Cc phng php nghin cu cu trc vt liu

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Chng I PHNG PHP HP PH A LP BET I. Khi nim v hp ph II. Phng php hp ph a lp BET. II.1.C s ca phng php II.2. Cu to, nguyn tc hot ng III. Kt qu o din tch b mt BET ca h xc tc ba cu t Bi-Mo-V Chng II PHNG PHP NHIU X TIA X I. Nhiu x tia X (XRD) I.1. Gii thiu v tia X. I.2. C s ca phng php nhiu x tia X II. Cu to, nguyn tc hot ng II.1. Cu to. II.2. Nguyn tc hot ng: II.3. Thc nghim phn tch nhiu x tia X II.4. Cc phng php tnh ton. III. ng dng ca phng php XRD IV. u nhc im ca phng php XRD V. nh gi kt qu ph XRD . TI LIU THAM KHO

LI M U

Mc ch ca mn hc nghin cu cu trc vt liu trong cng ngh ha hc: -Nghin cu thnh phn ca vt liu v xc nh cc tnh cht ca vt liu - Lin h gia thnh phn, tnh cht vt liu vi kh nng ng dng vo xc tc v hp ph. - Ch to xc tc v vt liu mi. xc nh cu trc ca vt liu, ngi ta s dng ch yu l cc phng php ha l. C nhiu phng php nh ph hng ngoi, X-ray, ph khi, cng hng t ht nhn, phn tch nhit, Cc phng php ny va mang tnh c lp, va mang tnh h tr. Vi mt cht phc tp phi s dng nhiu phng php, da trn nhiu kha cnh nh gi chnh xc v cu trc vt liu. Trong gii hn bi tiu lun ny, em xin bo co mt phng php phn tch cu trc thng dng ang c s dng ti phng th nghim Ha du thuc i hc Bch khoa H Ni l phng php: Phng php Ph hp th hng ngoi. Phng php Phn tch nhit. Phng php nhiu x tia X. Phng php hp ph a lp BET. Xin chn thnh cm n PGS.TS L Vn Hiu cng cc thy c ph trch phng th nghim Ha du-H Bch khoa H Ni to iu kin tt nht cho em hon thnh bo co ny. Hc vin Trn Th M Thm

Chng I

PHNG PHP HP PH A LP BET

I. Khi nim v hp ph
Hp ph l qu trnh t tp cc phn t kh, hi hoc cc phn t, ion ca cht tan ln b mt phn chia pha. B mt phn chia pha c th l lng rn, lng-kh, kh rn. C hai dng hp ph l hp ph vt l v hp ph ha hc. Hp ph vt l l qu trnh cc phn t b hp ph lin kt vi nhng tiu phn (nguyn t, phn t, cc ion,..) b mt phn chia pha bi cc lin kt Vander Walls yu hoc lin kt hydro. S hp ph vt l lun lun thun nghch v nhit hp ph khng ln. Hp ph ha hc l qu trnh hnh thnh lin kt ha hc gia cc phn t b hp ph v hp ph ngay trn b mt phn chia pha. Hp ph ha hc thng xy ra bt thun nghch v nhit hp ph rt ln. i vi xc tc phn chia thnh 3 dang: xc tc mao qun lnmacropores (> 50 nm), xc tc mao qun trung bnh mesopores (2 - 50 nm) v xc tc vi mao qun micropores (< 2 nm).

II. Phng php hp ph a lp BET.

II.1.C s ca phng php M hnh hp ph thng c s dng cho qu trnh hp ph a lp c gii thiu bi Brunauer, Emmett v Teller v c bit nh l phng trnh BET. N da trn nhng gi thit sau: - Nhit hp ph (, q Kcal/mol) khng i trong sut qu trnh hp ph. - Cc phn t b hp ph ln b mt xc tc khng cnh tranh ln nhau, c lp vi nhau. - Mi mt trung tm hp ph ch hp ph mt phn t. - S trung tm hp ph ca cht hp ph khng i. - Cc phn t b hp ph u tin c tng tc vi nhau to ra lc, lc ny to iu kin cho lp hp ph th 2, 3, n. - Tc hp ph (ra) trn lp hp ph th (i) bng vi tc nh hp ph (ra) ca lp (i+1). - Nhit hp ph lp u tin l rt ln so vi nhit hp ph ca nhng lp tip theo. Nhit hp ph t lp th hai tr ln n lp ngng t l bng nhau v bng nhit ngng t. Hd2 = Hd3 = = Hdn

Phng trnh c bn ca BET l:

Trong : V l th tch kh ( iu kin tiu chun) c hp ph v Vm l th tch kh ( iu kin tiu chun) c hp ph trong mt lp. c = exp(Q-L)/RT, trong Q l nhit ca qu trnh hp ph lp cht b hp ph u tin v L l n nhit ngng t ca kh, bng vi nhit ca qu trnh hp ph nhng lp tip theo. p sut tng i ca kh l P/Po[1]. Trong phng php BET p dng cho thc t, th tch ca kh c hp ph c o nhit khng i, khi n l hm ca p sut v th c xy dng l P/V(Po-P) theo P/Po. Xy dng biu m P/V(Po-P) ph thuc vo P/Po s nhn c mt on thng trong khong gi tr ca p sut tng i t 0,05 n 0,3. nghing (tg) v tung ca im ct cho php xc nh th tch ca lp ph n lp ( lp n phn t) Vm v hng s C. B mt ring xc nh theo phng php BET l tch s ca s phn t b hp ph nhn vi tit din ngang ca mt phn t chim ch trn b mt vt rn. Din tch b mt ring c tnh theo cng thc: S= nmAmN (m2/g) Trong : S : din tch b mt (m2/g). nm : dung lng hp ph (mol/g). Am : din tch b chim bi mt phn t (m2/phn t). N : s Avogadro ( s phn t/mol)[6]. Trng hp hay gp nht l hp ph vt l ca Nit (N2) 77K c tit din ngang ca N2 bng 0,162 nm2. Nu Vm c biu din qua n v cm3/g v SBET l m2/g th ta c biu thc: SBET = 4,35Vm. Vic xc nh tit din ngang ca phn t N2 c thc hin vi cc cht rn khc nhau khng c cu trc mao qun v c ht kh ng u. Bng phng php knh hin vi in t ngi ta xc nh c din tch b mt, bit Vm th suy ra tit din ngang. i vi cc cht b hp ph khc, ngi ta xc nh sn v lp bng. Cc gi tr tit din ngang khng phi l i lng tuyt i. chng c th ph thuc vo nhit hp ph v cc tnh cht vt l ca b mt. Chng hn nh, trng thi hp ph ca krypton 77K, tc l di im ti hn ca n, lun l vn tranh ci. Hoc nh, s hp ph cc phn t N2 c th c thc hin theo hng vung gc hoc song song vi b mt vt rn m Rouquerol v cc cng s xc nh theo phng php microcalorimet (phng php vi nhit lng k). Cn ht sc thn trng

i vi nhng trng hp cht hp ph tng tc vi b mt. Chnh v l do ngi ta thng la chn cc kh tr v nhit thp xc nh b mt ring. N2 l cht kh c s dng nhiu nht trong php o b mt BET. Trong mt s trng hp cn c s khuch tn tt trong cc vi mao qun ngi ta phi chn cc phn t hay nguyn t b hn nit. Argon l ng c vin s mt, sau l heli v hydro. Tuy nhin, hydro c th hp ph ha hc , cn heli th kh thao tc thc nghim, do , vic ng dng chng b hn ch. Hnh 12. th BET. II.2. Cu to, nguyn tc hot ng, cc c im ca thit b hp ph a lp BET II.2.1.Cu to v nguyn tc hot ng Mu c t trong cell o, sau dng bm chn khng cao ht chn khng n p sut 10-9 mmHg nhm loi b cc kh c trong mao qun ca mu. Cho mu hp ph cc cht b hp ph ( y dng N2 lng 77K). o p sut trc v sau khi hp ph, t suy ra lng hp ph, ta c mt im trn ng hp ph. Tin hnh cho n khi P/Po=1 th ngng hp ph, ri tin hnh nh hp ph, vi mi gi tr P/Po ta li c mt im trn ng nh hp ph. II.2.2. c tnh k thut ca ASAP 2010 Khong o din tch b mt ring 0,01 3.000 m2/g. Khong o ng knh mao qun 0,35 300 nm. 2 ng chun b mu: t nhit mi trng ti 450OC, chn khng 10-3 mmHg (torr). 1 cng phn tch: chn khng t ti 10-9 mmHg (torr), hp ph N2 ti nhit -196OC (Nit lng tinh khit). Xc nh din tch b mt vt liu rn theo phng php hp ph vt l tnh a im, xc nh phn b mao qun. II.2.3. Kh nng thc nghim Xc nh phn b mao qun theo phng php BJH (BarretJoyner-Halenda) t ng hp ph v nh hp ph. Xc nh phn b mao qun theo phng trnh HorvathKawazoe (cho vt liu micropore). Xc nh din tch b mt ring v th tch mao qun theo phng php Dubinin (cho vt liu micropore-C). Tnh ton nng lng hp ph theo DFT (Density Functional Theory).

II.2.4. Cc c im phn mm ASAP 2010 Hot ng trong mi trng Window quen thuc v thn thin. tch. Tnh ton theo cc phng trnh v cc phng php. Bo co dng file pdf rt thun tin khi chuyn sang word hoc ppt. II.2.5. c im phn cng ASAP 2010 H thng van iu khin c ch to trong tm thp khng r nguyn khi loi tr nh hng ca nhit . H thng chn khng bao gm chn khng s cp v chn khng th cp c th t 10-12torr. B cm bin p sut c nhy rt cao. Bnh Dewar c dung tch 3 lit cho php thc hin php o lin tc trong sut 72 h. C o nhit c bit cho ng ng mu m bo n nh nhit tuyt i trong sut qa trnh o isotherm. Cc cng chun b mu v phn tch c filter cho php o mu dng bt khng cn p vin. T ng iu khin ton b qu trnh chun b mu v phn

III. Kt qu o din tch b mt BET ca h xc tc ba cu t Bi-Mo-V

Cc mu xc tc Bitmut-Molypden-Vanadi bng phng php solgel v ng kt ta c o din tch b mt ring trn h Micromeritics ASAP 2010, PTN Lc Ho Du, HBK H Ni. Bi v h xc tc BismuthMolipden-Vanadi l h vt liu khng c mao qun nn b mt ring ca cc mu thng rt thp (1-4m2g-1). Do , khi tin hnh o trnh sai s chng ti a lng mu ln vo trong cell o (>1g xc tc). Do din tch b mt ca cc mu tng hp c u rt nh nn chng ti khng quan st thy s ph thuc ca hot tnh xc tc vo b mt ring. Do chng ti mi ch dng li kho st hot tnh xc tc ca cc mu theo thnh phn pha. y cng chnh l nhc im ca h xc tc Bismuth Molipdat cho nn cng c BET cha ng vai tr l cng c mnh trong nghin cu h xc tc ny. Mu xc tc Bi0,85V0,55Mo0,45O4 iu ch theo phng php ng kt ta c din tch b mt SBET = 2,103m2/g, nh hn so vi mu xc tc Bi0,85V0,55Mo0,45O4 iu ch theo phng php solgel c SBET = 2,96m2/g. iu ny c gii thch l vi mu xc tc iu ch theo phng php solgel, v c Citric nn khi nung, citric b chy ht, li phn b mt c

gii phng ca xc tc. Cng do citric b chy nh vy, cng lm cho cc ht trn b mt xc tc mt phn b thiu kt.

Chng II PHNG PHP NHIU X TIA X

(X-ray diffraction)

I. Nhiu x tia X (XRD):

I.1. Gii thiu v tia X. Vo nm 1895, nh vt l ngi c William Rontgen tm ra tia X v xc nh c chng c cc tnh cht sau y: truyn theo ng thng; tia X b hp th theo t l hm m theo khi lng ca cht hp th; lm en knh nh; to thnh hnh nh ca vt hp th trn giy nh. Sau . Rontgen c nhn gii Nobel vo nm 1901. Cuc tranh lun v bn cht sng ht ca tia X dn ti s ra i ca thuyt tng i v c hc lng t. Bn cht vt l ca tia X l bc x sng in t va c tnh cht sng va c tnh cht ht. Tia X c truyn i trong khng gian vi tc nh sng v mang nng lng t 200eV n 1 MeV xc nh theo phng trnh: E = h = hc/ Trong : l tn s ca bc x tia X, Hz :bc sng ca bc x tia X, (t 102 n 10-2 , trong nghin cu s dng = 0,5 2,5 ) c l s tc nh sng, c= 2,998 x 108 m/s h l hng s Plank, h= 4,136 x 10-15 eV.s Khi cho chm tia X c bc sng 0 v cng I0 i qua mt lp vt cht ng nht, ng hng c b dy l th cng ca n s b suy gim theo nh lut Lambert nh sau: I = I0 .e-.l / y: l l chiu dy ca lp vt liu l mt ca vt cht / l h s hp th khi Cc hiu ng xy ra khi chm tia X i qua vt liu: Hiu ng tn x (Scattering): + Tn x n hi (Rayleigh): l hin tng tia X khi i qua vt liu ch thay i phng truyn nhng khng thay i nng lng.

s =0 Nu vt liu c cu trc tinh th th hin tng tn x n hi ca tia X s a n hin tng nhiu x tia X (X-Ray Diffraction) + Tn x khng n hi (compton): l hin tng tia X khi i qua vt liu th b thay i phng truyn v nng lng. f 0 Cc hiu ng xy ra khi chm tia X i qua vt liu: + Hiu ng nhit: Tia X lm tng bin dao ng nhit ca in t v ca cc lin kt trong mng. + Hiu ng truyn thng: l hin tng tia X khi i qua vt liu th khng thay i phng truyn v nng lng. Hiu ng ny xy ra vi 1 s vt liu trong sut i vi tia X. + Hiu ng hunh quang tia X (X-Ray Fluorescent): Khi tia X c nng lng ln n c th kch thch cc nguyn t cha trong vt liu v lm cho chng pht ra cc vch ph tia X c trng cho cc nguyn t . + Hiu ng in t: L hin tng khi bc x tia X (k ) c sn sinh t 1 nguyn t nhng cha kp truyn ra ngoi nguyn t th b in t lp ngoi ca chnh nguyn t hp th v kch thch ri khi nguyn t. I.2. C s ca phng php nhiu x tia X C s ca phng php nhiu x tia X l da vo hin tng nhiu x ca chm tia X trn mng li tinh th. Khi bc x tia X tng tc vi vt cht s c hiu ng tn x n hi vi cc in t ca cc nguyn t trong vt liu c cu trc tinh th s dn n hin tng nhiu x tia X. Hin tng nhiu x tia X ch xy ra vi 3 iu kin sau: + Vt liu c cu trc tinh th. + C tn x n hi. + Bc sng ca tia X phi c gi tr cng bc vi khong cch gia cc nguyn t trong mng tinh th[5]. Chiu chm tia X ln mng li tinh th, mi nt mng tinh th tr thnh trung tm nhiu x. Cc tia ti v tia phn x giao thoa vi nhau hnh thnh ln cc vn sng v vn ti xen k nhau. Cc cc i nhiu x (vn sng) c xc nh theo phng trnh Bragg: n= 2dsin Trong : : bc sng tia X . d: l khong cc gia 2 mt phng tinh th k tip trong h cc mt phng tinh th (hkl) (m).

: l gc gia tia ti (hoc tia phn x) v mt phn x (). n : bc phn x v l s nguyn dng.

Hnh 3. Nhiu x trn tinh th.

II. Cu to, nguyn tc hot ng, thc nghim phn tch v cc phng php tnh ton ca phng php nhiu x tia X.
II.1. Cu to. Thit b phn tch nhiu x tia X bao gm: + Ngun pht tia X. + Detector. + Bn o gc. + Ngun in m mt chiu vi in th 2060kV, 545mA. + B vi x l v phn mm x l ph. Vi ngun pht tia X, nhn c hnh nh r nt v cu trc ca vt liu i hi tia X cng gn n sc cng tt. ng pht tia X v cc b phn in t ph tr to ra chm tia X trong khong tn s gii hn c cng ln. Cc b lc gng Gobel, cc b phn ph tr v cc phn mm iu khin cho php to c chm tia n sc c tn s thch hp phc v cho vic phn tch. Anot c lm bng kim lai tinh khit Cu, Co, Mo, Fe v Cr thng c s dng ph bin. Ti phng th nghim ha du v vt liu xc tc i hc Bch Khoa H Ni c 4 trong 5 s loi ng ni trn, vi cng ti a 40kV/40 mA, ca s 10 mm. + ng pht Cu, bc sng 1,5406 .

+ ng pht Co, bc sng 1,78897 . + ng pht Cr, bc sng 2,2897 . + ng pht Mo, bc sng 0,7093 Trong ng Cu l thng dng nht. ng pht c lm mt bng nc v t trong v bo v bng nhm Bng 2. c trng ca cc vt liu lm anot Hnh 4. S nguyn l ng pht tia X. Cu to ng pht tia X nh hnh 4. Trong ng l mi trng chn khng, lp v bn ngoi l thy tinh c bit. ng c cp in mt hiu in th t 20 n 50 kV qua my bin th. Si t bng Vonfram c t nng lm bt ra cc electron, di tc dng ca in trng mnh ti p vo bia lm pht ra tia X. Tia X i ra khi ng pht qua ca s lm bng Beri. Bia c lm c b phn lm mt bng nc. Tia X ra khi ng pht l chm tia vi cc bc sng lin tc , c c trng bng K1, K2, v K. C mt vi phng php c s dng c th bin i thnh chm tia n sc s dng trong phn tch nhiu x: + S dng b lc tia . + S dng detector nhp nhy v la chn theo chiu cao ca xung. + S dng detector bn dn rn Si(Li). + S dng b pht n sc hoc nhiu x n sc. Bng 3. B lc tia tng ng vi cc anot II.2. Nguyn tc hot ng: Ghi nh nhiu x theo phng php bt c thc hin bng mt my nh trn. Mu o dng bt ( Khong 1 mg) c t tm ca my nh. Chm tia X chiu vo mu v b chn li pha sau. Tia X n to gc vi mu, cn chm tia nhiu x to mt gc 2 vi hng i ca tia X[3]. Hnh 5 th hin nguyn tc hot ng ca thit b nhiu x tia X. Hnh 5. Nguyn tc ca thit b nhiu x tia X. II.3. Thc nghim phn tch nhiu x tia X trn my D8 Advance ca Bruker Nghin mn mu bt. Ly mu nghin vo cuvet v p lm phng b mt t cuvet cha mu vo b phn g mu v nh v. Bt my lm mt ng pht. Bt my phn tch.

 Bt cng tc ngun cao p. Khi ng phn mm iu khin X-Ray Commander. Ci t cc thng s qut mu: in p, gc , bc v thi gian qut. Nhn start ghi ph. Lu file d liu ph. S dng cc phn mm x l ph. II.4. Cc phng php tnh ton. Phn tch pha tinh th nh tnh dng phn mm EVA (Evaluation): + Tr nn. + Tm nh (so snh vi patent chun). + Chc nng ha ba chiu. + To file .pdf. + Lm trn ng nn. + Th vin chun vi 150000 cht. Phn mm Wincrysize, Winmetric: + Tnh ton kch thc tinh th, phn b ht. + Tnh ton cu trc tinh th. + Tnh ton vi bin dng ca tinh th. Phn mm Winindex: + Tm cu trc c th tng ng vi file d liu. + S dng vi mu n pha. + Tnh ton cc hng s mng. + Tnh ton kch thc mng. Ngoi ra cn c phn mm Winprofile v phn mm tnh ton Rietveld.

III. ng dng ca phng php XRD

Xc nh tnh pha tinh th Xc nh nh lng hm lng pha tinh th Xc nh cc hng s mng ca tinh th Xc nh phn b kch thc ht

IV. u nhc im ca phng php XRD

Tin hnh o trong mi trng bnh thng Chp nhanh, chp r nt (da trn mt loi detector hin i c th m ti 1 photon m khng c nhiu v mt thut ton c th phc hi li c nh ca mu.) Chp c cu trc bn trong cho hnh nh 3D v c th chp cc linh kin kch c di 50 nm, cu trc nhiu lp.

Tn km chi ph.

V. nh gi kt qu ph XRD vi mu xc tc Bi0,85V0,55Mo0,45O4theo cc phng php tng hp khc nhau.

y, ta xt mu xc tc c thnh phn Bi, Mo,V tng ng vi cng thc Bi0,85V0,55Mo0,45O4. y l mu xc tc gm ba cu t trn c nh gi l c hot tnh cao nht i vi phn ng oxy ha propylen to acrolein. Ph XRD ca mu xc tc Bi0,85V0,55Mo0,45O4 iu ch theo phng php ng kt ta v solgel. Ph XRD ca Bi0,85V0,55Mo0,45O4 iu ch theo 2 phng php ng kt ta v solgel c a ra trn hnh. Ta thy xc tc iu ch c ch yu l Bi0,85V0,55Mo0,45O4, xut hin peak c trng cc gc qut l 28,750; 30,470; 34,570; 42,540 v 53,270. Nh vy xc tc iu ch theo phng php solgel hay ng kt ta u cho xc tc c thnh phn nh nhau. Hnh 7. So snh ph XRD ca mu xc tc Bi0,85V0,55Mo0,45O4 iu ch theo phng php solgel trc v sau phn ng. T ph X-ray ca xc tc Bi0,85V0,55Mo0,45O4 iu ch theo phng php solgel trc v sau phn ng ta thy khng xut hin peak ca cc pha khc, ph hon ton trng nhau chng t khng c s bin i pha trong qu trnh din ra phn ng ha hc.

TI LIU THAM KHO

1. GS o Vn Tng. ng hc xc tc. NXB Khoa hc v k thut, 2006. 2. PGS, TS Nguyn Th Minh Hin. Bi ging cao hc, 2008. 3. Nguyn nh Triu. Cc phng php vt l ng dng trong ha hc. NXB i hc Quc gia H Ni, 1999. 4. Phm Ngc Nguyn. Gio trnh k thut phn tch ha l, 2006 5. L Minh Thng. The catalytic activity of bismuth vanado molybdate 6. Robert K. Grasselli. Catalyst Today, 1994.