645 ). ng thi, khi hm lng coban tng, rng vch nhiu x thay i. Bng 4.4 cho thy kch thc ht ca h vt liu nm trong khong t 9 n 24 nm, trong mu LFC4 c kch thc ht nh nht. iu ny ph hp vi kt qu o nhiu x tia X, cho thy rng cc vch ca mu LFC4 ln nht (hnh 4.10).

Bng 4.4. Kch thc ht v cc thng s mng ca h mu LaFe1-xCoxO3

Tn mu LFO LFC1 LFC2 LFC3 LFC4 LFC5 LFC6 LFC8 LCO Cu trc O O O O O R R R R a () 5,557 5,528 5,521 5,494 5,499 5,467 5,462 5,445 5,443 b () 7,837 7,820 7,794 7,773 7,759 5,467 5,462 5,445 5,443 c () 5,548 5,534 5,509 5,482 5,474 13,182 13,164 13,107 13,099 V ( 3) 241,62 239,23 237,06 234,11 233,56 237,37 236,50 233,71 232,92 D (nm) 12,0 24,5 20,7 11,7 9,6 19,4 18,2 17,4 13,6

4.3.2. Hnh thi hc b mt ca mu bt LFC

Hnh 4.11. nh SEM ca cc mu LFC2 (bn tri), LFC4 (bn phi).

kim tra hnh thi hc b mt ca vt liu, cc mu sau khi ch to u c em i chp trn knh hin vi in t truyn qua (SEM). nh SEM ca cc

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mu LFC2, LFC4 c th hin trong hnh 4.11, y l hnh nh cc ht kt m vi nhau. Cc m ht ny u c kch thc di 50 nm, trong khi kch thc ca tng ht ring r l t 9 n 24 nm tnh theo cng thc ca Scherrer t kt qu o nhiu x tia X. Kt qu phn tch thnh phn oxy ca h mu LaFe1xCoxO3-

Bng 4.5. Kt qu phn tch thnh phn oxy. Mu

LMO LFO LFC1 LFC2 LFC3 LFC4 LFC5 LFC6 LFC8 LCO

-0,0912 -0,0142 0,0063 0,0065 0,0071 0,0064 0,0060 0,0086 0,0062 0,0062

Cng thc ha hc
LaMnO3,0912 LaFeO3,0142 LaFe0,9Co0,1O2,9937 LaFe0,8Co0,2O2,9935 LaFe0,7Co0,3O2,9929 LaFe0,6Co0,4O2,9936 LaFe0,5Co0,5O2,9940 LaFe0,4Co0,6O2,9914 LaFe0,2Co0,8O2,9938 LaCoO2,9938

(0,0 x 1,0) c th

hin trong bng 4.5. T s liu trong bng 4.5, ta nhn thy rng trong cc mu khng cha thnh phn Co hm lng oxy trong mu l d. Vi cc mu cha thnh phn Co u thiu mt lng oxy nht nh. Nguyn nhn d oxy trong cc mu khng cha coban c th l do s tn ti ca cc ion Mn4+ v cc

ion Fe4+ v tr nt mng B. Mt khc i vi cc mu cha thnh phn coban, trong qu trnh thiu kt mu mt lng nh ion Co2+ khng b oxy ha hon ton thnh cc ion Co3+. Do vy ti v tr B khng ch c chim gi bi phn ln cc ion Co3+, m cn c s tham gia ca mt lng nh ion Co2+ khng c oxy ha hon ton dn n s khuyt thiu oxy. iu ny s gp phn to ra nhng thay i trong cu trc v tnh cht in ca vt liu. Cc kt qu kho st c trng nhy hi cn ca cc vt liu LaFe1xCoxO3-

(vi 0,0 x 1,0) ch ra rng, nhy ca h vt liu ny t cc i

khi hm lng thay th Co (x) bng 0,4 (phn 5.3.1). Nhit lm vic ti im cho gi tr nhy ln nht gim dn theo s tng ca hm lng thay th Co trong mu. Cc kt qu nghin cu v ch to cm bin nhy hi cn trn cc h vt liu LaFe1-xCoxO3- (vi 0,0 x 1,0) s c tho lun chi tit trong chng

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5 ca lun n ny. Bn cnh , yu t nh hng ca cc nguyn t t him trong h vt liu AFe0,6Co0,4O3 (A l La, Sm, Nd v Gd) ln cu trc v nhy hi cn cng cn c kho st.

4.4. H vt liu AFe0,6Co0,4O3 4.4.1. Cu trc tinh th

Gin nhiu x tia X ca cc mu AFe0,6Co0,4O3 (A l La, Sm, Nd v Gd) c biu din trn hnh 4.12. Kt qu cho thy rng, cc mu thu c l n pha v u c cu trc cu trc tinh th h trc thoi. Kch thc ht trung bnh v hng s mng c tnh ton bng phn mm WINFIT v FULLPROF. Cc kt qu tnh ton c lit k trong bng 4.6. Bn knh ion ca cc nguyn t h lantanoit gim dn t La ti Gd (rLa3+ = 0,118 nm; rNd3+ = 0,112 nm; rSm3+ = 0,109 nm; rGd3+ = 0,106 nm [49]), do vy cc hng s mng ca cc oxit ny cng gim dn.

Bng 4.6. Hng s mng, kch thc ht ca cc mu:

Oxit LaFe0,6Co0,4O3 NdFe0,6Co0,4O3 SmFe0,6Co0,4O3 GdFe0,6Co0,4O3 a () 5,499 5,499 5,353 5,319 b () 7,759 7,641 7,628 7,591 c () 5,474 5,371 5,494 5,532 D (nm) 9,6 10,7 8,7 9,6

4.4.2. Hnh thi hc b mt ca h mu AFe0,6Co0,4O3

Hnh 4.12. Gin nhiu x tia X ca h AFe0,6Co0,4O3 (A=La, Nd, Sm v Gd).

Hnh 4.13. nh SEM ca mu GdFe0,6Co0,4O3.

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Hnh thi hc ca cc oxit ny cng c thc hin bng nh SEM. Tt c cc mu u c kch thc ht khong 50 nm trong khi kch thc tinh th tnh ton c khong 10 nm. iu ny l do s t m ca cc ht tinh th. Hnh 4.13 minh ha vi cu trc ca oxit GdFe0,6Co0,4O3. Kt qu SEM cho thy cc ht kh ng u v cc mu ny u thch hp cho ch to cm bin.

4.5. Kt lun chng

Trong chng ny, chng ti trnh by phng php sol-gel to phc trong vic tng hp cc vt liu oxit pervoskit, cc yu t nh hng ln vi cu trc v kch thc ht ca vt liu. Cc vt liu oxit perovskit trong lun n c ch to theo cng mt ch cng ngh. Cc kt qu thu c c th tm tt nh sau: Vt liu LaFeO3 vi t l mol La:Fe:CA = 1:1:4; CA/EG = 4:6 v lng cht phn tn etanol 75% th tch cho mu bt LaFeO3 c kch thc ht nh v ng u nht. Kch thc ht ti u l 12 nm. Cc h vt liu LaBO3 (B= Fe, Co, Ni v Mn); LaFe1-xCoxO3- (0,0 x 1,0) v AFe0,6Co0,4O3 (A l La, Sm, Nd v Gd) c ch to thnh cng. Nghin cu vi cu trc v hnh thi hc cc oxit perovskit cho thy cc mu u n pha tinh th, kch thc ht nh, c nano mt, din tch b mt ln, thch hp cho ch to cm bin nhy kh.

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CHNG 5

CH TO V NGHIN CU CC C TRNG CA CM BIN NHY HI CN

Cc cm bin nhy hi cn c nghin cu, ch to trong phng th nghim cng nh c thng mi ha trn th trng hin nay ch yu l cm bin in ha da trn nn cc oxit kim loi pha rn. Cc cm bin in ha c u im l c chnh xc cao, chn lc tt. Tuy nhin, n i hi cng sut hot ng ln, nhy khng cao, thi gian p ng di v tui th ngn. Trong khi cc cm bin da trn oxit kim loi bn dn li c nhy cao (t nng vi ppm n vi chc phn trm), p ng nhanh, d ch to, kch thc gn nh, bn cao v tiu th t nng lng. Tuy nhin, loi cm bin ny cng c mt s nhc im cn khc phc l chn lc km v ph thuc mnh vo cc iu kin mi trng nh nhit v m. Mt khc, hin tng gi ha v hin tng u c xc tc cng lm nh hng n bn, chnh xc ca cm bin. Trong chng ny chng ti s trnh by v cm bin mng dy v kho st cc c trng nhy kh ca cc h vt liu oxit perovkit nh: h LaFeO3; h LaFe1xCoxO3

(vi 0,0 x 1,0); h AFe0,6Co0,4O3 (vi A l cc nguyn t t him La,

Sm, Nd v Gd). Cng ngh ch to cm bin nhy hi cn da trn cc vt liu ny v cc thng s nh nhy n nh ca cm bin sau khi c ch to cng s c kho st v tho lun trong chng ny.

5.1. Ch to cm bin
a s thit b o kh s dng cm bin c ng dng trong cng nghip u s dng cng ngh mng
(a) (b) Hnh 5.1. Mt ct ngang hai cu hnh cm bin.

dy do chng d ch to, d pha tp v c tui th tng i cao.

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T thc t , chng ti la chn cng ngh ch to cm bin mng dy. Cu trc ca cm bin bao gm mng nhy kh, in cc v l vi nhit u c tch hp trn phng. Do cm bin lm vic nhit cao nn l vi nhit phi c thit k ngay trn cm bin. L vi nhit c th c t trn mt i din (hnh 5.1a) hoc trn cng mt mt vi mng nhy kh (hnh 5.1b). Trng hp u tin, bin thin nhit trn dn ti lm tng cng sut tiu th ca cm bin. Trng hp th hai, do l vi nhit nm trn cng mt mt vi mng nhy kh nn cu to phc tp hn v ch to cng phc tp hn. Do vy, chng ti la chn cch ch to th nht. Mng nhy kh c th c ch to bng nhiu phng php nh in li, phun ph hoc nhng ph. Trong lun n ny, chng ti s dng phng php in li. Cm bin c thit k vi s c trnh by trn hnh 5.2 v c ch to bng phng php in li.

Hnh 5.2. Bn thit k mt n in li cho cm bin.

5.1.1. H in li
H in li c s dng nh hnh 5.3. H bao gm b phn g gm, gi gm nh bm ht chn khng; b phn di chuyn gm theo 2 chiu; li tch hp mt n. Li thp khng g tch hp mt n, mt li 400/25 m c thit k v ch to nh hnh 5.4.

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5.1.2. gm
Do cm bin thng lm vic nhit cao nn ca cm bin phi tha mn cc iu kin kht khe sau: cch in, chu nhit, dn nhit tt, khng phn ng vi kh cng nh vt liu nhy kh. Cc silic v gm p ng tt cc yu cu trn. Tuy nhin, nhit lm vic ca silic t c ti a l 400 oC, trong khi gm c th t n 700 oC. C rt nhiu loi gm c s dng nh: steatit (steatite), cocierit (cordierite),
Hnh 5.4. nh li tch hp mt n. Hnh 5.3. H in li

oxit ziconi (zirconia), oxit nhm, nhng cc gm trn nn oxit nhm thng c nh gi cao hn do n nh v bn ca n. Hn na, lin kt gia nhm v oxy to nn Al2O3 l mt trong nhng vt liu bn vng v tr nht cho ng dng trong mi trng khc nghit. Bn cnh Al2O3 c thng mi ha nhiu dng, hnh dng khc nhau hn. Do vy, gm trn nn oxit nhm c dng phng c la chn bi s tin li trong vic ch to in cc, l vi nhit v mng nhy kh bng k thut in li. gm c s dng trong vic ch to cm bin c kch thc: 25,4 x 25,4 mm (1,0 x 1,0 inch2), dy 0,25 mm mua ca hng AdValue Technology (M). Mt tm gm nh vy cho php ch to c 12 cm bin, kch thc mi cm bin l 8,46 x 6,35 mm.
2

5.1.3. Ch to h v qu trnh in li
H cha vt liu in li c ch to bng cch trn mu bt vi cht ph gia (bao gm: cht chng keo t propadyol hoc terpineol v cht kt dnh hu c etyl silicat). Hn hp ny s c in ln .

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Qu trnh in li c thc hin nhit phng, gm c t ln b g v c gi c nh nh bm ht chn khng. t li ln trn , dng tha nh cho mt lng c nh h ln li, dng con ln teflon dn u h ln khp mt n. Sau , nhc li ra, tip tc gi cht gm in li 30 pht mng c phng. Nng nhit t nhit phng ti 125 oC, tc gia nhit 5 oC/pht, gi nhit ny trong 15 pht lm kh mng, sau nng nhit tip ti khong nhit t 600 n 1000 oC (ty loi vt liu) v gi nhit ny trong 30 pht phn hy cc cht hu c, cc ht vt liu lin kt vi nhau v vi . Cui cng, n c h nhit t t v nhit phng v kt thc qu trnh . Bng phng php in li ny, cho php ch to cc mng cm bin vi dy t vi micro mt n 100 micro mt, ty thuc vo mt li, nht ca h v khong cch gia li v oxit nhm.
Hnh 5.5. nh l vi nhit c ch to bng phng php in li trn gm.

5.1.4. Ch to l vi nhit
Vt liu lm l vi nhit thng l Pt hay hp kim Ni-Cr. Vic n nh nhit ca l vi nhit rt quan trng trong ch to cm bin do lin quan n nhit lm vic ca cm bin. L vi nhit phi m bo mng nhy kh c gia nhit ng u vi s tiu hao nng lng l t nht. y, chng ti la chn vt liu ch to l vi nhit l platin. H platin thng mi ESL 5545 (Electro-Science, M) c s dng v theo khuyn ngh ca hng sn xut, h ny c s dng trn Al2O3 96% thch hp nht lm l vi nhit v nhit in tr. Hnh nh l vi nhit platin c ch to bng phng php in li ln n gm Al2O3 c trnh by trn hnh 5.5. Qu trnh kho st nhit trn b mt cm bin ph thuc th ngun nui c thc hin nh sau: t cm bin trong bung o nh, th tch 5 dm3, mc hai u ca l vi nhit vi ngun mt chiu, t cp nhit K st b mt sau ca gm,

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tng dn th t 0,25 n 5,0 V, bc thay i in p l 0,25 V. Dng tng ng c o bng ng h hin s. S ph thuc ca th ngun nui vo s bin i nhit v cng sut tiu th ca cm bin ti mi nhit lm vic c biu din trn hnh 5.6. Nhn thy rng cng sut tiu th Hnh 5.6. S ph thuc th nui vo nhit l vi ca cm bin ph thuc mt cch tuyn tnh vo s bin i nhit ca l vi nhit. Cng sut tiu th tng theo nhit . S ph thuc ny c th biu din mt cch gn ng theo phng trnh tuyn tnh c dng: P = 0,004 * Toper- 0,221 y P l cng sut tiu th ca cm bin v Toper l nhit lm vic. Cc kt qu kho st v s n nh nhit cm bin theo thi gian c trnh by trn hnh 5.7. Nhn thy rng, nhit gn 300 oC tng ng vi in p ngun nui l 3 V, cm bin t nhit n nh sau 7 pht. Trong khi nhit gn 450 oC tng ng vi in p ngun nui l 4,5 V, thi gian t n nh v nhit phi mt gn 15 pht.
Hnh 5.7. S n nh nhit cm bin theo thi gian.
nhit; c trng cng sut ca l vi nhit.

5.1.5. Ch to in cc cm bin
Cm bin kh i hi cc in cc kim loi phi tip xc in tt, chu c nhit cao trong thi gian di. Cc vt liu in tr thp nh vng v platin thng hay c s dng lm in cc nht. Vic la chn cc vt liu ny cng

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bi l do thc t l chng khng phn ng vi cc cht kh cn o v khng b oxy ha. Tuy nhin, trong trng hp cm bin kh thng hot ng nhit cao nn chng ti s dng in cc platin lm gim s gi ha sau thi gian s dng di. Qu trnh ch to in cc bng phng php in li c trnh by phn trn. Hnh 5.8a l hnh nh minh ha cc in cc sau khi gm Al2O3.
a) (b) Hnh 5.8. (a) - nh in cc cm bin ch to c ch to v c in li ln bng phng php in li; (b) nh mng nhy kh tch hp in cc, l vi nhit trn 2 mt.

5.1.6. Ch to mng nhy kh

ch to mng nhy kh cho cm bin, chng ti s dng cc loi bt oxit perovskit ch to bng phng php sol-gel to phc (chng 4). Cc mu bt c trn vi cht chng keo t, cht kt dnh hu c theo mt t l ph hp to thnh hn hp dng st (gi l h). Sau chng c ph ln in cc bng k thut in li ch to cm bin. Ch mng tng t nh trong phn 5.1.3. Hnh nh mng nhy kh LaFeO3 c in li ln Al2O3 tch hp in cc, l vi nhit c minh ha trn Hnh 5.10. Cm bin nhy hi cn c ch to hon chnh. hnh 5.8b. Mng nhy kh thu c kh phng v c chiu dy khong 40 m (hnh 5.9).
Hnh 5.9. Chiu dy mng nhy kh LaFeO3.
40,3 m

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in cc, l vi nhit u l platin nn dy dn ca cm bin chng ti cng s dng dy platin ca hng Good Fellow (Anh Quc). Vic hn dy dn platin vi in cc hoc l vi nhit c chng ti s dng phng php hn p nhit v hn h quang. Cc chp cm bin sau khi ch to c kim tra, phn loi, ng v hon chnh. Hnh 5.10 minh ha chp cm bin nhy hi cn (hnh bn tri) v cm bin ng v hon chnh.

5.2. H cm bin perovskit LaBO3 (B = Fe, Co, Mn v Ni)

Cc vt liu h LaBO3 (B = Fe, Co, Mn v Ni) c tng hp bng phng php sol - gel vi cc c tnh vi cu trc v hnh thi hc nh c trnh by trong chng 4, s c s dng ch to cc cm bin kh. Cc php o c trng nhy kh ca cc cm bin ny c thc hin ti Phng Cm bin v Thit b o kh, Vin Khoa hc Vt liu. Cc cm bin c mc theo s nh hnh 3.10 (xem chng 3). Tn hiu ly ra c ghi nhn lin tc tng giy bng ng h vn nng Keithley model DMM 2700 ghp ni vi my tnh.
Hnh 5.11. S ph thuc vo nhit ca dn cm bin trn c s vt liu LaBO3.

5.2.1. S ph thuc ca in tr cm bin vo nhit

Trong cc php o in, mi trng kho st c la chn c m t 90 n 95% RH,
Hnh 5.12. S ph thuc vo thng s nhit (1000/T) ca hm ln().

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tng ng vi m trong hi th ngi nhm hng ti ng dng cc cm bin ny trong thit b o nng cn trong hi th. S ph thuc vo nhit ca dn cm bin trong mi trng khng kh c m t 90 n 95% RH c biu din trn hnh 5.11. Cc kt qu thu c ch ra rng, cc vt liu LaBO3 (B = Fe, Co v Mn) c c trng bi tnh dn in ca cht bn dn loi p. Nng ht ti tng dn vi s tng nhit . Trong khi h vt liu LaNiO3 li th hin c trng ca tnh dn in kim loi. Ti nhit trn 300 oC, dn in ca LaCoO3 v LaMnO3 c s thay i t ngt, v ti gi tr 500 oC dn in ca LaCoO3 ln gp hai ln so vi dn ca h LaMnO3. dn ca cc cht bn dn loi ny c th biu din theo biu thc hm m sau:

~ 0* exp (-Ea/kT)

(5.1)

y, l dn ca cht bn dn; 0 l h s ph thuc vo bn cht vt liu; Ea l nng lng hot ha; k l hng s Boltzmann v T l nhit . Gi tr nng lng hot ha ca cc mu c th xc nh mt cch gin tip thng qua th biu din s ph thuc ca hm ln() vo tham s c trng cho nhit 1000/T (xem hnh 5.12). Cc kt qu thu c ch ra rng, trong h LaCoO3 c tn ti hai gi tr nng lng hot ha khc nhau, trong vng nhit di 150 oC c gi tr bng 0,174 eV. Trong khi vng nhit trn 150 oC, nng lng hot ha ca h cho gi tr bng 0,521 eV. Nguyn nhn ca s thay i ti vng nhit 150 oC ny c th l do xut hin s chuyn trng thi spin ca nguyn t kim loi chuyn tip coban. Mt phn trng thi spin thp ca cc ion Co3+ chuyn sang trng thi spin cao. Hoc c th do mt phn nh Co2+ cn d trong mu c oxy ha hon ton thnh Co3+ bi cc phn t O- c hp ph trn b mt - iu ny c kim chng bi lng oxy d tn ti trong mu thu c t kt qu xc nh thnh phn oxy (xem chng 4). Bn cnh , gi tr nng lng hot ha ca mu LaMnO3 v LaFeO3 thu c t phng php lm khp ny tng ng s l: 0,328 v 0,561 eV. T cc kt qu thu c trn, dn in ca h LaBO3 gim dn theo th t: LaCoO3 > LaMnO3 > LaFeO3. Cc kt qu thu c l kh ph hp vi cc kt qu c cng b trc y [81].

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i vi h LaFeO3, trong vng nhit thp (di 100 oC), khi nhit tng in tr ca vt liu tng theo. Nguyn nhn ca s tng in tr trong vng ny c th l do ti vng nhit thp, vt liu hp ph hi nc trn b mt to thnh cc tm hot ng. Cc tm ny hot ng nh cc tm donor tng tc vi cc l trng v cc ion oxy b mt (O-s) to thnh cc nhm hyroxyl OH trn b mt lm gim dn ca vt liu (tc l lm tng in tr). C ch hp ph hi nc b mt vng nhit thp ny c th c minh ha trn hnh 5.13 v phng trnh phn ng c biu din di dng sau:
OH2O + B(n-1)+ Bn+
o

Hnh 5.13. Gin minh ha c ch hp ph hi nc trn b mt cm bin LaFeO3.

H < 100 oC > 100 C

o

OH Bn+

O Bn+

(5.2)

Ti vng nhit trn 100 C, hi nc c gii phng ht, khi dn ca vt liu bt u thay i nh mt cht bn dn loi p. Khi nhit trn 260 oC, dn ca vt liu LaFeO3 thay i mt cch t ngt. S thay i ca in tr v nhy ca cm bin trong mi trng vi s c mt ca hi cn cng c cp n. Mi trng kho st cho trng hp ny l mi trng kh th c m t 90 n 95% RH v nng hi etanol l 0,4 mg/l (y l nng cn gii hn i vi ngi iu khin phng tin giao thng trn

ng, Lut Giao thng ng b Vit Nam nm 2001, nm 2008 iu chnh kht khe hn thnh 0,25 miligam/1lt kh th). nhy ca cm bin c nh ngha l
t s in tr ca vt liu c o trong mi trng kh cn pht hin (Rgas) v trong mi trng khng kh (Rair) ti cng nhit . Mi lin h gia nhy v in tr in tr ca cm bin trong cc mi trng khc nhau c biu din di dng biu thc sau:

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donhay LF O

S=R

gas

air

(5.3)

Vi Rgas v Rair l in tr cm bin trong mi trng c etanol v trong khng kh. Cc kt qu kho st s ph thuc nhit ca nhy cm bin trong mi trng cha etanol 0,39 mg/l v trong khng kh m c biu din trn hnh 5.14. Trong vng nhit kho st, nhy hi cn
Hnh 5.14. nhy cm bin LaBO3 (B = Fe, Co, Mn v Ni) ph thuc vo nhit trong mi trng cha etanol 0,39 mg/l.

ca cc cm bin c ch to t cc vt liu LaMnO3 v LaNiO3 l khng ng k. nhy ca cm bin c ch to t vt liu LaCoO3 t gi tr l 2,7 nhit 150 oC. Trong khi , cc cm bin da trn nn LaFeO3 cho gi tr nhy ln nht l 27,8 vng nhit 260 oC. Trong cc vng nhit di 150
o

C v trn 300 oC nhy ca cm bin l khng ng k. S ph thuc ca

nhy cm bin ny vo nng hi cn cng nhit hot ng 260 oC cng c nghin cu. Cc nng cn c chn kho st nm trong di t 0,00 n 2,00 mg/l. Cc kt qu thu c v s ph thuc ca nhy vo nng hi cn c trnh by trn hnh 5.15. Ta nhn thy rng, nhy ca cm bin nh hm ph thuc vo nng cn c trong mi trng kho st, nhy ca cm bin tng vi s tng ca nng cn. S ph thuc ny c th c lm khp v biu din theo hm c dng: S = * Cetanol. Vi, v l cc tham s hm m. Nh chng ti cp trong chng mt v chng hai, cc vt liu LaMnO3, LaCoO3 v LaNiO3 u cho gi tr hp ph O2 v hot tnh xc tc vi CO cao hn rt nhu so vi oxit LaFeO3. Bn cnh , theo cc kt qu kho st thu c vi etanol, oxit LaFeO3 li cho nhy ln nht trong khi cc oxit khc cho nhy vi etanol l khng ng k. Nguyn nhn ca s khc bit ny c th l do cc oxit LaBO3 (B = Mn, Co, Ni) c hot tnh xc tc cao, kh etanol b

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oxy ha gn nh hon ton vng pha ngoi v ch mt lng nh c th khuch tn vo trong khi n vng trong cng ti cc in cc c nh x dn n nhy rt thp. Oxit LaFeO3 c hot tnh xc tc trung bnh, mt lng ng k kh etanol c th thm vo vng trong cng cho nhy cao hn. Ngc li, cm bin c hot tnh khng ng k th hin nhy thp do s tiu th oxy hp ph thp vng trong cng thay v hu nh kh thm vo hon ton. Cc kt qu kho st s gii hp oxy ca cc vt liu ny cng khng nh rng, oxit LaMnO3 cho nh gii hp 1 v 2, khng c nh gii hp . Ngha l khng c s khuch tn oxy vo trong khi. nh gii hp (oxy khi) ca cc oxit LaCoO3 v LaNiO3 l rt thp so vi cc nh gii hp 1 v 2. Trong khi oxit perovskit LaFeO3 cho nh gii hp cc i nh 2 v l ln nht. Cc gii thch tng minh cho s khc bit v nhy vi etanol ca cc oxit perovskit LaBO3 (B = Mn, Fe, Co, Ni) s c trnh by trong phn tip theo.

5.2.2. Thi gian p v thi gian hi phc ca cm bin LaFeO3

Vi cc c tnh u vit v nhy vng nhit lm vic 260
o

C, vt liu LaFeO3 (LFO) s c Hnh 5.15. S thay i nhy cm bin LFO

theo nng hi etanol.

la chn ch to cm bin nhy hi

cn. Cc tham s v cc tiu ch cn thit cho mt cm bin nh thi gian p, thi gian hi phc, n nh v chn lc ca cm bin s c trnh by chi tit di y. Thi gian p ng kh l khong thi gian cn thit in tr ca cm bin t 90% gi tr cc i khi c t trong mi trng c cha kh cn pht hin. Thi gian hi phc l khong thi gian cn thit in tr ca cm bin tr v t gi tr cc i n 10% gi tr khi kh i qua.

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o c trng hi p ca cm bin, cc cm bin LFO c thit k t trong mt bung o nh vi th tch 0,5 dm3, tc thi kh 1,0 l/pht. H thng cung cp kh cho bung o vi thnh phn khng kh cha hi cn hoc khng cha hi cn c m t 90 n 95% RH. c trng hi p ca cm bin LFO 260 oC c trnh by
Hnh 5.16. c trng hi p ca cm bin LFO ti 260 oC, nng cn 0,39 mg/l.

trn hnh 5.16. Cc kt qu thu c ch ra rng, thi gian p l 30 giy trong khi thi gian hi phc ca cm bin l 80 giy.

5.2.3. chn lc ca cm bin

Mt tham s quan trng khc i vi cc cm bin kh l tnh chn lc ca chng. V mt l thuyt, cm bin c chn lc tt vi mt kh ngha l n cho nhy cao i vi mt cht kh v km nhy vi cc kh khc cng tn ti trong mi trng kim tra. Cc cm bin c ch to trn nn LaFeO3 s c kim tra tnh chn lc vi cc cht kh th khc nhau. Cc cht kh tham gia kho st bao gm: metanol, axeton v cacbonic. Nng kho st tiu chun l: 0,39 mg/l; nhit lm vic: 260 oC. S ph thuc ca nhy cm bin vo nhit trong cc mi trng kh cn pht hin khc nhau c minh ha trn hnh 5.17. Cc kt qu thu c ch ra rng, nhy ca cm bin i vi cn cho gi tr ln nht nhit 260 oC (Smax = 27,8), vi metanol cho gi tr cc i nhit 250 oC (Smax = 15,8), vi axeton t gi tr ln nht (Smax = 18,2) 250 oC v cm bin gn nh khng nhy vi s c mt ca kh CO2. nhit lm vic 260 oC, nhy ca cm bin vi cc kh etanol, metanol v axeton ln lt l 27,8 ; 10,5 v 12,5. H s chn lc ca cn so vi cc kh th khc c nh ngha theo biu thc: Ketanol/x = Setanol/Sx, trong Setanol v Sx l nhy ca cn v ca kh th khc cng nhit hot ng v nng cn kho st. Ti nhit 260 oC, h s

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Ketanol/metanol c gi tr bng 2,65 v Ketanol/axeton c gi tr l 2,22. Trn thc t, tiu ch cng ngh cho mt cm bin nhy hi cn i hi h s chn lc Ketanol/x phi ln hn hoc bng 5 mi c xem nh cm bin nhy vi etanol m khng nhy vi kh khc. Cc kt qu thu c t s tnh ton v chn lc ca cn vi cc kh khc c trnh by trn hnh 5.18. Vic cm bin khng nhy vi kh cacbonic c xem nh l mt thun li trong vic s dng cm bin ch to thit b o nng cn trong hi th v kh cacbonic chim lng ln trong hi th ngi. Mt khc, cm bin khng ch c nhy cao vi cn, m cn kh nhy vi vi metanol (ng ng ca etanol) v axeton.
Hnh 5.18. nhy ca cc cm bin LaFeO3 vi etanol, metanol, axeton. Hnh 5.17. S ph thuc nhit ca nhy cm bin LFO vi cc kh etanol; metanol; axeton v cacbonic nng 0,39 mg/l.

iu ny c th xem nh l mt bt li cho vic s dng cm bin nu nh trong mi trng kho st c tham gia ca cc kh ny cng vi etanol, s lm nh hng trc tip n kt qu o. T kt qu c trnh by trn hnh 5.18 cho ta mt gi l, nu nng nhit lm vic ca cm bin t 260 oC ln 270 oC, khi nhy ca cm bin vi cc kh etanol s gim xung 23,7, trong khi vi metanol v axeton ln lt l 4,1 v 5,2. H s chn lc Ketanol/x trong trng hp ny c gi tr 5,78 v 4,56 tng ng vi metanol v axeton. Nh vy ti 270 oC nh hng ca metanol v axeton ln nhy ca cm bin s gim v c th xem nh y l nhit

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lm vic ti u cho cm bin s dng vt liu LaFeO3. Mt lu na l y l kt qu o nhy cm bin cc nng metanol v axeton l 0,39 mg/l. Khi nng cc kh ny c mt nh hn th chnh xc ca thit b o s c ci thin hn rt nhiu. Tuy nhin, khi nng nhit lm vic ca cm bin cng ng ngha vi vic tng cng sut tiu th ca cm bin. Nu chuyn nhit hot ng ca cm bin ln 220 oC nhm lm gim nhit hot ng ng thi gim c cng sut tiu th ca cm bin. Ti 220 oC, Setanol bng 23.02 th Smetanol bng 6,5, Saxeton bng 3,7 tc l Ketanol/metanol bng 6,22 v Ketanol/axeton bng 3,54 li khng tha mn iu kin K ln hn 5.

5.2.4. n nh ca cm bin
Vi mc ch ng dng cm bin vo vic ch to thit b o nng hi cn trong hi th, tnh n nh ca cm bin cng rt quan trng cn c kho st. S n nh ca cm bin trn nn LaFeO3 (LFO) c kim tra theo cc quy trnh o nh sau: Mi ngy o li cm bin hai ln vo cc thi im 10 gi sng v 4 gi chiu trong khng kh v nng hi cn l 0,39 mg/l, tc thi kh 1,0 l/pht. Trc mi ln o u lm mi b mt cm bin bng cch gia nhit cm bin 400 oC trong 1 pht, sau lm ngui cm bin v nhit phng ri mi tin hnh o in tr cm bin trong mi trng khng kh v mi trng cha cn 0,39 mg/l. Kt qu kho st n nh thi gian ngn (khong 01 thng) v thi gian di (06 thng). Cc kt qu kho st v n nh ca cm bin theo chu trnh trn c trnh by trn hnh 5.19. Nhn thy rng cm bin LFO cho n nh thi gian ngn kh tt, cc kt qu o dao ng xung quanh gi tr trung bnh cha n 5%, trong khi n nh thi gian di, gi tr o dao ng ln hn, nht l khi o trong mi trng cha hi cn c gi tr ln n 10%.

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Hnh 5.19. n nh thi gian ngn ca cm bin LFO (a); v n nh thi gian di (b) trong mi trng hi cn 0,39 mg/l.

5.3. H cm bin perovskit LaFe1-xCoxO3 (0,0 x 1,0)

Hot tnh xc tc ca cc oxit perovskit lin quan mt thit n linh ng oxy (trn b mt v trong khi) v cc tnh cht oxy ha kh ca cc kim loi chuyn tip. Cc ha tr phc tp ca cc ion kim loi truyn tip v tr B trong phi tr to ra cc hiu ng d hoc thiu oxy nh c trnh by phn trn i vi cc h LaBO3 (B = Mn, Fe, Co v Ni). Hn na, cc ion Co3+ thng tn ti trng thi spin thp trong h LaBO3. iu ny gi rng, nu pha tp tng phn Co vo v tr Fe trong h LaFeO3 s khng ch lm bin i ha tr ca cc kim loi chuyn tip v tr B v nh hng n linh ng ca oxy, m cn lm thay i tnh dn in v hiu ng xc tc ca h. Cc kt qu kho st s nh hng ca hm lng x ca nguyn t thay th Co vo tnh cht in v hot tnh xc tc ca h LaFe1-xCoxO3 (0,0 x 1,0) s c tho lun chi tit trong cc phn di y.

5.3.1. Kt qu o in tr ca cm bin theo nhit

S ph thuc vo nhit ca dn cm bin da trn nn vt liu LaFe1xCoxO3

(0,1 x 0,4) trong mi trng khng kh m c trnh by trong hnh

5.20. Cc kt qu thu c ch ra rng, cc mu u th hin tnh dn ca bn dn loi p. Khi nng pha tp thay i, khng lm thay i bn cht dn ca vt liu ban u. vng nhit di 100 oC, bn cht dn ca cc cm bin ny c c trng ging nh h vt liu LaFeO3. Ngha l in tr ca cm bin tng vi s tng

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ca nhit . Nguyn nhn ca s tng in tr trong vng ny c th l do ti vng nhit thp b mt vt liu hp ph hi nc to thnh cc tm hot ng. Cc tm ny hot ng nh cc tm donor tng tc vi cc l trng v cc ion oxy b mt (O-s) to thnh cc nhm hyroxyl OH trn b mt lm gim dn ca vt liu. n hn 100 oC, hi nc c gii phng ht, khi dn ca vt liu bt u thay i nh mt cht bn dn loi p. Ti cc nhit 260, 252; 225 v 200 oC tng ng vi vi cc vt liu c thnh phn thay th Co l 0,1; 0,2; 0,3 v 0,4, dn in ca cm bin c s thay i t ngt. C ch dn theo m hnh
Hnh 5.21. S ph thuc nhit ca nhy cm bin LFC vi nng etanol 0,39 mg/l Hnh 5.20. S ph thuc nhit ca dn cm bin LaFe1-xCoxO3 (0,1 x 0,4).

khong nhy bin thin Mott theo quy lut ~ f(1/T), ng trong khong nhit kho st (t 100 n 500 oC). T ng cong s ph thuc ca hm ln(1/R) vo tham s nhit 1000/T, cho php xc nh c nng lng hot ha ca cc mu kho st. Cc mu vi nng thay th ln hn hoc bng 0,5, quy lut v s ph thuc ca dn vo nhit ca cc mu ny hu nh khng thay i. dn ca cc mu ny cng bc vi h LaCoO3. S ph thuc ca nhy hi cn nng 0,39 mg/l ca cc cm bin LFC theo nhit hot ng c trnh by trn hnh 5.21. Cc kt qu cho thy cc cm bin u c mt gi tr nhy ln nht (Smax) trong khong nhit t 50

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n 450 oC. Tuy nhin, vi thnh phn thay th Co trong vt liu khc nhau cc cm bin cho gi tr cc i khc nhau cc nhit hot ng khc nhau. S khc nhau v nhy v nhit hot ng ca cc cm bin h LFC c biu din trn hnh 5.22. Nhn thy rng, khi nng thay th Co nh hn 0,4 nhy ca cm bin tng vi s tng ca nng thay th. nhy ca cm bin t gi tr ln nht khi hm lng thay th t gi tr bng 0,4. Hnh 5.22. nhy ln nht (Smax) v nhit Khi nng coban ln hn 0,4, nhy gim dn theo s tng ca ca nng thay th. Mt khc nhit hot ng cho gi tr nhy cc i gim dn theo s tng ca nng thay th (hnh 5.22). Tm li, trong h vt liu LaFe1-xCoxO3 (0,0 x 1,0), vt liu LaFe0,6Co0,4O3 cho cc c tnh ti u nht c v Hnh 5.23. S thay i nhy cm bin LFC4 theo nng hi cn. nhy (Smax = 52) v nhit hot ng (T = 228 oC) trong vic ng dng ch to cm bin. Cc tham s c trng cho cm bin nh thi gian p, thi gian hi phc v chn lc ca cc cm bin c ch to trn nn vt liu ny s c tho lun chi tit trong cc tiu mc di y. S ph thuc ca nhy cm bin trn nn vt liu LaFe0,6Co0,4O3 (LFC4) vo nng hi cn ti nhit hot ng 228 oC cng c nghin cu. Cc nng cn c chn kho st nm trong di 0,00 n 2,00 mg/l. Cc kt qu thu c v s ph thuc ny c trnh by trn hnh 5.23. Ta nhn thy rng, nhy
hot ng ph thuc hm lng coban (x).

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ca cm bin nh hm ph thuc vo nng cn c trong mi trng kho st, nhy ca cm bin tng vi s tng ca nng cn. S ph thuc ny c th c lm khp v biu din theo hm m c dng: S = Cetanol, ging nh h LaFeO3 c kho st trc y.
Hnh 5.24. c trng hi p ca cm bin LFC4 ti 228oC

5.3.2. Thi gian p v thi gian hi phc ca cm bin

Qu trnh kho st c trng hi p v thi gian hi phc ca cc cm bin LFC4 c tin hnh ging nh vi cc cm bin LFO. Ch c s khc bit duy nht nhit hot ng ca cm bin l 228 oC. Cc kt qu kho st thi gian p v thi gian hi phc ca cm bin c trnh by trn hnh 5.24. Cc kt qu thu c ch ra rng, thi gian p l 22 giy trong khi thi gian hi phc ca cm bin l 78 giy. Cc thng s ny tha mn iu kin t ra i vi mt cm bin kh trong vic s dng ch to thit b o nng cn trong hi th ngi.

5.3.3. chn lc ca cm bin

Hnh 5.25 biu din s ph thuc nhit ca nhy cm bin vi cc kh etanol; metanol; axeton v cacbonic nng 0,39 mg/l. Kt qu cho thy cm bin nhy hi cn nht nhit 228 oC, gi tr Smax t gi tr bng 51,1. Trong khi cho nhy metanol ln nht (Smax = 23,7) v nhy axeton ln nht (Smax = 26,5) 220 oC v cm bin gn nh khng
Hnh 5.25. S ph thuc nhit ca nhy cm bin LFC4 vi cc kh etanol; metanol; axeton v cacbonic (0,39 mg/l)

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nhy vi s c mt ca kh CO2. Nu metanol hay axeton cng c mt ng thi vi etanol th chng nh hng khng nh ln nhy cn ca cm bin. Qua dng iu ng cong s ph thuc nhy vo nhit cho ta nhn xt rng, khng ch nh hng ny chng ta c th chn nhit hot ng ca cm bin cao hn, tc l nhy cn gim nhng cng lm gim nhy xin vi metanol hay axeton.

5.3.4. n nh ca cm bin
Kt qu kho st n nh thi gian di (06 thng) c minh ha trong hnh 5.26. Chng ti nhn thy rng cm bin LFC4 cho n nh kh tt, cc kt qu o dao ng xung quanh gi tr trung bnh cha n 5%.

5.4. H cm bin perovskit AFe0,6Co0,4O3 (A = La, Sm, Nd v Gd)

Chng ta bit khi LFO pha tp Co mc 40% (LFC4) cho nhy cn ln nht. Nhm hiu r hn v vai tr ca nguyn t v tr A ln cc c trng nhy hi cn ca cm bin, chng ti la chn nng pha tp Co ny v thay v tr ca La bng mt s nguyn t t him khc v kho st cc c trng ca cm bin.
Hnh 5.26. n nh ca cm bin LFC4

5.4.1.in tr ca cm bin
S ph thuc ca nghch o in tr (1/R) vo nhit kho st ca cc vt liu AFe0,6Co0,4O3 (A = La, Sm, Nd v Gd) trong mi trng khng kh m c biu din trn hnh 5.27. Cc kt qu thu c ch ra Hnh 5.27. S ph thuc nhit ca dn cm bin da trn vt liu AFe0,6Co0,4O3 rng, khi thay th La bng cc nguyn

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t t him khc bn cht dn ca vt liu khng thay i. Cc mu kho st u th hin tnh dn ca cht bn dn loi p. Bc ln ca in tr ca cc mu l cng bc. Trong h cha La cho dn ln nht, ngc li dn nh nht xut hin h cha Gd. C th sp xp tnh dn in ca h vt liu AFe0,6Co0,4O3 (A = La, Gd, Nd v Sm) AFC4 theo th t gim dn v dn in theo th t sau: LaFC4 > SmFC4 > NdFC4 > GdFC4. dn ca cc mu kho st u thay i t ngt ti nhit 228 oC.

Hnh 5.28. S ph thuc nhit ca nhy cm bin AFC4 vi nng etanol 0,39 mg/l.

Hnh 5.29. S thay i nhy cm bin AFC4 theo nng hi cn.

nhy hi cn ca cc vt liu ny trong mi trng cha nng hi cn 0,39 mg/l cng c kho st. S ph thuc ca nhy vo nhit ca cc mu nghin cu c trnh by trn hnh 5.28. Kt qu thu c ch ra rng, cc vt liu kho st u cho gi tr nhy ln nht cng mt nhit 228 oC. Tuy nhin, s thay th cc nguyn t t him khc nhau cho nhy khc nhau. Khi A l Sm nhy cho gi tr Smax ln nht, v A l La cho gi tr Smax nh nht (xem hnh 5.28). iu ny cho thy cu hnh in t 4f ca cc nguyn t t him cng nh hng n nhy ca vt liu. S ph thuc nhy vo nng cn ca cc vt liu AFC4 (A = La, Gd, Nd v Sm) nhit hot ng 228 oC c trnh by trn hnh 5.29. Nhn thy rng quy lut ph thuc ca nhy vo nng cn trong mi trng kho st l cng quy lut. Ch c s khc bit duy nht l ln ca nhy hi cn.

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5.4.2. Thi gian p v thi gian hi phc ca cm bin AFC4

Kt qu o thi gian p ng v thi gian hi phc ca cc cm bin AFC4 c lit k trong bng 5.1. Nh vy cc cm bin AFC4 u cho thi gian p v thi gian hi phc khng khc nhau nhiu, trong cm bin SmFC4 cho thi gian p v thi gian hi phc nhanh hn c.

Bng 5.1. Thi gian p (tres) v thi gian hi phc (trev) ca cc cm bin AFC4 (A = La, Gd, Nd v Sm) Cm bin tres (s) trev (s) LaFC4 22 78 GdFC4 18 78 NdFC4 21 80 SmFC4 15 75 5.4.3. chn lc

Hnh 5.30. nhy ca cc cm bin AFC4 vi etanol, metanol, axeton v cacbonic nng 0,39 mg/l ti 228 v 245 oC.

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Kt qu o nhy ca cm bin AFC4 vi cc kh etanol, metanol, axeton v cacbonic nng 0,39 mg/l ti 228 v 245 oC (hnh 5.30) cho thy ti nhit hot ng ca cc cm bin (228 oC), nhy ca cc cm bin vi etanol cao nht v hu nh khng nhy vi cacbonic. T s nhy K = Setanol/Smetanol hay Setanol/Saxeton u xp x bng 3. Nhng nu o nhy cm bin ti 245 oC th nhy vi cc kh u gim xung nhng t s nhy Setanol/Smetanol hay Setanol/Saxeton u ln hn 6, tc l c th p ng iu kin ch to thit b.

5.4.4. n nh
Kt qu kho st n nh thi gian di (06 thng) c minh ha trong hnh 5.31. Chng ti nhn thy rng cm bin LaFC4, NdFC4 v SmFC4 cho n nh kh tt, cc kt qu o dao ng xung quanh gi tr trung bnh cha n 5%, trong khi vi GdFC4, gi tr o dao ng ln hn ln n 10%.

Hnh 5.31. n nh thi gian di trong mi trng hi cn 0,39 mg/l (a) LaFC4; (b) GdFC4; (c) NdFC4 v (d) SmFC4.

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5.5. C ch dn in v c tnh nhy hi cn ca cc oxit perovskit 5.5.1. Tnh cht dn ca cc oxit bn dn loi p
C ch oxy ha kh cc cht kh ca cc oxit kim loi c th c miu t thng qua ba khi nim sau: (1) Chu trnh xc tc b mt; (2) S trao i v cn bng in tch (3) Cc trng thi oxy b mt khc nhau. dn ca oxit c c trng bi dn in t, dn l trng v ion. nhit di 500 oC s ng gp ca dn ion l khng ng k bi linh ng ca n l rt thp. Ta c th biu din dn tng cng theo biu thc sau [15]:

T = h + e + I
Hay

(5.4)

T = |q| ([h*]h + [e-]e) i l linh ng ca phn t i.

(5.5)

y [h*] v [e-] l nng l trng v nng in t tng ng; q l in tch;

Trong cht bn dn loi p, nng l trng [h*] >> [e-]. Mt khc, i vi cc cm bin dng mng, dn c quyt nh bi nng in tch trn b mt mng. Khi , dn ca mng cm bin c th biu din theo nng l trng trn b mt theo biu thc gn ng sau:

T g*q* [h*]s*h vi [h*] >> [e-].

(5.6).

Trong , g l tham s cu trc; [h*]s l nng l trng trn b mt mng.

5.5.2. C ch hp ph b mt
Qu trnh tng tc ca hi cn vi cc oxit c th c biu din theo hai bc nh sau:

Bc th nht: phn ng hp ph oxy trong mi trng xung quanh ln cc tm

hp ph (cc nt khuyt oxy) trn b mt lp vt liu nhy kh ca cm bin ti nhit cao, to nn cc phn t ion nh O2-, O- v O2-, vi cc in t c ly t lp bn dn: O2(kh) O2(hp ph) O2-(hp ph) 2O-(hp ph) 2O2-(hp ph) (5.7)

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Cc phn ng ny to ra vng ngho bin ht, lm cho bin vng dn b un, in tr ca vt liu tng hoc gim ph thuc vo nhit , mi trng kh. Ta c th vit li cc phng trnh phn ng trn theo dng tng qut sau:
k1 1 O2 + V0 ( O ) + h* 2

(5.8)

Trong : V0 l nt khuyt oxy; k1 l h s tc phn ng; (O)- l cc trng thi oxy hp ph trung gian (O2-, O- v O2-).

Bc th hai: cc phn ng oxy ha etanol bi cc phn t ion oxy hp ph. Trong

khong nhit lm vic ca cm bin (di 500 oC), cc phn t O- hot ng v n nh nht, n s tng tc vi cc phn t etanol. Phn ng ny c th xy ra theo cc giai on sau:

O C2H5OH + B
(n-1)+

C2H5 H O O O-(hp ph) Bn+ Bn+ + e-

(5.9) in t c to ra t phn ng oxy ha ny c tim tr li vo trong khi vt liu. Sn phm ca phn ng trn c th nhm OH to ra cc sn phm anehit, nc v mt nt khuyt anion theo phn ng sau:

n+

H3C C2H5 H O O Bn+ Bn+ C O Bn+ B(n-1)+ + H2O

(5.10) Cc anehit ny s b oxy ha ln hai bi oxy hp ph to ra cc sn phm trung gian c biu din theo phng trnh phn ng sau:
H3C C O Bn+ +

CH3 H O2
-

H O Bn+ O + O Bn+

Bn+

(5.11)

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Hoc: H3C
C O Bn+ +

CH3 H O2
-

C* O Bn+

O+

H O Bn+

(5.12) Giai on ny ty thuc vo mt ca oxy trn b mt mu m c ch phn ng din ra theo phng trnh (5.11) hoc (5.12). Khi qu trnh oxy ha ln hai bi cc cc phn t O- (oxy - ), cc sn phm thu c t cc phng trnh trn li b oxy ha tip v km theo s gii hp oxy ti mt s tm hot ng b mt. Phng trnh phn ng minh ha cho giai on ny c biu din di dng:
CH3 H O Bn+ O O2 Bn+ O Bn+ O Bn+ O OBn+ B(n-1)+ + H2O CH2O

Bn+

(5.13)

Qu trnh gii hp to ra sn phm kh CO2 c biu din di dng:

CH2O O CO2
+

O Bn+

OBn+

(5.14)

Gin minh ha cho c ch oxy ha etanol bi cc phn t O- c biu din trn hnh 5.32. Phng trnh phn ng tng qut cho qu trnh oxy ha trn b mt c vit li di dng:
k2 C2 H5OH (kh) + ( O ) + h* CO 2(kh) + H 2O(kh)

(5.15)

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Hnh 5.32. S minh ha c ch oxy ha etanol ca cc vt liu LaBO3.

Nu gi l bao ph b mt ca cc oxy ring phn, t cc phng trnh (5.8) v (5.15) ta c th xc nh c qu trnh ng hc trao i oxy trung gian (O)- theo biu thc:

d 0.5 = k1 [ O 2 ] * (1 ) k 2 [ etanol] * h* * dt

(5.16)

Mt khc, trng thi cn bng d/dt = 0; bao ph etanol nh hn rt nhiu bao ph ca oxy trn b mt oxit perovskit. Khi bao ph oxy trn b mt c biu din theo biu thc:
= k1 [O 2 ] + k 2 [ etanol ] * h * k1 [O 2 ]
0.5

0.5

(5.17)
S

Trong trng hp cc tm hp ph c bao ph kn bi cc ion O-, nng l trng trn b mt oxit perovskit c th c vit li di dng:
1 k1 [ O 2 ] h* = S k [ etanol ] 2
0.5

(5.18)

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C ch dn v qu trnh oxy ha xc tc ca cc oxit perovskit ph thuc vo cc trng thi oxy hp ph, trong khi cc trng thi oxy hp ph c th thay i. Ngha l cng mt thi im, s thiu ht cc trng thi oxy ring phn O- hay O2t mng tinh th dn n s gim mt hoc hai l trng. S thiu ht ng thi ca c O- v O2- thng din ra vng nhit ln hn 300 oC [109]; Cc ion O2- dn dn thay th cc ion O- ko theo s gim mt l trng bng s suy gim hai l trng. Trong khi, hai ion ny ch khc nhau duy nht v in tch. Nu biu din nhy ca cm bin S, nh hm ph thuc vo nhit v nng etanol di dng: S = Rgas/Rair =

[etanol] = * Cetanol; trong , l cc tham s v [etanol]

l nng cn. T cc kt qu thu c trong cc phn trn ch ra rng, cc tham s v l cc tham s hm m c th lin quan mt thit n h s tc Hnh 5.33. S ph thuc ca hm ln(R /R ) vo tham g a s ln(Cetanol). phn ng gia etanol vi cc ion oxy O- hoc O2-. Tham s c th xc nh c thng qua th biu din s ph thuc ca hm ln(Rgas/Rair) vo tham s ln(Cetanol) ( y, nng etanol, Cetanol, c quy i sang n v ppm). S ph thuc ny c minh ha trn hnh 5.33. Cc kt qu ch ra rng gi tr nh hn 0,5. Tham s s nh i khi nhit lm vic tng. Khi nhit trn 300 oC nhy ca cm bin nh hn 0,5. iu ny gin tip chng minh rng, trng thi ion O- tn ti trong vng nhit di 300 oC. Khi , vng nhit trn 300 oC, nng l trng s c vit li di dng:
1 k1 [ O 2 ] h = S k 2 [ etanol ]
* 2 0.5

T > 300 o C

(5.19)

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Mi lin h gia nng l trng [h*]S v bao ph c th c xc nh thng qua phng trnh cn bng in tch (e- + h*
qNS ( 0 )

0). Mi tng quan gia

bao ph v nng l trng (tm hot ng) c biu din theo biu thc sau:
d = h* h* 0 S S

(5.20)

y, NS l s trng thi ion bao ph b mt c in tch q; o l bao ph ban u; d l chiu dy hiu dng ca mng cm bin; v [h*0]S l nng l trng b mt ban u. iu ny ch ra rng, nng l trng trn b mt mng l mt hm ph thuc vo nng hi cn v oxy c trong pha kh. Nu nng oxy trong pha kh l mt hng s, khi t phng trnh (5.15) v (5.16) ta c th biu din dn ca cm bin nh mt hm ph thuc vo nng l trng v nng hi cn nh sau:

~ [h*]S ~ f(T,Cetanol)

(5.21)

Theo phng trnh 5.12, h s tc phn ng oxy ha xc tc c th c biu din theo biu thc:
r = k 2 h * etanol
S

(5.22)

Th t phng trnh 5.14 vo phng trnh trn ta thu c phng trnh xc nh tc :

r=
k 1 [O 2 ]

k 1k 2 h * [ O 2 ] etanol S
0.5 0.5

+ k 2 h * etanol S

(5.23)

Phng trnh (5.20) ch ra rng, h s tc phn ng nh mt hm ph thuc vo nng l trng v lin quan trc tip n tnh dn in ca cc oxit perovskit. Tm li, trn b mt cm bin, etanol c xem nh cc donor trong h LaFeO3. Hin tng dn in ca cc mng cm bin bn dn lin quan trc tip n qu trnh hp ph trn b mt mng. Ngha l tnh xc tc v dn in ca mng cm bin ph thuc vo p sut ring phn ca pha kh, tnh cht hp ph gii hp; bao ph ca ion oxy trn b mt v nhit lm vic. Mt khc, ca

104

hm ln(Rg/Ra) vo tham s ln(Cetanol) c trnh by trn hnh 5.33 ch ra rng, gi tr l rt nh ( < 0,5). iu ny mt ln na khng nh rng, mt lng ng k kh etanol c th c khuch tn mt phn vo bin ht v khi. Ngha l kh etanol vo vng trong cng ni t in cc dn n s thay i in tr ca mng cm bin ln s cho nhy cao.

5.5.3. S tham gia ca oxy mng v vai tr ca ion kim loi chuyn tip trong qu trnh oxy ha xc tc etanol
S thiu ht oxy c th dn n phn ng vi nhm hyroxyl ban u to ra sn phm cha hai cacbon, sau khi c gii hp vng nhit cao (trn 500 oC). Ngha l qu trnh oxy ha etanol v cc sn phm trung gian c s tham gia ca oxy mng tinh th to thnh nt khuyt oxy V**0 (nt khuyt oxy c in tch 2-) nh c minh ha trong phng trnh phn ng di y: Phng trnh phn ng khi c dng:
CH3 C O Bn+ O O Bn+
-

CH2O H O Bn+ C O Bn+ + 2H+

(5.24)

S gii hp ca cc sn phm cacbonat ny c th to ra kh CO2 vng nhit cao:

CH2O C O Bn+ O Bn+ OB(n-1)+ Bn+ + CO2 + H2O

(5.25)

Tuy nhin hai nt khuyt anion c to bi qu trnh oxy ha c th c th c proton ha bi hai ion H+ c to ra t phng trnh (5.24). S gii hp bi cc phn t O2- (oxy - ) ti cc nt khuyt anion kim loi 3d c th do s tham gia ca cc ion oxy trong mng tinh th vo qu trnh xc tc. Phng trnh phn ng tng qut cho bc hai c th c biu din di dng:

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C2H5OH(kh) + 6O 2 (khi) 2CO 2(kh) + 3H 2O(kh) + 6V**O

(5.26)

Tnh dn in ca cc h vt liu LaBO3 (B = Mn, Fe, Co, Ni) s ph thuc mnh vo thnh phn oxy; trng thi spin ca cc in t 3d ca cc kim loi chuyn tip. S khc bit v dn in lin quan trc tip n cu trc vng nng lng v nng lng vng cm ca mi vt liu [81]. Nguyn nhn ca s thay i ny c th do s dch chuyn in tch thng qua lin kt B-O-B. S dch chuyn in tch c thc hin bi s trao i cc trng thi in t ca cc nguyn t kim loi chuyn tip gia trng thi B4+ v B3+ thng qua chui B4+ O-B c th c biu din di dng:
e tan ol ** B3+ O2 B3+ B3+ VO B3+ + CO2 + H 2O
2 ** B3+ VO B3+

O2-

B3+. Gii

thit rng cc in t ca nt khuyt V**0 l khng nh x, khi mng lin kt B-

1 3

2 3

1/2O

B3+ O 2 B3+
(II)

(5.27)

(I)

** B4+ O2 B4+ B4+ VO B4+ + O2

** B4+ VO B4+ (I)

1 2

B3+ VO B3+
(II)

(5.28)

S phn b in t trong h s bao hm c trng thi (I) v (II). Hiu ng nt khuyt oxy trong trng hp ny c th l do: (a) s tn ti ng thi ca cc cation B4+ v B3+ ti v tr B trong phi tr; (b) s hnh thnh tm sai hng trong qu trnh tng hp vt liu; v (c) s thay i trng thi spin ca cc cation B. S tn ti ng thi cc cation c ha tr khc nhau (nh B3+; B4+ hay B2+ ) ti v tr B c kim chng bi phng php phn tch thnh phn oxy trong mu (xem chng 4). Cc kt qu phn tch ch ra rng, cc mu khng cha thnh phn Co c hm lng oxy trong mu l d: LaMnO3,0912; LaFeO3,0142. Nguyn nhn ca s d oxy ny c th l do s tn ti ca cc ion Mn4+ v cc ion Fe4+ v tr nt mng B. Cc mu cha thnh phn Co - (LaCoO2,9938) li lun cho kt qu v s thiu ht mt lng oxy nht nh, c to bi s tn ti mt lng nh ion Co2+

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khng b oxy ha hon ton thnh cc ion Co3+. Do vy ti v tr B khng ch c chim gi bi phn ln cc ion Co3+, m cn c s tham gia ca mt lng nh ion Co2+ khng c oxy ha hon ton dn n s khuyt thiu oxy. Trong trng tinh th ca BO5 (i vi b mt) v BO6 (trong khi), cc in t trng thi eg t hp mnh vi trng thi 2p ca oxy chu nh hng mnh ca hiu ng tng quan mnh v lun trng thi spin cao. Cc in t eg tr ln linh ng v thm ch tr thnh in t dn, nht l trong trng hp mu b pha tp. Cc qu o vi s c mt ca cc in t cha ghp i trong cc perovskit ABO3 c th ng mt vai tr nh cc tm hot ng xc tc bi xu hng chim gi mc phn lin kt * gia cation B trn b mt vi phn t O-. Trong khi cc in t trng thi t2g ni chung t t hp vi qu o 2p ca oxy nn s b nh x bi hiu ng tng quan mnh v lun trng thi spin thp. iu ny ch ra rng, cc trng thi spin thp hay trng thi spin cao trong vt liu l nguyn nhn ch yu lm gim hay tng nng lng hot ha trong phn ng trao i oxy. Trong h LaBO3 (B = Mn, Fe, Co, Ni) cc ion Co3+; Mn4+ v Ni3+ u tn ti trng thi spin thp, trong khi cc ion Fe3+; Fe4+ ch tn ti trng thi spin cao [23, 88]. Ngha l cc ion trng thi spin cao y hot ng nh cc tm hp ph etanol nh phng trnh phn ng (5.12). Cc ion trng thi spin thp ng vai tr vn chuyn cc ion oxy khi (O2-) ra b mt ti phn t etanol. C ch phn ng vn chuyn din ra theo phng trnh (5.27) v (5.28). Cu hnh spin ca cc ion kim loi chuyn tip trong h vt liu LaBO3 c trnh by trong hnh 5.34 di y.

Hnh 5.34. Cu hnh spin trong khi bt din BO5 trn b mt vt liu LaBO3.

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i vi cc cm bin da trn nn vt liu LaFe1-xCoxO3 (0,0 x 1,0) khi nng thay th Co trong mu tng ln khng ch lm tng tnh dn ca ca cm bin m cn lm tng nng trng thi spin thp trong mu ko theo s tng kh nng vn chuyn cc ion oxy khi (O2-) ra b mt ti phn t etanol. Khi nng thay th Co t gi tr bng 0,4, s vn chuyn cc ion oxy khi (O2-) ra b mt t gi tr cc i. Khi gi tr thay th ln hn 0,4, nhy ca cm bin gim c th l do s suy gim trng thi spin cao ca cc ion Fe3+, ng ngha vi vic lm suy gim cc tm hp ph etanol trn b mt. Mt bng chng na l, cc kt qu kho st vi cu trc ca h vt liu ny (xem chng 4) cng ch ra rng, h vt liu LFC4 c kh nng hp ph v gii hp tt hn c bi kch thc ht trung bnh ca chng l nh hn c so vi cc h vt liu khc c kho st (9 nm).

5.5.4. Vai tr ca cu trc, kch thc ht v cc nguyn t t him ln hot tnh xc tc etanol
Cc kt qu kho st v vi cu trc c trnh by trong chng bn ch ra rng, cc oxit LaCoO3, LaNiO3 v LaFe1-xCoxO3 (0,5 x 1,0) c cu trc tinh th h mt thoi; cc oxit LaFeO3, LaFe1-xCoxO3 (0,1 x 0,4) v AFe0,6Co0,4O3 (A l La, Sm, Nd v Gd) c cu trc tinh th h trc thoi; oxit LaMnO3 c cu trc tinh th h lc gic. Cc mu c cu trc tinh th h trc thoi u cho hot tnh xc tc cao hn cc mu c cu trc khc. Hn na, cc kt qu kho st v kch thc ht cng ch ra rng, cc mu c hot tnh xc tc tt nht u cho knh thc ht nh hn cc cc mu khc trong cng h nh: LaFeO3 (12,1 nm) thuc h LaBO3; LaFe0,6Co0,4O3 (9,6 nm) thuc h LaFe1-xCoxO3 (0,0 x 1,0) v SmFe0,6Co0,4O3 (8,7 nm) thuc h AFe0,6Co0,4O3. iu ny ch ra rng, cc mu c kch thc ht nh s cho din tch b mt ht ln dn n lm tng hiu sut xc tc ca mu. Tuy nhin, vi s sai khc v mt cu trc cng nh kch thc ht ca cc mu l khng ln, nn vai tr nh hng ca cc tham s ny n hot tnh xc tc etanol ca cc mu kho st l khng nhiu. Trong cc h AFe0,6Co0,4O3 (A l La, Sm, Nd v Gd), bn knh ion ca cc nguyn t h lantanoit gim dn t La ti Gd (rLa3+ = 0,118 nm; rNd3+ = 0,112 nm;

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rSm3+ = 0,109 nm; rGd3+ = 0,106 nm [3]), dn n s khc nhau ca cc hng s mng trong cu trc v tnh dn in ca vt liu. Nhng mi tng quan gia cu trc, tnh dn in vi hot tnh xc tc etanol hay s nh hng ca cc nguyn t t him nn tch cht nhy kh l khng r rng quy lut. iu ny cng c kt lun bi mt s cng trnh c cng b trc y [58, 116].

5.6. Kt lun chng

Cc kt qu thu c trong chng ny c th tm tt nh sau: Tnh dn in ca h vt liu LaBO3 (B = Mn, Fe, Co) c c trng bi tnh dn ca cht bn dn loi p. dn in ca h LaBO3 gim dn theo th t: LaCoO3 > LaMnO3 > LaFeO3. S oxy ha etanol ch din ra trn h LaFeO3. nhy etanol cc i bng 27,8 nhit 260 oC. S pha tp tng phn Co trong h LaFe1-xCoxO3 (0,0 x 1,0), khng ch lm bin i ha tr ca cc kim loi chuyn tip v tr B, m cn lm thay i tnh dn in v hiu ng xc tc ca h. Mu LaFe0,6Co0,4O3 cho hot tnh xc tc vi etanol cao nht. Cm bin da trn vt liu ny cho nhy cc i S = 52 nhit 228 oC. dn in ca h vt liu AFe0,6Co0,4O3 (A = La, Gd, Nd v Sm) AFC4 gim n theo th t: LaFC4 > SmFC4 > NdFC4 > GdFC4. Vt liu SmFe0,6Co0,4O3 cho hot tnh xc tc vi etanol l cao nht. nhy ca cm bin t gi tr cc i Smax = 78 ti nhit 228 oC. Thi gian p, thi gian hi phc, n nh v chn lc ca cc cm bin c ch to trn nn cc vt liu: LaFeO3 v AFe0,6Co0,4O3 u tha mn cc tiu ch cn thit v c th s dng trong vic ch to thit b o nng cn trong hi th ca ngi.

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CHNG 6 CH TO THIT B O HI CN
Thit b phn tch hi cn rt quan trng trong y t, sn xut ru bia, cng ngh ln men thc phm v kim tra hi th con ngi. Vic phn tch etanol cng rt cn thit cho vic kim sot cht lng cn trong cng nghip. C nhiu phng php pht hin nng hi cn nh sc k kh, trng lng ring, khc x k, quang ph. Mc d cc phng php ny u c th pht hin nng etanol mt cch chnh xc nhng chng khng th thch hp cho vic phn tch hi etanol ngoi hin trng do chng l cc thit b tinh vi v vn hnh phc tp. Nng cn trong cc sn phm ru, bia v nc hoa qu ln men l rt a dng. Mt vi bia 4,5o (khong 500 ml) s c 20,2 g cn; mt ly ru vang 12o (100 ml) s c 9,48 g cn. Nh vy nu ngi iu khin cc phng tin giao thng ung nhiu bia, ru s khng kim sot c tay li v d gy ra cc tai nn ng tic. Tiu chun chung ca quc t, nng cn cho php i vi ngi tham gia giao thng trong khong 50-80 mg/100 ml mu (BAC Blood Alcohol Content) hay 0,25-0,40 mg/l kh th (BrAC Breath Alcohol Content). Thng thng t s BAC/BrAC dao ng trong khong 2000/1-2300/1 ty thuc vo trng lng ngi ung ru v thi gian ly mu sau khi ung [99, 24]. nc ta, quy nh gii hn v nng cn trong mu i vi ngi li xe c quy nh trong Ngh nh s 36/CP (2005) ca Chnh ph v bo m trt t an ton giao thng ng b v trt t th. Nm 2001, quy nh ny c a vo Lut Giao thng ng b, vn bn c tnh php l cao hn: Nghim cm

ngi li xe ang iu khin xe trn ng m trong mu c nng cn vt qu 80 miligam/100 mililt mu hoc 40 miligam/11t kh th hoc c cc cht kch thch khc m php lut cm s dng. S tng trng kinh t nhanh ti Vit Nam
trong 10 nm gn y ko theo s lng t, mt tng rt nhanh (t khong 10%, mt khong 14%/nm), trong khi vi phm quy nh nng cn i vi ngi iu khin phng tin cn ph bin, l nguy c tim n gia tng tai nn giao thng. Lut Giao thng ng b 2008 va c Quc hi Kha XII thng

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qua quy nh nng cn nghim ngt, kht khe hn bo m an ton cho ngi iu khin phng tin v hn ch tai nn giao thng: Nghim cm ngi

iu khin xe t, my ko, xe my chuyn dng trn ng m trong mu hoc hi th c nng cn; nghim cm ngi iu khin xe mt, xe gn my m trong mu c nng cn vt qu 50 miligam/100 mililt mu hoc 0,25 miligam/1lt kh th (Khon 8, iu 8) v c hiu lc thi hnh t ngy 1 thng 7 nm 2009.
Vic kim tra nng cn trong mu phc tp v cch thc ly mu cng nh cc thit b phn tch mu. Cch thc c bn v ph bin nht hin nay l xc nh nng cn trong hi th bng cc thit b o cm tay [1]. Xut pht t tnh hnh thc t, vic ch to cm bin nhy hi cn vi di o 0-2 mg/l v cc thit b c chc nng ph hp vi cc yu cu dnh cho cnh st giao thng ng b l cn thit. Mt thit b o hi cn cm tay thng gm cc b phn sau: Cm bin nhy hi cn: thng l cm bin kiu in ha, kiu in tr. y c th coi l b phn quan trng nht ca thit b. Phn mch in iu khin. Phn mm tch hp nh gi v lu tr d liu. Cc thit b cn chy th v kim chun theo tiu chun Vit Nam. Ti liu hng dn s dng v vn hnh thit b. Cc bc ch to, vn hnh v chun thit b o nng hi cn trong hi th s c tho lun chi tit trong chng ny.

6.1. Nghin cu ch to thit b o nng cn trong hi th

Sau khi nghin cu cc h oxit perovskit nh c trnh by trong cc chng bn v cc c trng ca cm bin nhy hi cn trong chng nm, vt liu NdFC4 s c s dng cho vic ch to thit b o nng cn trong hi th. Cc thng s k thut ca thit b c o c v nh gi theo tiu chun LVN 107: 2002 ca Tng cc Tiu chun o lng Cht lng Vit nam quy nh. Qu trnh gia cng ch to my c tin hnh trc tip ti Phng Cm bin v Thit b o kh, Vin Khoa hc Vt liu.

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6.1.1. Cc iu kin v yu cu kim nh my o nng cn.

Cc php kim nh cc my o hm lng cn trong hi th c phm vi o 0,0003,000 mg/l c tin hnh vi chu k kim nh 1 nm theo cc bc sau: 1. Kim tra bn ngoi: Kim tra bng mt xc nh s ph hp ca my o vi cc yu cu quy nh trong ti liu k thut v hnh dng, kch thc, hin th, ngun in s dng, nhn hiu, hng dn s dng v cc ph kin km theo. 2. Kim tra k thut: Kim tra trng thi hot ng bnh thng ca my o theo hng dn vn hnh. 3. Kim tra o lng: a. Kim tra im 0 ca my: Bt my, kim tra im 0; o kh khng chn lu lng quy nh. Ghi kt qu vo bin bn kim nh. Sai lch cho php gi tr o 0,005 mg/l. b. Kim tra sai s: Chn t nht 2 loi kh chun nm trong phm vi ca my o. o 3 ln lin tip gi tr hm lng cn ca mi kh chun chn, mi ln o cch nhau t 10 n 15 pht lu lng quy nh. Ghi kt qu o vo bin bn kim nh. Sau tnh sai s tng i. Sai s khng c ln hn 0,020 mg/l khi phm vi o < 0,400 mg/l; 5% gi tr o khi phm v o t 0,400 - 2,000 mg/l v 20% gi tr o khi phm v o vt qu 2,000 mg/l. c. Kim tra lp li: o t nht 5 ln lin tip hm lng cn ca mt loi kh chun chn, mi ln o cch nhau t 10 n 15 pht. Ghi kt qu vo bin bn kim nh. lch chun khng c vt qu 0,007 mg/l vi phm vi o < 0,400 mg/l; 1,75% gi tr o vi phm vi o trong khong t 0,400 n 2,000 mg/l v 6% gi tr o vi phm vi o trn 2,000 mg/l.

6.1.2. Thit k v ch to thit b o nng cn a) La chn phng n thit k

C s la chn phng n thit k l yu cu v ch tiu k thut i vi thit b v cc tnh nng k thut ca cm bin. Cc ch tiu kim tra thit k c tin hnh theo cc bc sau:

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Ngun nui: c la chn l c qui, pin xc loi NiMH vi dung lng 2200
mAh. Vi 4 pin xc, in p khi c np y l 5,6 V (4 x 1,4 V) v khi gn ht l 4,8 V (4 x 1,2 V). Nh vy, thit b cn c b phn theo di in p ngun nui dng hot ng khi pin sp ht (in p ngun thp hn ngng di). Dung lng pin cho php thit b hot ng lin tc trong thi gian khng di 8 gi (1 ca lm vic), vi dng tiu th ti a l 250 mA khi o. Cn c tnh ton dng tiu th ti a l cng sut t ca cm bin. Cm bin ch nhy kh khi hot ng ti nhit t 250 n 450 oC, v vy cn cung cp in nng cho l vi nhit ca cm bin. Theo thit k hin nay ca cm bin, in p t ti a l 2,8 V, dng t khong 180 mA. y l ngun tiu tn dng ln nht trong thit b.

Linh kin: Do ngun nui l ngun n, nn cc loi linh kin (k c khuch i,

bin i AD...) u c la chn l linh kin s dng ngun n (khng dng ngun in p m) gim tiu tn nng lng v th tch my.

Hin th: S dng mn hnh tinh th lng LCD (2 hng x 16 k t) nhm gim in
nng tiu th (so vi LED) v cung cp ti a cc thng tin cho ngi s dng.

b) Thit k ch to phn cng

i vi cc thit b o nng cao, sau nhiu ln th nghim s mch cu cho kt qu tt nht. S khi ca thit b o c trnh by trn hnh 6.1.

Ngun in p chun (Vreference) c nhim v: Cung cp in p n nh (Vheater) cho si t ca cm bin. L ngun chun, trn c s tnh ton in p pin ( kim tra tnh trng
pin) v in p t cm bin (tc l nng kh sau khi qui i). Do mang tnh cht quyt nh ti chnh xc ca php o khi in p pin thay i, nn in p chun phi rt n nh. Trong thit b ny, ngun in p cung cp in p chun 2490 mV ti 25 oC vi tri 54 ppm/oC, tc l khong 3,36 mV trong di nhit hot ng t 0 n 50 oC (sai s tng i 0,14 %).

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Hnh 6.1. S khi thit b o nng kh. Khuch i thut ton (Amplifier):
Cc vi mch khuch i thut ton trong thit b u s dng ngun n (t 3 V tr ln). Sai s do vi mch khuch i thut ton gy ra ch yu l do tri in p offset (khong 7 V/oC, tng ng 0,18 mV trong di 0 oC - 50 oC). Bn thn in p offset (7 mV ti a) c b tr bng phn mm, cho sai s khng qu 0,5 mV ton thang.

Bin i tng t - s AD:

Phng n c la chn l s dng b bin i t in p sang tn s (VFC) loi LM331. u im ca la chn ny l : s dng ngun n (t 4 V tr ln), tuyn tnh cao (0,03 %), di in p vo rng (0 - 2/3 V+) v phn gii cao (ti 15 - bit, tu theo la chn linh kin v thi gian ly mu).

Vi iu khin v cc khi ngoi vi :

Ton b hot ng ca thit b do vi iu khin MC (Micro Controller) iu hnh. Vi iu khin hot ng vi tn s chun 11,059 MHz, c cc chc nng sau :

Nhn tn hiu t cc phm iu khin (control switches) chn ch vn hnh ca thit b.

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o v tnh ton cc in p u vo (V+, Vref v Vx) thng qua b bin i VFC. tit kim nng lng, ngun V+ ch c cung cp cho phn analog (gm l vi nhit ca sensor, khuch i thut ton v VFC) trong qu trnh o. Khi ngun pin yu, MC s dng o v thng bo trn mn hnh LCD. Nu nng kh o vt ngng cho php, s c bo hiu bng m thanh.

Hin th lu tr v c li (Backup) cc kt qu o. B nh EEPROM cho php lu tr ti a 999 kt qu o. Nu s ln o vt qu 999, s liu ca cc ln o u s b xo b.

Cng giao tip RS - 232 cho php truyn s liu lu tr vo my tnh x l tip. Cho pht in kt qu mi ln o qua my in xch tay.

Np pin:
B np pin c cung cp ngun mt chiu 12 V t bn ngoi. Dng np 0,5 A, t ngt khi pin y. Thi gian np khong 05 gi lin tc. Trong cu trc phn cng ca thit b, phn tng t (analog) l phn quan trng nht, quyt nh ti chnh xc ca php o. S nguyn l ca phn tng t c trnh by trn hnh 6.2. Cc in tr trong s u l linh kin hn b mt, c sai s 1% v h s nhit 100 ppm/oC.

Hnh 6.2. S nguyn l phn tng t (analog).

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Khi c cp ngun V+ (khi o), in p chun 2490 mV (hiu chnh bng chit p VR1). in p ny c Q1 khuch i thm khong 20 %, to ra in p Vref vi gi tr khong 3 V. C th coi Vref l t (analog ground), cho php khuch i thut ton hot ng vng tng i tuyn tnh, khi in p li vo thay i t 0,5 V n 3,3 V. in p t cho cm bin c cp t ngun pin E+ nh Q2 v T1. Gi tr in p t c hiu chnh bng chit p VR2. in p tn hiu t cm bin c a vo Q3. Trong mi trng sch, in p ny c b tr (tc l hiu chnh im 0) nh chit p VR3. Khi c kh, tn hiu t Q3 c Q4 khuch i o pha (m hn so vi Vref) 10 ln, nh c th t phn gii ti 0,1 mV trong di in p t 0 ti 250 mV ly t cm bin. Thng qua b chn tn hiu (Analog Multiplexer MUX - Hnh 6.1), cc in p V+ / Vref / Vx ln lt c a vo VFC bin i sang tn s. Nh tuyn tnh cao nn tn s ra ca VFC hu nh ph thuc tuyn tnh vo in p vo theo cng thc: Fout = G .Vin (6.1)

trong G l h s chuyn i. Gi tr G ph thuc vo cc linh kin ca VFC. Ta c th nhn thy l cc gi tr V+ v Vx khng ph thuc vo h s chuyn i G ca VFC. V vy, nh hng tri theo nhit ca VFC hu nh khng ng k.

c) Lp rp thit b o hi cn
Lp rp thit b o hi cn, bao gm: - Lp rp mch in t. - Ch to b np pin c qui. - Lp cc b phn khc vo v my thnh thit b o hon chnh. - o c cc c trng k thut ca thit b, nh ng chun ti cc nng trong khong o v thi gian p ng.

Hnh 6.3. nh my o Alco-I cm tay ghp ni vi my in mini.

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- Np ng chun, kim tra n nh ca thit b. - nh gi sai s php o v kim tra cc chc nng ca thit b. - Dn nhn mc. - Kim tra v hiu chnh hot ng ca thit b. Thit b c th c kim tra bng kh chun v hiu chnh bng phn mm sau mt thi gian s dng. Phn mm hiu chnh kt qu o: gm c phn thay i tri ca in p offset (gi tr o trong mi trng ch c khng kh sch, hoc c hm lng kh cn o nh hn gii hn m phng tin o c th pht hin c); phn thay i dc ca hm tn hiu ph thuc nng kh. Hnh nh my o Alco-I cm tay ghp ni vi my in mini c minh ha trn hnh 6.3 v cc tnh nng k thut c bn ca my o nng cn trong hi th c trnh by trong bng 6.1.

Bng 6.1. Cc thng s k thut ca thit b o nng cn TT 1 2 3

4 5 6 7 8 9 10 11 12

Thng s k thut Di o phn gii chnh xc

Dung lng b nh Dng lu tr Mn hnh (LCD) Nhit mi trng m tng i Kch thc Trng lng Ngun nui S ln o

Alco-I
0,000 - 2,000 mg/l 0,001 mg/l 0,005 mg/l 999 ln o S th t ln o; gi tr nng ; thi gian 2 x 16 k t 0 - 40 oC Ti a 90 % 155 x 85 x 35 mmm < 300 g AC/DC - 12 V, 500 mA > 600 ( 1 pht / ln o vi cqui np )

6.2. Kim tra o lng thit b a) Kim tra im khng ca thit b

Th nghim 10 ln lin tip vi vic thi khng kh sch vo bung o, thit b u hin th 0,000 mg/l.

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b) Kim tra sai s

Chng ti la chn hai nng th nghim l 0,390 v 1,989 mg/l. o 04 ln mi nng , mi ln cch nhau 15 pht. Kt qu nh sau:

Nng (mg/l)

Hin th nng (mg/l)

0,385 0,394 0,397 0,402 1,983 1,899 2,017 2,005

Sai s tng i (%)

1,28 1,02 1,79 3,07 0,30 4,52 1,41 0,80

0,390

1,989

Nh vy sai s nh hn 5% vi nng 1,989 mg/l v vi nng 0,390 mg/l, thit b hin th khng vt qu 0,02 mg/l. Nh vy thit b hon ton p ng tiu chun.

c) Kim tra lp li
Chng ti thc hin vic o lin tip 10 ln ti nng 0,809 mg/l, mi ln cch nhau 15 pht, kt qu o nh sau:

STT
1 2 3 4 5 6 7 8 9 10

Hin th nng
0,797 0,795 0,803 0,798 0,800 0,807 0,814 0,819 0,816 0,823

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Tnh ton lch chun S = 0,0101. Theo tiu chun cho php th khi nng hi cn kho st nm trong khong t 0,400 n 2,000 mg/l cho php S = 0,0175, nh vy thit b p ng tiu chun.

6.3. o th nghim nng cn trong hi th mt s cng nhn Cng ty TNHH Ch bin thc phm ng
Chng ti tin hnh o th nghim nng cn trong hi th mt s cng nhn Cng ty TNHH Ch bin thc phm ng ti thn 2 x ng M, huyn Thanh Tr, H Ni. Thi gian tin hnh o: 13h, sau gi n tra, trc gi vo ca lm vic bui chiu. Chng ti o nng cn trong hi th mi cng nhn 02 ln bng thit b o c ch to th nghim v thit b o i chng Lion alcolmeter SD - 400 ca hng Lion Laboratories Limited, Anh quc. Kt qu cho thy kt qu o trn thit b ch to th nghim kh ph hp vi thit b o thng mi vi chnh lch di 5% (xem ph lc).

6.4. nh gi hot ng, vn hnh ca cc thit b

Qua qu trnh th nghim, chng ti c mt s nhn xt nh sau: My gn, d thao tc; Tuy nhin thi gian ly im 0 sau mi ln o hi lu; Khi o lin tc nhiu ln trong ngy th mi ngy phi sc pin mt ln; Khng th bit ngi c kim tra c thi mnh hay khng v mu kh th su mi cho nng chnh xc.

6.5. Kt lun chng

Chng ti ch to thnh cng thit b o nng cn trong hi th vi di o 0,000 n 2,000 mg/l p ng cc yu cu o lng theo tiu chun Vit Nam. Tuy nhin, do thit k thiu cm bin p sut ( c th yu cu ngi c kim tra thi mnh) nn thit b ca chng ti cn tip tc nghin cu, thit k thm cm bin p sut cng nh ci thin v k thut in t c th p ng tiu chun kim nh thit b.

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KT LUN CHUNG
Lun n l mt cng trnh nghin cu thc nghim v nghin cu ch to v cc tnh cht ca cm bin nhy hi cn da trn vt liu oxit perovskit nhm ng dng trong thit b o nng cn trong hi th vi nhng kt qu chnh nh sau: 1. Ti u ha cng ngh ch to vt liu oxit perovskit da trn phng php sol-gel to phc vi t l mol La:B:axit xitric = 1:1:4; axit xitric/etylen glycol = 4:6 v lng cht phn tn etanol 75% th tch. 2. Ch to thnh cng cc vt liu oxit perovskit LaBO3 (B = Fe, Co, Ni v Mn), LaFe1-xCoxO3 (vi 0,0 x 1,0) v AFe0,6Co0,4O3 (A = La, Gd, Nd v Sm). Vi cu trc, hnh thi hc ca cc mu oxit u c kho st cho thy cc mu u c kch thc ht nano mt, din tch b mt ring ln, p ng tt cc yu cu nghin cu ca lun n. 3. hon thin cng ngh ch to cm bin nhy hi cn da trn nn vt liu LaFeO3; h LaFe1-xCoxO3- (vi 0,0 x 1,0) v AFe0,6Co0,4O3 (A: La, Sm, Nd v Gd). Cc kho st c trng vt l, hot tnh xc tc v nhy ca cc cm bin ny cho thy: Tnh dn in ca h vt liu LaBO3 (B = Mn, Fe, Co) c c trng bi tnh dn ca cht bn dn loi p. dn in ca h LaBO3 gim dn theo th t: LaCoO3 > LaMnO3 > LaFeO3. S pha tp tng phn Co trong h LaFe1-xCoxO3 (0,0 x 1,0), khng ch lm bin i ha tr ca cc kim loi chuyn tip v tr B, m cn lm thay i tnh dn in v hiu ng xc tc ca h. dn in ca h vt liu AFe0,6Co0,4O3 (A=La, Gd, Nd v Sm) AFC4 gim n theo th t: LaFC4 > SmFC4 > NdFC4 > GdFC4. nhy v nhit hot ng ca cm bin ph thuc vo bn cht ca vt liu; vi LaFeO3 cho nhy cc i S = 27,8, nhit lm vic 260 oC; vi LaCo0,4Fe0,6O3 cho S = 52 nhit 228 oC; Vt liu SmFe0,6Co0,4O3 cho hot tnh xc tc vi etanol l cao nht. nhy ca cm bin t gi tr cc i Smax = 78 ti nhit 228 oC. Thi gian p, thi gian hi phc, n nh v chn lc ca cc cm bin c ch to trn nn cc vt liu: LaFeO3 v AFe0,6Co0,4O3 u tha

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mn cc tiu ch cn thit v c th s dng trong vic ch to thit b o nng cn trong hi th ca ngi. 4. ch to thnh cng thit b o nng cn trong hi th s dng cm bin mng dy da trn oxit perovskit vi di o t 0,000 n 2,000 mg/l; phn gii 0,001 mg/l, chnh xc 0,005 mg/l.

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