i

Mc lc. Danh mc hnh

i iv

Danh mc b ng vi Danh mc s . vii

Danh mc vit tt viii M u . CHNG 1: TNG QUAN V VT LIU MOFs 1.1. Khi nim 1.2. Cu trc vt liu MOFs ....... 1.2.1. n v cu trc c bn SBUs 1.2.2. S kt chui .. 1.2.3. S nh hng ca nhit n cu trc 1.3. Tng h p MOFs .. 1 3 .3 3 4 7 8 11

1.3.1. S lc v cu trc vt liu MOFs ... .... 11 1.3.2 Phng php t ng hp vt liu MOFs 12

1.3.2.1. Phng php nhit dung mi . 13 1.3.2.2 Phng php vi sng .. 13 1.3.2.3 Phng php siu m . 13 1.3.2.4 Phng php khng dung mi .. 13 1.4. Tnh ch t ca MOFs .. 13 1.4.1 xp v din tch b mt ln 13

1.4.2 Kch thc l xp 15 1.5 ng d ng ca vt liu MOFs .. 15 1.5.1 Lu tr kh 16

1.5.1.1 Lu tr kh H2 16

ii

1.5.1.2 Lu tr kh CO2 .. 1.5.2 Tinh ch kh .

18 20

1.5.3 Xc tc 21 1.5.4 Kh nng pht quang 26

1.5.5 Thit b cm bin . 27 1.6 Cc phng trnh nghin cu s hp ph 27

1.6.1 Phng trnh hp ph Langmuir . 27 1.6.2 Phng trnh hp ph ng nhit Freundlich .. 28 1.6.3 Phng trnh hp ph ng nhit BET 29 CHNG 2: TNG HP V PHN TCH CU TRC 32 CA VT LIU MOFs 2.1 Vt li u IRMOF-3 ........................................................................................... 32 2.1.1 Tng hp IRMOF-3 ............................................................................ 32 2.1.2 Kt qu v bn lun .................. ........................................................... 34 2.1.3 Phn tch cu trc ca vt liu IRMOF-3............................................. 35 2.1.2.1 Ph XRD ... 35 2.1.2.2 Ph hng ngoi IR ..................................................................... 35 2.1.2.3 Hnh SEM ................................................................................ 36 2.1.2.4 Hnh TEM .................................................................................. 37 2.1.2.5 Phn tch TGA ........................................................................... 37 2.2 Vt Liu MOF-5 ............................................................................................. 38 2.2.1 Tng hp MOF-5 ................................................................................ 38 2.2.2 Kt qu v bn lun ............................................................................. 41 2.2.3 Phn tch cu trc vt liu MOF-5 ..................................................... 41 2.2.3.1 Ph XRD 41

2.2.3.2 Ph hng ngoi IR . 42

iii

2.2.3.3 Hnh SEM .. 43 2.2.3.4 Hnh TEM . 44 2.2.3.5 Phn tch nhit TGA . 45 CHNG 3: NGHIN CU KH NNG HP PH KH H2 ..................... 46 CA CC VT LIU MOFs TNG HP C 3.1 Nghin c u kh hp ph kh H2 ca IRMOF-3............................................... 47 3.2 Nghin c u kh nng hp ph kh H2 ca MOF-5 ......................................... 50 3.3 Kho st kh nng hp ph kh H2 ca cc vt liu MOFs theo .. 52 Phng trnh Langmuir 3.4 Kho st kh nng hp ph kh H2 ca cc vt liu MOFs ............................ 53 theo phng trnh Freundlich CHNG 4: KIN NGH V KT LUN Ti liu tham kho ... 56

iv

DANH MC HNH
Hnh 1.1 V d SBUs ca MOFs cacboxylat. .. 3 Hnh 1.2 S to MOFs t ion kim loi v linkers hu c... 4 Hnh 1.3 Cu ni Zn-O-C ca mng li... Hnh 1.4 Mt s SBU . Hnh 1.5 Minh ha s to thnh MOF-5 Hnh 1.6 Minh ha s to thnh MOF-199.. Hnh 1.7 S kt chui khung.. Hnh 1.8 Mt s MOFs dng chui khc Hnh 1.9 Cu trc nm giai on hnh thnh Colt succinate Hnh 1.10 nh hng thi gian v nhit ln s hnh thnh cobalt pyridine-3,4- dicarboxylate Hnh 1.11 Cu trc ca mt s ligand... Hnh 1.12 Din tch b mt ca vt liu l xp... Hnh 1.13 Din tch b mt ca cc mnh graphite... Hnh 1.14 ng dng ca MOFs.... Hnh 1.15 Cc ng ng nhit H2 trn cc MOFs khc nhau...... Hnh 1.16 S hp ph bo ha H2 ca cc loi MOFs khc nhau Hnh 1.17 Cu trc cc IRMOF v MOF-177 Hnh 1.18 ng ng nhit H2 trn cc IRMOF v MOF-177 ti 770K... Hnh 1.19 Mt s MOFs dng lu tr kh CO2 Hnh 1.20 Kh nng lu tr CO2 ca MOF-177.. Hnh 1.21 So snh kh nng hp ph CO2 trn cc MOFs khc.. Hnh 1.22 Kh nng bt gi lu hunh ca Cu-EMOF Hnh 1.23 Cu trc khung MOF-5. Hnh 1.24 Minh ha xc tc MOF-5 trn phn ng ankyl ha......................... l xc tc d th Hnh 1.25 Kho st leaching c a Zn4O(BDC)3................................................ Hnh 1.26 Mch v c MIL -53 c nhm
2 -OH

5 6 6 6 7 7 9 10 11 14 14 15 17 17 18 18 19 20 20 21 22 23 25 25 26 27 28

l trung tm acid...................

Hnh 1.27 Hai hng tng hp to khuyt im v cu trc............................. Hnh 1.28 V d mt s cu ni pht quang...................................................... Hnh 1.29 ng dng MOFs lm thit b cm ng............................................

Hnh 2.1 Tinh th IRMOF-3............................................................................. Hnh 2.2 Ph XRD ca IRMOF-3: a) thc nghim v b) tham kho Hnh 2.3 Ph FT-IR:a) IRMOF-3 v b) NH2-BDC Hnh 2.4 a) nh SEM ca IRMOF-5, b) tham kho.. Hnh 2.5 nh TEM c a IRMOF-3.. Hnh 2.6 Gin TGA/DTA ca IRMOF-3. Hnh 2.7 Tinh th MOF-5 trong dung mi DMF v sau khi hot ha.............. Hnh 2.8 Ph XRD ca MOF-5 t ng hp a) v tham kho b).. Hnh 2.9 Ph FT-IR ca MOF-5...................................................................... Hnh 2.10 nh SEM ca MOF-5 v nh SEM ca MOF-5 tham kho.. Hnh 2.11 nh TEM ca MOF-5 Hnh 2.12 Gin TGA/DTA ca MOF-5....................................................... Hnh 3.1 H thng hp ph p sut cao HPVA. Hnh 3.2 ng hp ph H2 ca cc vt liu IRMOF-3.................................. Hnh 3.3 ng hp ph v gii hp ca IRMOF-3. Hnh 3. 4 ng hp ph H2 ca MOF-5 . Hnh 3. 5 ng hp ph v gii hp ca MOF- . Hnh 3.6 ng hp ph H2 ca IRMOF-3 theo Langmuir Hnh 3.7 ng hp ph H2 ca MOF-5 theo Langmuir Hnh 3.8 ng hp ph H2 ca IRMOF-3 theo Freundlich Hnh 3.9 ng hp ph H2 ca MOF-5 theo Freundlich

35 36 37 38 38 39 42 43 44 45 45 46 48 49 49 51 51 52 53 54 55

vi

DANH MC BNG
Bng 1.1 D liu Cobalt succinate v cobalt pyridine -3,4-dicarboxylate

10 12 24 48 50 54 55

Bng 1.2 B mt ring c a MOFs v IRMOFs c tng hp theo phng php nhit dung mi Bng 1.3 So snh MOF-5 vi cc xc tc khc trong phn ng transester ha Bng 3.1 S liu p sut v khi lng hp ph kh H2 ca IRMOF-3............ Bng 3.2 S liu p sut v khi lng hp ph kh H2 ca IRMOF-3............ Bng 3.3 Cc h s ca phng trnh Langmuir i vi cc vt liu MOFs.... Bng 3.4 Cc h s ca phng trnh Freundlich i vi cc vt liu MOFs...

vii

DANH MC S
S 1.1 Phn ng ghp CO2 vi cc epoxide khc nhau................................ S 1.2 MOF-5 ng dng lm xc tc cho phn ng alkyl ha S 1.3 MOF-5 lm xc tc cho phn ng acyl ha . S 1.4 Transester ha DMC vi DEC to EMC.. S 2.1 Quy trnh tng hp IRMOF-3........................................................... S 2.2 Quy trnh tng hp MOF-5.............................................................. S 2.3 Minh ha phn ng to cu trc MOF-5..................................... 22 22 23 23 33 40 .40

viii

DANH MC CH VIT TT
MOFs IRMOFs SBUs BDC ABDC BTB bpdc BPY BTC DMF DEF DCM TCM FT-IR XRD TGA DTA BET TEM EtOH MeOH Metal Organic Frameworks Isoreticular Metal Organic Frameworks Secondary Building Units 1,4-benzenedicarboxylate 2-aminobenzene-1,4-dicarboxylate 1,3,5-benzenetribenzoate 4,4-biphenyldicarboxylate 4,4-bipyridine 1,3,5-benzenetricarboxylate N,N-dimethylformamide N,N-diethylformamide Diclorometan Triclorometan Fourier transform infrared X-ray diffraction Thermal Gravimetric Analyzer Differential Thermal Analysis Brannaur-Emmett-Teller Transmission Electron Microscopy Ethanol Methanol

ix

MIL SEM TGA ZIFs

Material Institut Lavoisier Scanning electron microscope Thermogravimetric analysis Zeolitic Imidazolate Frameworks

M U
Kh hydro, mt trong nh ng nguyn t phong ph nht trn Tri t, tng c coi l cu tr li cho ngun nng lng xanh thay th cho cc loi t chy xng truyn thng, nh d sn xut, sn c v khng gy nhim khi t chy. Hot ng giao thng vn ti hng nm thi thm 13% kh CO2 vo bu kh quyn, trong khi hydro khng h to ra kh thi khi t chy. Mt khc, ngi ta c th to ra hydro t nc thng qua phn ng in phn, hoc thu gi hydro nh mt ph phm t phn ng ht nhn v cc nh my ha cht. Tuy nhin, nng lng hydro ang i mt vi khng t thch thc v nh ng tr ngi nh nguy c chy n cao, bnh cha hydro cho t vn ln v nng n, ng thi thiu ht mng li tip nhin liu. Do , ngoi ngun nng lng sch bit n t lu nh: nng lng gi, nng lng Mt Tri th mt ngun nng lng mi c pht hin v ngy cng c ng d ng nhiu trong thc tin, khng gy nhim mi trng, chnh l ngun nng lng t kh hydro. c th s dng kh hydro trong i sng th cn phi dng bnh cha n. Nhng dng bnh cha th ch c mt lng va phi, vn t ra l phi c mt loi nguyn vt liu no c th cha c th tch ca kh hydro ln hn gp nhiu ln th tch c a n, khi cc nh khoa hc ngh n nh ng vt liu c kch thc l xp nh zeolit, silica, than hot tnh, Bn c nh nh ng vt liu xp truyn thng c ng dng nhiu trong k thut i sng nh : Than hot tnh d ng trong x l kh thi v nc thi; Zeolite dng nhiu trong khoa hc k thut xc tc, hp ph; Silica dng lm cht hp ph trong k thut phn ring sc k nh sc k lp m ng, ct sc k iu ch, lm sch khng kh m Hin nay, vt liu khung c kim (Material Organic Frameworks - MOFs) c khm ph ra bi nh khoa hc Omar M. Yaghi ang tr thnh ti hp dn trong nhiu ngnh khoa hc vi nhiu ng dng trong lnh vc xc tc, tch v d tr kh ... so v i cc vt liu truyn thng c xp cao. Tuy vy, vt liu MOFs vn cha c nghin cu nhiu nc ta v y l mt hng i cn rt mi cho cc nh khoa hc Vit Nam.

MOFs c xc nh l vt liu c cu trc tinh th ng u nht, din tch b mt ring l n, cu trc vch ngn dng phn t khc bit vi nh ng vch ngn dy trong cu trc vt liu xp v c thng thng. C u trc khng gian ca vt liu MOFs rt a dng nh: hnh que, hnh xon, hnh khi a din... vi kch thc khc nhau l do cu to cc phn t hu c lin kt vi cc tm kim loi. MOFs c din tch b mt ring t vi trm n gn 10.000 m2/g. Nh nh ng tnh cht vt tri , vt liu MOFs ng c nghin c u v ng dng trong xc tc ha hc hu c, hp ph chn lc cc loi kh c, lm sch khng kh v c bit l lu tr kh CO2, CH4, kh thin nhin v H2.

Chng 1. TNG QUAN V MOFs

1.1. Khi ni m MOFs l vt liu c b khung kim loi - hu c (Metal-organic frameworks). L nhm vt liu mi, dng tinh th c hnh thnh t nh ng ion kim loi hay nhm oxit kim loi lin kt phi tr vi nh ng phn t hu c [1] [3]. Khng ging nh nh ng tinh th l xp nano khc vi nh ng b khung v c, MOFs c b khung lai 3D, bao gm nh ng khung M-O lin kt vi 1 cu ni hu c khc. MOFs c din tch b mt ln, vt qua tt c nh ng vt liu khc. Hn th na, MOFs c li th hn nh ng cht hp ph truyn thng nh l alumino silicat, zeolit, than hot tnh. Cu trc c bn ca vt liu MOFs l thuc loi vt liu tinh th, c cu to t nh ng cation kim loi hay nhm cation kim lo i lin kt vi cc phn t hu c hnh thnh cu trc khng gian ba chiu xp v c b mt ring ln. MOFs c nghin cu u tin bi gio s O.M. Yaghi v cc cng s trng i hc UCLA (USA) vo nhng nm 1997. 1.2. Cu trc vt liu MOFs d on cu trc MOFs l phi hiu c cch hnh thnh b khung v cch chng t c s n nh v cu trc [3]. Vic t ng hp khung li c xem l vic ghp thnh chui nh ng phn t vi nhau bng nh ng lin kt v ng chc nh l lin kt M-O, C-O, C-C. Cu trc MOFs bao gm kim loi (nh l nt) v linkers (nh l cu ni) c dng mng li m rng bng nh ng lin kt phi tr.
Cluster building block + Organic Link MOFs

Hnh 1.1 V d SBUs ca MOFs cacboxylat. Error! Reference source not found.

Hnh 1.2 S to MOFs t ion kim loi v linkers hu c [4] 1.2.1 n v cu trc c bn SBUs SBUs (Secondary building units) l thut ng n v cu trc c bn, m t cu trc khng gian hnh hc c a cc n v c m rng trong cu trc vt liu nh cc nhm kim loi, nhm carboxylate. SBUs c xem nh l nhng nt v phi tr cho cu ni hu c [5]. Cu trc b khung c a vt liu MOFs c v ng chc hn nh cc cu ni carboxylate, do kh nng nh ng cu ni ny c th kha cc cation kim loi oxygen carbon vi nhng im m rng (nguyn t carbon trong nhm carboxylate) xc nh hnh dng hnh hc cho nhng n v cu trc c b n SBUs. Nng lng lin kt nguyn t ca cc nguyn t trong mi SBUs nh li n kt C O c nng lng 372 KJ/mol mi lin kt; lin kt C C c nng lng 358 KJ/mol mi lin kt; lin kt Zn O c nng lng l 360 KJ/mol cp lin kt. Nh lm cho cu trc ca SBUs c lc lin kt v ng ch c.

Hnh 1.3 Cu ni Zn-O-C ca mng li [27]. Nhm tc gi Michael OKeeffe, Omar M. Yaghi m t hnh hc ca 131 SBU, thnh ph n v lin kt ca chng. Trong khi SBUs kim loi oxygen a din l xanh dng, khi a din xc nh bng nguyn t carbon mu . Trong khi SBUs a din hu c, mi c u ni l mi n v C6H4 mu xanh lc. Cc cu trc hnh hc ny l mt SBUs bao g m 4 SBUs tam gic mu xanh l cy, cc n v carboxylate ny l mt nh c a lng tr tam gic. Sau y l mt s SBU in hnh [8] SBUs Tam gic (triangle) Zn-xanh, O- Lng tr tam gic (trigonal prism) Kim loi (Fe, Cr, Kim lo i (W, Nb, Mo-hng, C-en, O Ru, Mn, V, Ni, Mo)-xm, C-en, , Br:-nu, P-xm Sc,)-cam, C- O- en, O - Bt din (octahedra) Fe-a din vng, CC-en, Co-xanh, C-en, en, O -, S-vng O-, S-vng

Kim loi (Zn, Co, Kim lo i (Er, Yb, Tb-ta, C-en, O - Be)- xanh, C-en, Nd), C-en, O - O- Cuboctahedron C-en, Kim lo i (Fe, V)vng, C-en, O - Hnh 1.4 Mt s SBU Cc MOFs c to nn t cc SBU khc nhau s c hnh dng v cu trc khc nhau. Bn cnh iu kin tng hp nh dung mi, nhit , ligand cng nh hng t i cu trc hnh hc ca MOFs. V d nh MOF-5 c dng hnh khi c to nn t Zn4O lin kt vi BDC (hnh 1.5), MOF-199 c to nn t Cu2(CO2)4 hnh bt din lin kt vi BTC c v tr kim loi m OM (hnh 1.6) [9]. Do ngi ta c th da vo dng hnh hc ca cc SBU d on c dng hnh hc ca cu trc MOFs to thnh [27].

Ni-xanh, O-

Hnh 1.5 Minh ha s to thnh MOF-5 [12].

Hnh 1.6 Minh ha s to thnh MOF-199 [3]. 1.2.2 S kt chui Khung MOFs kt chui to tnh i x ng hnh hc cao, bng cch xuyn su hoc cun vo nhau dn n cc khung b chim ch t cc khung khc, kt qu dn n gim ng knh l xp. S an xen vo nhau ca 2 hay nhiu b khung l mt tr ngi chnh trong qu trnh kin to tinh th rt xp v lm gim th tch khng gian bn trong. S trn ln vo nhau c a 2 hay nhiu b khung hnh thnh nh ng l xp c kch thc nh hn, nhng qu trnh tr n ln lm gia c tnh v ng chc ca tinh th [1] [8].

(a) SBU, s kt chui xon 2 khung lm gim kch thc l xp: b) xon vng, (c) vch dy hn, (d) gim tip xc gn gia cc khung.to kt chui lin tc Hnh 1.7 S kt chui khung [15]

Hnh 1.8 Mt s MOFs dng chui khc

1.2.3. S nh hng ca nhit n cu trc Vic nghin c u v c ch hnh thnh MOFs do c nhiu bin lin quan cha c quan tm nghin c u nhiu; bn c nh nh ng bin n gin nh nhit , thi gian c quan tm nhng rt t. Ngoi ra, cng c mt s nghin cu v s cnh tranh gia yu t nhit ng v ng lc hc, kt qu yu t nhit ng quan trng hn yu t ng hc. Cheetham v cc cng s trnh by nh hng nhit trong qu trnh hnh thnh cobalt succinate. Theo , khi tng nhit lm cho phn t tng kch thc hn do ko di lin kt -M-O-M- v phn t c bn nhit cao. Tc gi nghin cu nm giai on hnh thnh cobalt succinate vi t l phn ng gia cobalt (II) hydroxide v acid succinic l 1:1, kho st nm nhit khc nhau trong khong t 60oC - 250oC. Khi n 100oC, cc trung tm kim loi b hydrate ha to c u trc mt chiu, n 150 oC cc trung tm kim loi to cu trc hai chiu v t cu trc ba chiu nhit cao. iu ng lu l khi nhit tng th H2O phi tr vi cc nguyn t Co gim, lm tng entropy, cc nguyn t Co gn hn, to lin kt M-O-M- v gia tng t trng tng c a h thng. Nghin cu ny m ng cho cc hng nghin cu khc nh thi gian, pH, nng , nhit ng v ng hc khi hnh thnh cu trc MOFs m r ng.

Hnh 1.1 Cu trc nm giai on hnh thnh Colt succinate Kitagawa cng cng s nghin c u nh hng c thi gian v nhit hnh thnh cobalt pyridine-3,4-dicarboxylate. Hn hp CoCl2.6H2O, acid pyridine-3,4dicarboxylic, NaOH, H2O vi t l 1:1:2:555. Tng t vi cc giai on ca Cobalt succinate, 150 oC, H2O phi tr vo cc trung tm Co to cu trc hai chiu v 180 oC to cu trc ba chiu, kt qu ny ph h p vi nghin c u ca Cheetham.

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Hnh 1.10 nh hng thi gian v nhit ln s hnh thnh cobalt pyridine -3,4-

dicarboxylate Bng 1.1 D liu Cobalt succinate v cobalt pyridine-3,4-dicarboxylate Hp cht T oC/gi H2O/M2+a g.cm-3 Chiu Co(H2O)4(C4H4O4) Co(H2O)2(C4H4O4) Co4(H2O)2(OH)2(C4H4O4)3 2H2O Co6(OH)2(C4H4O4)5 H2O Co5(OH)2(C4H4O4)4 Co(H2O)2(C3H3NO4) H2O 60/20 100/20 150/20 4(4) 2(2) 1(1/2) 1.945 1.926 2.085 1 1 2

190/20 250/20 150/24

1/6(0) 0(0) 3(2)

2.197 2.337 2.038 2.361

3 3 2(0) 3(1)

Co3(OH)2(C3H3NO4)2(H2O)2 150/24+180/24 2/3(2/3)

(a): ct u ch hm lng H2O tng, ct k ch s phn t H2O phi tr

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1.3. Tng hp MOFs 1.3.1. S lc v cu trc vt liu MOFs MOFs c cu to t hai thnh phn chnh: oxit kim loi v linkers hu c. Nh ng tnh cht ca linker ng vai tr quan trng trong s hnh thnh c u trc khung c a MOFs. ng thi, hnh dng c a ion kim loi li ng vai tr quyt nh n kt cu ca MOFs sau khi tng hp. Ion kim loi v cc oxit kim loi thng gp l: Zn2+, Co2+, Ni2+, Cu2+, Cd2+, Fe2+, Mg2+, Al3+, Mn2+,v oxit kim loi thng dng l ZnO4. Ion kim loi trung tm hay oxit kim loi ng vai tr nh trc bnh xe. Cc linker hu c trong vt li u MOFs l cc c u ni hu c, ng vai tr nh l nhng chn chng. Mt s hp cht hu c l dn xut ca axit cacboxylic thng dng lm linker trong t ng hp vt liu MOFs nh: 1,4 -benzendicacboxylic axit (BDC); 2,6-naphthalendicacboxylic axit (2,6-NDC); 1,4-naphthalendicacboxylic axit (1,4-NDC); 1,3,5-benzentricacboxylic axit (BTC); 2-aminoterephthalic axit (NH2-BDC); 4,4Bipyridin (4,4 -BPY),.

Hnh 1.11 Cu trc ca mt s ligand So vi cc vt liu truyn thng m ta t ng bit: bentonite, zeoliteth cu trc ca MOFs c l xp ln v t khi thp nht do s phi tr gia cation kim loi v cc linker hu c.

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1.3.2. Phng php tng hp vt liu MOFs 1.3.2.1. Phng php nhit dung mi (solvothermal) y l phng php thng s dng tng hp MOFs. Cc phn ng thc hin theo phng php ny xy ra trong nc hay cc dung mi hu c. Khi nc l dung mi th gi l phng php thy nhit. Phng php ny cn c iu kin thun li l dung mi phi bo ha hnh thnh tinh th v lm bay hi dung mi bng cch tng nhit , lm lnh hn hp tinh th s xut hin MOFs c tng hp bng cch kt hp linker hu c vi mui ion kim loi di tc dng c a nhit trong dung mi ph hp. Nh ng thng s nh hng n qu trnh tng hp MOFs bng phng php nhit dung mi l: nhit , s ha tan c a tc cht trong dung mi, s lin kt ca ion kim loi v linker, pH c a dung d ch, a s cc MOFs v cc IRMOFs tng hp theo phng php ny c b mt ring kh ln c thng k bng 1.2. Bng 1.2 B mt ring c a MOFs v IRMOFs c tng hp theo phng php nhit dung mi [6,21]. Tn B mt ring (m2/g) IRMOF-3 2446 IRMOF-6 2476 IRMOF-9 1904 IFRMOF-20 3409 MOF-5 3900

1.3.2.2 Phng php vi sng Masel et al. s dng l vi sng tng hp MOFs trong 30 giy n 2 pht t hiu sut t 30 % n 90 % [1]. Nhm tc gi Jong-San Chang tng hp Cu3(BTC)2 theo phng php vi sng. Hn hp ph n ng gm H3BTC (2mmol), Cu(NO3)2. 3H2O (3.65 mmol) ha tan trong 24 ml hn hp H2O, C2H5OH (1:1), khuy khong 10 pht, sau gia nhit bng vi sng trong 10 pht. Sau phn ng hn hp c lm lnh xung to phng, ra vi hn hp H2O, C2H5OH nhiu ln, lm khan qua m 100 oC.

13

y l mt phng php y trin vng vi khong nhit s dng tng i rng, thi gian kt tinh ngn (thc hin gia nhit trong l vi sng t 25 giy n 1 pht). Tuy nhin, phng php ny c mt s hn ch nh khng cho d liu tt v cu trc MOFs thu c, do s thiu thng tin v cu trc tinh th thu c 1.3.2.3 Phng php siu m Hn hp Cu(CH3COO)2.H2O v H3BTC ha tan bng trong dung dch DMF: Ethanol: H2O vi t l 3:1:2 v th tch, phn ng thc hi n trong siu m t op v p sut kh quyn sau mt thi gian ngn 560 pht to MOF-199 vi hiu sut cao (62.685.1%). Kch thc nano c a MOF-199 theo phng php ny nh hn so vi phng php nhit dung mi. Tuy nhin, phng php siu m rt ngn thi gian t ng hp t 20 n 50 ln so vi phng php thng thng. 1.3.2.4. Phng php khng dung mi Trong phng php ny, mu i kim loi v cc linker hu c c trn vo nhau, hn hp sau c gia nhit, c th n mc mc nng chy xy ra phn ng oxy ha kh. 1.4 Tnh cht ca MOFs 1.4.1. xp v din tch b mt ln So vi cc vt liu c cu trc xp truyn thng nh zeolite, silica gel hay cc phn t c cu trc rng khc, MOFs l loi vt liu c cu trc tinh th ng u, din tch b mt ln, t trng thp. ng thi, so vi vt li u xp truyn thng c vch ngn dy, MOFs c cu trc vch ngn dng phn t, chnh iu ny to cho vt liu MOFs c rng v din tch b mt ring ln. kho st b mt ring, Omar M. Yaghi ct cc mnh ln thnh nh ng mnh nh tnh ton din tch b mt, theo th di n tch b mt c a mt lng ln cc vng n lin kt vi nhau c din tch 2965m2/g, nu chng ch ni nhau v tr para th din tch 56832/g, cn nu lin kt v tr 1,3,5 ca vng th din tch ln ti 6200 m2/g v khi cc vng ny nm ri rc th din tch c a chng c th ln ti 7745m2/g, hnh 1.13 [11].

14

. Hnh 1.12 Din tch b mt ca vt liu l xp Gio s O.M.Yaghi ct mng ln thnh m nh nh hn theo Hnh (a, b,c,d). Din tch b mt mnh ln graphene l 2,965 m2/g, chui cc vng su lin kt v tr para tng gp i 5,683 m2/g, chia mnh graphene ln thnh cc n v 3 vng lin kt vi vng trung tm v tr 1,3,5-, t 6,200 m2/g, vng n t 7,745 m2/g. T kt qu phn tch ny tc gi nhn nh nghin c u trnh cu trc vng c s lm tng ti a din tch b mt [11].

Hnh 1.13: Din tch b mt ca cc mnh graphite. a) Mnh graphene t cu trc graphite c din tch b mt 2,965 m2/g. b) Chui poly lin kt v tr para ca mch

15

graphene, din tch b mt 5,683 m2/g. c) Lin kt v tr 1,3,5 - ca vng, din tch b mt 6,200 m2/g. d) Din tch b mt ti a 7,745 m2/g [11]. 1.4.2 Kch thc l xp Cc vt liu xp c phn chia theo cc nhm kch thc l xp sau: Microporous: ng knh l xp nh hn 2 nm. Mesoporous: ng knh l xp t 2-50 nm. Macroporous: ng knh l xp ln hn 50 nm. Hu nh cc loi vt liu MOFs u thuc nhm microporous v mesoporous. Do din tch b mt v cu trc l xp ln, MOFs c nhiu ng dng trong hp ph kh, trong xc tc phn ng ha hc, 1.5 ng dng c a vt liu MOFs. Trong sut thp k qua, MOFs c bit n l vt liu c nhiu tnh cht c trng vi kh nng ng dng trong nhiu lnh vc nh: xc tc, hp ph, tc cht, dc phm, quang hc, t tnh, quang ha. c rt nhiu nghin c u v s a dng trong cu trc ca MOFs v xu hng gn y ngy cng i su hn vo nh ng ng d ng y tim nng ca loi vt liu ny [5] [13].

Hnh 1.14 ng dng ca MOFs

16

1.5.1 Lu tr kh MOFs (Metal-Organic Frameworks) l nhm vt liu lai mi i di n cho loi vt liu xp c kch thc nano cho thy mt trin vng ln v kh nng lu tr kh mt cch an ton v vt tri. V i c tnh nh: cu trc tinh th d ng l xp ln, t khi thp v din tch b mt ln MOFs c ng dng trong vic lu tr kh, c bit l kh H2 v metan nhin liu dng trong t v cc thit b khc. 1.5.1.1 Lu tr kh H2 S s dng qu mc ngun nhin liu ha thch nh hin nay lm cho chng ngy cng cn kit dn. Do i hi phi tm mt ngun cung cp nng lng thay th, an ton v t nhim mi trng l i u v cng cp thit. Hydro c xem l ngun nng lng cho nh ng hot ng trong cng ngh tng lai v l nhin liu sch khng pht sinh kh thi nh knh khi t chy v sn phm chy c a hydro l nc. Tuy nhin, vic lu tr v vn chuyn hydro mt cch an ton phc v cho nh ng nhu c u hng ngy c a con ngi vn l mt thch , v tch tr H2 lng ln rt kh v tn km. Nu tch tr dng kh phi p sut cao hay dng l ng th nhit phi rt thp, gy mt an ton do d chy n hay phi tn nhiu nng lng cho vic lm lnh. Vic lu tr hydro mt cch hiu qu, n nh v ng dng trong vic tip nhin liu ng c l ng lc thc y cc nh khoa hc trn th gii nghin c u vt liu mi hin nay. Vt li u MOFs c din tch b mt ln c xem l vt liu y trin vng cho vic lu tr kh hydro, ng thi MOFs d ch to v a vo sn xut. Tuy vy, cng c mt s vn lin quan n s n nh nhit v ng knh l xp ca MOFs. Trong qu trnh t ng hp MOFs, l xp trong vt liu ny b in y bi nh ng phn t dung mi. Do , vic di chuyn nh ng phn t dung mi ny ra khi MOFs c th lm v vn cu trc l xp, khi chng s tr nn v ch cho bt k mt ng dng k thut no. c gn 5000 MOFs vi cu trc 2D v 3D c bo co t lu, nhng ch c mt s MOFs c l xp n nh c th nghim lu tr hydro. Theo nghin c u ca Taner Yildirm v Michael Hartman, MOFs -5 vi kch thc mng li 3 chiu c vai tr nh nh ng chic lng nano c kh nng nhi nht phn t kh hydro. Tc gi Omar M. Yaghi v cc cng s nghin c u s hp ph hydro c a 7 loi vt liu MOFs ti 77K. Kt qu thp nht vi MOF-74, s hp ph bo ha ti 26 bar

17

l 2.3 wt% trong khi MOF-177 ln ti 70 80 bar v s hp ph hydro l 7.5 wt% [15]

Hnh 1.15 Cc ng ng nhit hp ph H2 trn cc MOFs khc nhau

Hnh 1.16 S hp ph bo ha H2 ca cc loi MOFs khc nhau

18

Hnh 1.17 Cu trc cc IRMOF v MOF-177

Hnh 1.18 ng ng nhit H2 trn cc IRMOF v MOF-177 ti 77 oK 1.4.1.2 Lu tr kh CO2 c hn 23 loi MOFs c to ra vi mc ch bt gi v lu tr kh CO2, di y l mt s loi MOFs c tng hp [10]

19

MOF-2: Zn2(BDC)2

MOF-505: Cu2(BPTC)

MOF-74: Zn2(DHBDC)

MOF-177: Zn4O(BTB)2

MOF-199: Cu3(BTC)2

IRMOF-11: Zn4O(HPDC)3

IRMOF-1:Zn4O(BDC)3

IRMOF-3:Zn4O(NH2BDC)3

IRMOF-6:Zn4O(C2H4BDC)3

Hnh 1.19 Mt s MOFs dng lu tr kh CO2 Lng kh thi CO2 pht sinh t xe c, nh my pht in, t cc nh myngy cng gy nh hng trm trng n mi trng l nguyn nhn trc tip gy ra hiu ng nh knh. V vy vic gii quyt lng kh ny l mt bc xc ton cu. t mi trng hp ph hiu qu v kh nng hp ph lu di, cht hp ph phi c hai c trng sau: cu trc tun hon nhm t s hp ph v phng thch CO2 hon ton thu n nghch v cu trc khung mm do. MOFs l loi vt li u c nhng c

20

tnh thun li hn so vi cc vt liu thng dng silicate, carbon, Nhm tc gi Omar M. Yaghi nghin c u kh nng hp ph CO2 t i nhit phng c a cc MOFs khc nhau, kt qu cho thy MOF-177 c th cha 33.5 mmol/g CO2 hn hn cc vt liu xp khc.

Hnh 1.20 Kh nng lu tr CO2 ca MOF-177

Ti p sut 35 bar, mt thng cha MOF-177 c th cha gp 9 ln lng CO2 so vi thng khng cha cht hp ph [18].

Hnh 1.21 So snh kh nng hp ph CO2 trn cc MOFs khc 1.5.2 Tinh ch kh MOFs c th c dng loi b hm lng vt ppm cc thnh phn lu hunh do cu trc MOFs c v tr kim loi m thch hp vi cc phn t c mi thm, giu in

21

t nh cc amine, phosphine, oxygenate, alcohol, H2O, phn t cha S. V d c th loi tetrahydrothiophene (THT) t kh thin nhin, ti nhit phng lng vt 10-15ppm lu hunh b bt gi hon ton cn thp hn 1 ppm khi dng Cu-EMOF in ha trong bnh phn ng tng c nh [19,41].

Hnh 1.22 Kh nng bt gi lu hunh ca Cu-EMOF 1.5.3 Xc tc MOFs c b mt ring ln cng c nghin c u p d ng lm cht xc tc lm tng nhanh vn tc cho cc phn ng ha hc trong nh ng ng dng v sn xut vt liu v dc phm. Tnh xc tc c a MOFs khng cnh tranh c vi zeolite trong iu kin phn ng bt buc nhng c gi tr cao trong cc phn ng sn xut ha cht tinh. Mt s MOFs c c tnh vi xp vnh cu ging zeolites, nhng mt s th khng cn vi xp khi dung mi c ui i, tnh bn ca vi xp sau khi ui dung mi cn thit cho ng dng tch kh, d tr kh, xc tc pha kh [19]. Vi cu trc tinh th trt t cao, kch thc l xp ca MOFs c th iu chnh cho php n xc tc tt trong mt phn ng c th. a. V tr kim loi hot tnh Gandara v cc cng s to MOF dng In(III) MOF cha cc knh hnh vung, cc knh trng vi In(OH)L, in y pyridine trong In(OH)L.Py,L l 4,4(hexafluoroisopropylidene)bis(benzoic acid). Vt liu ny bn nhit, l xc tc hiu qu

22

cho phn ng acetyl ha aldehyde, s khc nhau v hot tnh xc tc gia cc cht c knh trng v knh in y dung mi ch ng t xc tc thc s xy ra bn trong l xp [1]. Nhm tc gi Buxing Han dng h MOF-5/n -Bu4NBr lm xc tc phn ng t ng hp carbonate vng t epoxide v CO2 iu kin thng [1].

Hnh 1.23 Cu trc khung MOF-5 [24]

S 1.1 Phn ng ghp CO2 vi cc epoxide khc nhau [24] Ngoi ra tm km ca MOF-5 cn ng vai tr nh mt acid lewis lm xc tc d th cho phn ng alkyl ha v acyl ha [1,23].

S 1.2 MOF-5 ng dng lm xc tc cho ph n ng alkyl ha [23].

23

Hnh 1.24 Minh ha xc tc MOF-5 trn phn ng ankyl ha l xc tc d th [23].

S 1.3 MOF-5 lm xc tc cho phn ng acyl ha [1]. Tc gi Yinxi Zhou nghin c u tng hp ethyl methylcarbonate b ng cch transester ha dimethyl carbonate v diethyl carbonate dng Zn4O(BDC)3 nh xc tc acid Lewis. Kt qu Zn4O(BDC)3 xc tc tt phn ng so vi cc xc tc cn li, kho st leaching ch ng t Zn4O(BDC)3 tht s d th v c th thu hi ti s dng 3 l n m khng gim hot tnh ng k. [25]

S 1.4 Transester ha DMC vi DEC to EMC

24

Bng 1.3 So snh MOF-5 vi cc xc tc khc trong phn ng transester ha Xc tc Khng Zn4O(BDC)3 MgO ZnO Ti(OBu)4 Zn(NO3)2.6H2O Zn4O(BDC)3 L2 Zn4O(BDC)3 L3 Zn4O(BDC)3 L4 Hiu sut (%) chn lc (%) 50.1 40.9 0.2 21.1 0.2 49.7 46.7 48.4 100 100 100 98.5 100 100 100 100

iu kin phn ng: DMC 1.802g (20 mmol), DEC 2.362 (20 mmol), xc tc 2 wt%, 100 oC, 3 gi. Hiu sut v chn lc xc nh bi GC.

Hnh 1.25 Kho st leaching ca Zn4O(BDC)3

25

b. Cu trc khuyt [21] Ugo Ravon v cng s trnh by hai phng php tng h p MOFs c hot tnh xc tc cho phn ng alkyl ha. Th nht l phng php bt chc Zeolite zeolite mimetic, ch n MOFs dng M-OH c v tr Bronsted, tm Al hay Zn, cu -OH (MOF-69, MIL-53 Al). Hai vt liu Al(OH)(bdc) v Zn3(OH)2(bdc) u c nhm OH trong cng thc phn t. MIL-53 to thnh t mch di v h n AlO4(2-OH)2, MOF-69C gm cc chui ZnO2(OH)2 t din, ZnO4(OH)2 bt din v 3-OH (Hnh 1. 26).

Hnh 1.26 Mch v c MIL -53 c nhm 2-OH l trung tm acid Phng php hai l tng hp vt liu c cu trc khuyt, to cc trung tm hot tnh xc tc. S tng hp theo phng php kt tinh nhanh dn n thiu mt phn trong s cc cu n i mng li hay tng hp MOFs t h n hp cc cu ni poly-dentate v mono-dentate to khuyt im ti cc nt gn k mono-dentate vi t s khi lng gia di- v mono -carboxylic acid l 2.5%, 5%, 10% (Hnh 1. 27).

Hnh 1.27 Hai hng tng hp to khuyt im v cu trc

26

1.5.4 Kh nng pht quang S pht quang l s pht ra nh sng c kch thch khi hp thu nng lng, dng nng lng kch thch c trng dng photon nhng cng c th c to ra bi in trng hay bc x ion ha. C hai loi pht quang c bn l s pht hunh quang v s pht ln quang, ln quang khc vi hunh quang ch vic electron tr v trng thi c km theo nh photon l rt chm. Trong hunh quang, s ri v trng thi c ca electron gn nh tc th gip photon c gii phng ngay. Do , cc cht ln quang hot ng nh nh ng b d tr nh sng: thu nhn v nh ch m nh sng ra sau [21][22]. c tnh pht quang c a MOFs thu ht s quan tm gn y, MOFs nh l cht rn siu phn t c lin kt mnh, cc n v cu ni c th bin i nh vo qu trnh tng hp hu c v c cu trc hnh hc hon ton xc nh. T nm 2002 n nay, c gn 200 bi bo trnh by v s pht sng v mt s bi review v kh nng pht quang ca MOFs. Cu n i ligand: nhm pht quang, hp cht hu c hp thu vng UV v vng thy c. S pht sng c th trc tip t cu ni hoc c th l s chuyn in tch vi ion kim loi phi tr.

3-D Zn4O(SDC)3

Hnh 1. 28 V d mt s c u ni pht quang -D Zn3(SDC)3(DMF)2 -D Cd3(SDC)3(DMF)2 -D Mn3(SDC)3(DMF)2

Ion kim loi khung: cc ion lanthanoid nh Eu (III), Tb (III) pht quang yu do s chuyn in t b chn bi lp v 5d. gii quyt vn ny to cu hp thu mnh. Vi ni dao ng mnh gia kim loi v cu ni s c s chuyn nng lng trc tip d dng t cu ni, kch thch t ti tr ng thi mc nng lng thch hp ca kim loi. iu ny lm gia tng ln kh nng pht quang nn gi l hiu qu antenna. Tng tc gia cc cu ni lin hp k nhau hoc gia cu ni vi phn t khch c th to phc kch thch.

27

1.5.5 Thit b cm bin MOFs s h u trong n kh nng pht quang cng vi kh nng hp ph c ch n lc v mt kch thc v hnh dng phn t, do vt liu ny cn c ng dng vo thit b cm bin. Ngoi ra, do MOFs c cu trc d ng tinh th nn khi c tia electron n b mt ca n s xy ra kh nng tn x n hi. iu ny c ng dng trong vic pht hin bc x ion. V qua kim nh cho thy kh nng chu ng c a mt s MOFs trong mi trng bc x kh tt so vi mt s cm bin ang c s dng. Mt s MOFs cn c ng dng trong cm bin p lc do c tnh n hi v hp ph thay i theo p sut [23].

Hnh 1.29 ng dng MOFs lm thit b cm bin

1.6 Cc phng trnh nghin cu s hp ph 1.6.1 Phng trnh hp ph Langmuir Nm 1915 Langmuir a ra thuyt hp ph n phn t trn cht hp ph rn, Phng trnh hp ph Langmuir [36][37][38] c xy dng da trn c s cc gi thuyt sau: - Mi trung tm ch hp ph mt phn t kh, v vy trn b mt cht hp ph to nn mt lp hp ph n phn t.

28

Lc hp ph c bn cht ca lc hp ph. Nng lng hp ph l ng nht v s hp ph l thun nghch.

Phng trnh c dng:

hay

(1-1)

x/m: Khi lng cht hp ph trn 1 g cht hp ph rn. W: l lng ca cht b hp ph p sut P/P0 Wm: l khi lng ca cht b hp ph trong lp n. C: l hng s lin hp nng lng ca qu trnh hp ph

Phng trnh c vit li di dng tuyn tnh cho php xc nh h s gc (1/Wm) t gin ca (P/Po)/W vi P/Po.

hay

(1-2)

Khi lng c a lp n phn t Wm c th dng tnh ton tng th b mt ca mu t phng trnh:

(1-3)

N l s Avogado (6.023x1023 phn t/mol) Acs di n tch b mt phn t b hp ph (m2/phn t). M khi lng phn t cht b hp ph.

1.6.2 Phng trnh hp ph ng nhit Freundlich. Phng trnh Freundlich [36][37][38] p dng cho s hp ph cht kh hay cht ha tan trong dung d ch lng :

29

hay (1-4)

Vit di dng logarite:

hay

(1-5)

Nh vy, nu biu din logx/m theo logP, ta s c mt ng thng c h s gc 1/n v tung gc logK. Thc nghim cho thy gi tr 1/n c gi tr trong khong 0.2 1.0, phng trnh ny thch hp trong khong p sut trung bnh. 1.6.3 Phng trnh hp ph ng nhit BET - Do phng trnh Langmuir ch thch ng vi mt s trng hp, nm 1938 BET [35][38] (Bruauer-Emmett-Teller) xut quan i m hp ph vt l t o thnh nhiu lp, lp u tin c a hp ph do tng tc lc VanderWaals gia cht hp ph v cht b hp ph, lp k tip ch tng tc vi phn t lp trc n v sau n. - Phng php BET l phng php thng dng dng lm quy tc xc nh din tch b mt ca v t liu rn.

(1-6) + W l khi lng ca kh hp ph p sut hp ph + Wm l khi lng ca cht hp ph cn xc nh b mt + Po l p sut ban u (760 mmHg, 1 atm) + P l p sut hp ph

30

+ C l hng s BET, lin h nng lng qu trnh hp ph trong lp h p ph u tin v do gi tr ca n ch ra tm quan trng tng tc ln nhau c a cht hp ph v cht b hp ph . Phng php BET nhiu im Phng trnh BET ph thuc mi lin h tuyn tnh gia vi P/Po ca hu ht cht rn l gii hn trong mt vng gii hn ca qu trnh hp ph ng nhit nhng ch ng cho khong P/Po t 0.050.3. Khi s dng N2 nh l cht hp ph thng thng s dng t s P/Po t 0.050.35. Vng tuyn tnh ny thay i thp hn p sut thc t cho vt liu l xp. Quy nh ca phng php BET nhiu im, tiu chun yu cu ti thiu 3 im trong dy p sut thch hp. Khi lng ca lp n hp ph Wm c h s gc s v tr c y ca gin BET. (1-7)

(1-8) Nh vy khi lng ca lp n hp ph Wm c th tnh bng hai phng trnh (17) v (1-8). (1-9) Bc k tip p dng phng trnh BET tnh ton din tch b mt. Tng din tch b mt St c th tnh theo phng trnh (1 -3).

Nitrogen l kh thng d ng s dng lm cht b hp ph xc nh din tch b mt khi n c cng b, gi tr C l h ng s (50250) trn hu ht b mt r n. 77K, din tch b mt Acs c a nitrogen l 16.2 2. c bit, din tch b mt S c a cht rn c th tnh ton t tng din tch b mt St v khi lng mu W theo phng trnh.

31

S=St/W
Phng php BET mt im

(1-10)

Phng php xc nh din tch b mt n gi n nht c th p d ng, s dng duy nht mt im hp ph ng nhit trong vng tuyn tnh c a biu BET. Gi tr hng s C ca nitrogen thng ln c th gi nh v chp nhn phng trnh BET i qua im 0. Nh vy, phng trnh BET lc gi cn. (1-11) Bng cch o khi lng ca cht hp ph nitrogen ti mt gi tr c lin quan n p sut (P/Po=0.3) trn mt khi lng cht hp ph Wm c th s dng phng trnh trn v phng trnh kh l tng. Ta c phng trnh: (1-12) Tng din tch b mt c tnh t phng tr nh.

(1-13)

32

CHNG 2: TNG HP V PHN TCH CU TRC VT LIU MOFs

2.1 Vt liu IRMOF-3 2.1.1 Tng hp IRMOF-3 Tng hp IRMOF-3 da trn tc cht l mu i Zn(NO3)2.6H2O v linker 2-Aminoterephthalic axit trong dung mi DMF theo phng php nhit dung mi. a. To tinh th Hn hp mui Zn(NO3)2.6H2O (0.740 g, 2.9 mmol) v 2-Amino-terephthalic axit (0.156 g, 0.86 mmol) c ha tan vo 10 ml dung mi DMF. Hn hp c khuy cho n khi tan han ton nhit phng. Sau , hn hp ny c gia nhit n 100oC v c gi nhit ny trong 2 ngy. Cc tinh th hnh lp phng, c mu en c hnh thnh. b. Trao i dung mi Sau khi c lm ngui n nhit phng, dung mi s dng trong qu trnh tng h p c ht ra, tinh th IRMOF-3 va thu c, s c ra 3 ln, mi ln 10ml DMF ((3 ln x 10 ml)/3 ngy). Sau mi ln ra, cc tinh th IRMOF-3 c ngm tip trong dung mi DMF trong vng 24h ((3 ln x 10 ml)/3 ngy). Tip n, cc tinh th IRMOF-3 c ra vi dung mi dichloromethane 3 ln, mi ln l 10 ml, cc tinh th IRMOF-3 cng c ngm 24h trong DCM c. Hot ha IRMOF-3 Sau khi ra bng DCM cui cng. Tinh th IRMOF-3 thu c mang i hot ha trong h thng Shlenk-line nhit 1600C trong 6 h thu c 1.56 g, hi u sut t c l 67% (tnh theo 2-Amino-terephthalic axit).

33

S tng hp:

(3.70g, 14.5mmol) Zn(NO3)2.6H2O + 50 ml DMF

Khuy t

(0.78g, 4.3mmol) NH2BDC + 50 ml DMF

Hn hp phn ng

Gia nhit

100oC trong 2 ngy

Ra tinh th

10ml3 DMF/3 ngy

Trao i dung mi

10ml3 DCM/3 ngy

Hot ha

Chn khng, 160oC,6h

IRMOF-3
S 2.1 Quy trnh tng hp IRMOF-3

34

OH NH2

Zn2+

HO

S 2.2 Minh ha phn ng to cu trc IRMOF-3 [Zn4O(C8H5NO4)3]

Hnh 2.1 Tinh th IRMOF-3 2.1.2. Kt qu v bn lun Trong cu trc c a IRMOF-3 [Zn4O(C8H5NO4)3], cc ion Zn c km bi cc nhm carboxylate c a axit v to thnh cc bt di n Zn4O. Cc bt din ny s c kt ni bi cc vng benzen c a axit terephthalic, hnh thnh khung h u c -kim loi ca vt liu IRMOF-3. IRMOF-3 c tng hp bng phng php nhit dung mi. Trong DMF c s dng nh dung mi phn cc, c vai tr ha tan tt cc cht ph ng, to iu kin

35

thun li cho qu trnh proton ha cc nhm chc c a cc ligand hu c, t gip cho qu trnh pht trin tinh th din ra tt hn. Giai o n ra tinh th IRMOF-3 bng dung mi DMF nhm ha tan cc tc cht khng phn ng trong qu trnh hnh thnh tinh th. Sau , tinh th IRMOF-3 tip tc c ra bng DCM, nhm thay i cc lin kt mnh ca DMF bng cc lin kt yu ca DCM vi khung hu c kim loi. Qu trnh ny s gip cho giai o n hot ha tinh th sau cng c thun li hn. Cc c tnh c a IRMOF-3 c xc nh bng cc k thut phn tch hin i nh XRD, SEM, TEM, AAS, FT-IR, TGA,... 2.1.3 Phn tch cu trc ca vt liu IRMOF -3 2.1.2.1 Ph XRD Hnh ph XRD ca IRMOF-3 c th hi n trn Hnh 2.2. Qua hnh ny ta thy vt liu ny c c u trc tinh th cao, r rng, c peak nhn c trng ti 2=7 hon ton ph hp vi kt qu cng b ca tc gi Zhenqiang Wang, tc gi Omar M. Yaghi [32].

b)

a)

Hnh 2.2 Ph XRD ca IRMOF-3: a) thc nghim, b) tham kho 2.1.2.2 Ph hng ngo i IR Ph FT-IR ca IRMOF-3 v NH2-BDC c th hi n trn Hnh 2.3.

36

Qua ph FT-IR ta thy, nhm C=O trong IRMOF-3 hp th ti s sng 1567 cm-1, tc l c s d ch chuyn vi s sng ngn hn so vi gi tr dao ng ko cng ca nhm C O trong gc axit cacboxylic t do hp th ti 1691 cm-1. Peak m nh ti 1567 cm-1 l kt qu ca s ko cng ca anion cacboxylat hi n din trong vt liu IRMOF-3. iu ny ch ng t rng nhm COOH b kh proton trong phn ng vi cc ion kim loi. iu ny c th l do vic gim hiu ng lin hp do nguyn t O lin kt vi Zn. S xut hin 2 mi mnh ti 3507 cm-1 v 3393 cm-1 trong ph ca NH2-BDC l kt qu ca s ko cng dao ng c a N-H trong nhm NH2. Hai mi mnh ny khng xut hin trn ph ca IRMOF-3. iu ny c th gii thch l do gc -NH2 b anion ha, hay l s ko cng dao ng ca nhm OH c a nc trong vt liu che lp s xut hin c a 2 mi ny.
100

80

947

899

1153

1070

Transmittance [%] 60

(b)
1253

(a)

836 799

40

20

3314

1422

3507

3393

2997

2646 2577

1691

1592 1553

1567

1496 1452 1420

1374

1318

1236

1122

913 882

781 754

769

676

699

587

578

3800

3500

3200

2900

2600

2300

2000

1800 1600 Wavenumber cm-1

1400

1200

1000 900

800

700

600

500

Sample: H2N-BDC VA IRMOF-3 Technique: KBr

Nr. of Scans: 32 Scanner Velocity: 10 KHz Hnh 2.3 Ph FT-IR: a) IRMOF-3, b) NH2-BDC Source: MIR

Resolution: 2

Aperture: 6mm

Intruments: TENSOR37

Measured by: NGUYEN QUOC VIET

2.1.2.3 Hnh SEM Hnh SEM c a vt liu IRMOF-3 tng hp v hnh tham kho th hin tinh th dng khi lp phng 3D. Tuy nhin ta cng nhn thy khi lp phng khng ng u, b mt tinh th c nhiu vt nt.

514

527

37

a)

b)

Hnh 2.4 nh SEM ca IRMOF-3 a) v tham kho b) [30] 2.1.2.4 Hnh TEM Qua hnh TEM ta thy, y l vt liu c dng l xp, kch thc l xp ln.

Hnh 2.5 nh TEM ca IRMOF-3 2.1.2.5 Phn tch TGA S n nh nhit ca tinh th IRMOF-3 thu c sau khi hot ha c kim tra bng phng php phn tch trng lng nhit TGA, kt qu c th nh sau: Nhit bt u phn h y tinh th IRMOF-3 l 408.2oC, vng nhit 408.2450oC, mu b gim thm 17.03% trng lng do giai on ny c s t chy mt phn cc hydrocacbon c a NH2-BDC.

38

vng nhit 450834.7oC, mu b mt thm khong 35.48% trng lng do giai on ny c s t chy tt c cc hydrocarbon. vng nhit 834.7900oC, mu b gim thm 2.17%, lng tro cn li khng bn b phn h y cho lng tro bn hn v li 45.31% lng tro 899.8oC. Qua kt qu ny cho thy, IRMOF-3 c nhit phn h y kh cao, hn 400oC, c s n nh nhit rt tt, tha mn c yu cu ca vt liu MOFs.

Hnh 2.6 Gin TGA/DTA ca IRMOF-3

2.2 Vt Liu MOF -5 2.2.1 Tng hp MOF -5 MOF-5 c tng hp bng phng php nhit dung mi, theo qui trnh c cng b ca gio s Yaghi. Theo , qu trnh tng hp MOF-5 bao g m 3 giai on: to tinh th, trao i dung mi v giai on hot ha. a. Giai on to tinh th Hn hp c a Zn(NO3)2.6H2O (0.1188g, 0.4mmol) v 1,4 benzenedicarboxylic axit (0.0126g, 0.13mmol) c ha tan trong 10ml DMF. Hn hp c khuy cho n khi tan hon ton nhit phng. Sau hn hp ny c gia nhit n 1000C v c

39

gi ti nhit ny trong vng 24h. Cc tinh th hnh lp phng, c mu hi vng c hnh thnh. b. Trao i dung mi Sau khi c lm ngui n nhit phng, dung mi s dng trong qu trnh tng h p c ht ra, tinh th MOF-5 va thu c, s c ra 3 ln, mi ln 10ml DMF ((3 ln x 10 ml)/3 ngy). Sau mi ln ra, cc tinh th MOF-5 c ngm tip trong dung mi DMF trong vng 24h ((3 ln x 10 ml)/3 ngy). Tip n, cc tinh th MOF-5 c ra vi dung mi dichloromethane 3 ln, mi ln l 10 ml, cc tinh th MOF-5 cng c ngm 24h trong DCM c. Hot ha MOF-5 Tinh th thu c mang i hot ha trong h thng Shlenk-line nhit 1200C trong 6 h thu c 0.59 g vi hiu sut t c: 86% (tnh theo Terephtalic axit).

40

S tng hp:

(2.49g, 9.76mmol) Zn(NO3)2.6H2O + 100 ml DMF

Khuy t

(0.45g, 2.7mmol) H2-BDC + 110 ml DMF

Hn hp phn ng

Gia nhit

100oC trong 1 ngy

Ra tinh th

10ml3 DMF/3 ngy

Trao i dung mi

10ml3 DCM/3 ngy

Hot ha

Chn khng, 120oC,6h

MOF-5
S 2.2 Quy trnh tng hp MOF-5

Zn2+ +

S 2.3 Minh ha phn ng to cu trc MOF-5

41

a)

b)

Hnh 2.7 Tinh th MOF-5 trong dung mi DMF a) v sau hot ha b) 2.2.2. Kt qu v bn lun Trong c u trc c a MOF-5 (Zn4O(BDC)3), cc ion Zn c km bi cc nhm carboxylate c a axit v to thnh cc bt din Zn4O. Cc bt din ny s c kt ni bi cc vng benzen c a axit terephthalic, hnh thnh khung hu c-kim loi ca vt liu MOF-5. MOF-5 c tng hp bng phng php nhit dung mi. Trong DMF c s dng nh dung mi phn cc, c vai tr ha tan tt cc cht ph ng, to iu kin thun li cho qu trnh proton ha cc nhm chc ca cc ligand hu c, t gip cho qu trnh pht tri n tinh th din ra tt hn. Giai on ra tinh th MOF-5 b ng dung mi DMF nhm ha tan cc tc cht khng ph n ng trong qu trnh hnh thnh tinh th. Sau , tinh th MOF-5 tip tc c ra bng DCM, nh m thay i cc lin kt mnh c a DMF bng cc lin kt yu ca DCM vi khung hu c kim loi. Qu trnh ny s gip cho giai on hot ha tinh th sau cng c thun li hn. Cc c tnh c a MOF-5 c xc nh b ng cc k thut phn tch hin i nh XRD, SEM, TEM, AAS, FT-IR, TGA,... 2.2.3 Phn tch cu trc vt liu MOF -5 2.2.3.1 Ph XRD

42

Ph XRD ca MOF-5 tng hp c c peak nhn c trng ti 2=7 v c cc v tr peak tng thch vi kt qu nghin cu ca tc gi Nam T.S. Phan, tc gi Jesse L. C. Rowsell and tc gi Omar M. Yaghi.

b)

a) Hnh 2.8 Ph XRD ca MOF-5 tng hp a) v tham kho b) [26][27][31]

2.2.3.2 Ph hng ngoi IR Phn tch ph hng ngoi ca MOF-5 ta thy hai peak c cng hp thu cao nht ti 1581 cm-1 v 1384 cm-1 l dao ng C=O c a ion carboxylate. V tr peak ti 1502 cm-1 l dao ng khung c a nhn thm, peak ti 747 cm-1 v 819 cm-1 l cc dao ng bin d ng ca cc nguyn t H benzene c hai nhm th v tr para. Cc di rng 36063401 cm-1 chng t c s hin din c a H2O trong vt liu. V tr peak ti 3.606 cm-1 l lin kt ca nhm -OH t do.

43

Hnh 2.9 Ph FT-IR ca MOF-5

2.3.2.3 Hnh SEM Kt qu phn tch tinh th MOF-5 qua knh hin vi in t qut SEM c dng hnh lp phng, ph hp vi nghin c u c a gio s O.M.Yaghi vi cc tinh th lp phng cao.

44

a) Hnh 2.10 a) nh SEM ca MOF-5, b) nh SEM ca MOF-5 tham kho [28]

2.2.3.4 Hnh TEM Phn tch TEM cho nh tht cu trc bn trong vt rn, kt qu nh hin vi in t truyn qua cho thy MOF-5 c t ng hp c cu trc xp cao.

Hnh 2.11 nh TEM ca MOF-5

45

2.3.2.5 Phn tch nhit TGA

Hnh 2.12 Gin TGA/DTA c a MOF-5 Kho st bn nhit ca MOF-5, sau khi hot ha trong chn khng c nghin cu bng phng php phn tch nhit trng lng TGA cho thy c s gim trng lng nh khi ti 400oC v bt u b phn h y tht s khi n 450oC, sau qu trnh phn h y cn khong 49,14% oxide kim loi. Cu trc MOF-5 gm cc n v Zn4O lin kt vi cu ni hu c 1,4 benzenedicarboxylate hnh thnh mng li lp phng thng qua lin kt cng ha tr bn vng. V th MOF-5 c bn nhit cao, nhit phn hy t 350oC-400oC chng t c th ng dng MOF-5 trong khong nhit rng.

46

CHNG 3: NGHIN CU KH NNG HP

PH KH HYDRO CA VT LIU MOFs TNG HP C
Nh bit, th gii chng ta ang b ph thuc vo ngun cung cp nng lng t nhin liu ha thch. Nhin liu c a a s cc phng tin giao thng hin ti: xe hi, xe la, my bay l xng du. Hn na, mt t l kh cao cc nh my in l nhit in dng du ha, kh thin nhin hay than . Nu khng c nhin liu ha thch, nn kinh t cng vi cc phng tin giao thng lin lc, v n ti, s ri vo khng hong, ngng tr. Gn nh ton b nn kinh t, chnh xc hn l ton b x hi hin i ph thuc vo nhin li u ha thch. Nhng n cng tn ti nh ng vn nhc nh i ln: nhim khng kh, cc vn mi trng nh trn du, nguy him v nng bng hn c l vn bin i kh hu ton cu cng vi s nng ln c a tri t Vn hin nay l tm ngun nng lng thay th ngun nng lng ha thch ang s dng rng ri trn ton th gii bng nh ng ngun nng lng sch nh: Nng lng mt tri, nng lng gi, nc,.. Nhng vic s dng ngun nng lng sch cng hn ch do chi ph cao v khng cung cp nng lng cho sn xut v i sng. Hydro c xem l ngun nng lng c a tng lai, sch v c nhiu u im s dng nh : khng gy nhim, khng thi ra kh gy hiu ng nh knh, Hydro c th c sn xut t nhiu ngun khc nhau, Tuy nhin, vic lu tr v vn chuyn hydro vn cn c nhiu thch thc, i hi cn phi c nhiu nghin cu c th ng dng cho vic s dng hydro trong cuc sng thng ngy. Do , trong lun vn ny chng ti tin hnh Nghin cu kh nng hp ph kh H2 c a cc vt liu MOFs (MOF-5, IRMOF-3) vi mc tiu l lu tr kh hydro cng nh nghin c u nh ng kh nng ng d ng ca vt liu MOFs trong hp ph v lu tr kh.

47

Vt liu MOFs c o hp ph kh H2 bng my hp ph p sut cao HPVA.

Hnh 3.1 H thng hp ph p sut cao HPVA.

3.1 Nghin cu Kh hp ph kh H2 ca IRMOF-3. Vt li u IRMOF-3 sau khi c hot ha trong h thng Shlenk-line, c cho vo my hp ph kh HPVA gii hp 8 h nhit 100oC sau mi tin hnh o hp ph kh H2 t i nhit khng i 25oC cho kt qu nh sau:

48

Hp ph mt ln:

Bng 3.1 S liu p sut v khi lng hp ph kh H2 ca IRMOF-3

p Sut (Bar)
2.26 5.32 10.12 15.48 20.90 25.74 30.29 35.31

Th tch (cm3/g)
1.15 2.64 5.21 7.74 10.24 12.71 14.74 16.33

Khi Lng (mg/g)

0.21 1.15 4.32 9.80 17.52 26.78 36.54 47.20

49

Hnh 3.2 ng hp ph kh H2 ca IRMOF-3

Hnh 3.3 ng hp ph v gii hp ca IRMOF-3

Qu trnh hp ph H2 ca IRMOF-3 l kh tt mc hp ph cao nht l 47,2 mg/g ti p sut 35,31 bar, ng gii hp v ng hp ph gn nhau, iu ny c th khng nh

50

trong qu trnh hp ph cu trc tinh th IRMOF-3 khng b thay i di iu kin p sut cao. 3.2 Nghin cu kh nng hp ph kh H2 c a MOF-5 Vi vt liu MOF-5, cng tin hnh nghin cu tng t nh cc vt liu IRMOF-3, cho kt qu nh sau: Hp ph mt ln Bng 3.2 S liu p sut v khi lng hp ph kh H2 ca MOF-5 p Sut (Bar) 2.28 5.38 10.41 16.00 21.01 25.56 30.42 35.49 Th tch (cm3/g) 1.10 2.41 4.80 6.94 9.14 11.56 13.88 16.24 Khi Lng (mg/g) 0.21 1.06 4.09 9.09 15.72 24.18 34.57 47.18

51

Hnh 3.4 ng hp ph kh H2 ca MOF-5

Hnh 3.5 ng hp ph v gi i hp ca MOF-5

52

ng hp v gii hp gn nhau, ch ng t r ng vt liu MOF-5 n nh p sut cao v c tim nng trong lnh vc lu tr kh. 3.3 Kho st kh nng hp ph kh H2 c a cc vt liu MOFs theo phng trnh Freundlich. T phng trnh hp ph Freundlich

V ng hp ph ng nhit.

Kho st cc vt liu MOFs tng hp c c tun theo phng trnh hp ph ng nhit Freundlich hay khng. T s liu hp ph thu c v phng trnh hp ph cho cc biu sau:

Hnh 3.6 ng hp ph H2 ca IRMOF-3 theo Freundlich

53

Hnh 3.7 ng hp ph H2 ca MOF-5 theo Freundlich Bng 3.3 Cc h s ca phng trnh Freundlich i vi cc vt li u MOFs Vt liu MOFs IRMOF-3 MOF-5 1/n 0.505 1.980 lnK 1.592 -3.242 R2 0.999 0.999

T cc ng hp ph ta c th thy rng tt c cc vt liu u tun theo phng trnh hp ph Fruendlich.

54

CHNG 5: KT LUN V KIN NGH

Cc vt liu IRMOF-3, MOF-5 l nh ng vt liu c cu trc tinh th dng xp, c tng hp thnh cng bng phng php nhit dung mi, bng cc phng php phn tch cu trc nh XRD, FTIR, SEM, TEM , TGA, cc kt qu thu c ph hp vi cc nghin c u cc tc gi trc y. Cc vt liu tng i bn nhit, MOF-5 c b n nhit kho ng nhit 450oC, IRMOF-3 c bn nhit khong 4000C mi bt u b phn h y. Cc vt liu MOFs tng hp c c kh nng hp ph kh H2 cao, IRMOF-3 vi 47.2 mg/g, MOF-5 l 47,18 mg/g v bn p sut cao, qua kho st cc vt liu IRMOF3, MOF-5 c th thy rng cc vt liu ny c kh nng ti s dng tt sau khi hp ph nhiu ln. IRMOF-3 v MOF-5 u tun theo phng trnh hp ph Fleundlich *** Kin ngh cho cc phng php nghin cu tip theo: - Nghin c u kh nng lu tr kh H2 ca mt s loi MOFs khc - Tip t c nghin cu bn c a cc vt liu MOFs trong iu kin nhit , p sut v cc iu kin dung mi khc nhau - Nghin c u kh nng lu tr kh CH4 - Tinh ch kh.

55

TI LIU THAM KHO

[1] Jeongyong Lee, Synthesis and gas sorption study of microporous metal organic frameworks for hydrogen and methane storage, The State University of New Jersey, 2007. Ly Tu Uyen, Synthesis and Characteriztion of High Porous Metal-Organic Frameworks: MOF-199 and ZIF-8, 2009, thesis, HCMC University of Technology

[2]

[3]

Xueyu Zhang, Hydrogen storage and carbon dioxide capture by highly porous Metal-Organic Frameworks, 2010. [4] Mohamed Eddaoudi, D.B.M., Hailian Li, Banglin Chen, Theresa M. Reineke, Michael Okeeffe, And Omar M. Yaghi, Acc. Chem. Res. 2001. 34: p. 319-330. [5] R Saravanakumar and S Sankararaman, Molecule Matters: Metal Organic Frameworks (MOFs), Feature Article, 2007. [6] David J. Tranchemontagne, Z.N., Michael O Keeffe, and Omar M. Yaghi, Angew. Chem. Int. Ed. 2008. 47: p. 5136 -5147. [7] Hiroyasu Furukawa, J.K., Nathan W. Ockwig, Michael O Keeffe, Omar M. Yaghi, J. Am. Chem. Soc. 2008. 130: p. 11650-11661. [8] David J. Tranchemontagne, J.L.M.-C.s., Michael OKeeffe and a.O.M. Yaghi, Chem. Soc. Rev. 2009. 38: p. 12571283. [9] Jesse L. C. Rowsell and Omar M. Yaghi, Strategies for Hydrogen storage in Metal-Organic Frameworks, Angew. Chem. Int. Ed., 2005, 44, 4670-4679. [10] Omar M. Yaghi, Porous crystals for carbon dioxide storage. [11] Steven S. Kaye, A.D., Omar M. Yaghi et al., J. Am. Chem. Soc. 2007. 129: p. 14176-14177. [12] Claudia Prosenjak, Experimental and theoretical adsorption studies in tuneable organic-inorganic materials, The University of Edinburgh Institute for Materials and Processes, USA, 2009 [13] Leonard R. MacGillivray, Metal-Organic Frameworks: Design and Application, John Wiley & Sons, Inc., Hoboken, New Jersey, Canada.

56

[14] Ryan J.K, Daren J.T, Qian-Rong Fang, Jian-Rong Li, Trevor A.Makal, Potential application of metal-organic frameworks, Coodination Chemistry Reviews, 2009, 253, 3042-3066. [15] Antek G. Wong-Foy, A.J.M., Omar M. Yaghi, J. Am. Chem. Soc. 2006. 128: p. 3494-3495. [16] Jesse L. C. Rowsell, A.R.M., Kyo Sung Park, Omar M. Yaghi, J. Am. Chem. Soc. 2004. 126: p. 5666-566 [17] Insilicotech Co. Ltd, Metal Organic Frameworks: Rational Design to Materialization for Hydrogen Storage, 2008, Accelrys Korea [18] Andrew R. Millward, O.M.Y., J. Am. Chem. Soc. 2005. 127: p. 1799817999. [19] Alexander U. Czaja, N.T., Ulrich Muller, Chem. Soc. Rev. 2009. 38: p. 12841293. [20] Jeong Yong Lee, Omar K. Farha, John Roberts, Karl A. Scheidt, Son Binh T. Nguyen and Joseph T. Hupp, Metal-Organic Frameworks Materials as catalysts, Chem. Soc. Rev., 2009, 38, 1450-1459. [21] Shilun Qiu, G.Z., Coordination Chemistry Reviews. 2009. [22] M. D. Allendorf, C.A.B., R. K. Bhakta, R. J. T. Houk, Chem. Soc. Rev. 2009. 38: p. 13301352. [23] Sabine Achmann, Gunter Hagen, Jaroslaw Kita, Itamar M. Malkowsky, Christoph Kiener and Ralf Moos, Metal-Organic Frameworks for Sensing Applications in the Gas Phase, Sensors., 2009, 9, 1574-1589. [24] William G. Schulz, Lauren K. Wolf, Size -Selective acid catalysis, C&EN News of the week, 2008. [25] David J. Tranchemontagne, Joseph R. Hunt, Omar M. Yaghi Ro om temperature synthesis of metal-organic frameworks: MOF-5, MOF-74,MOF-177, MOF-199, and IRMOF-0, Tetrahedron 64,2008, P.85538557 [26] Nam T.S. Phan, Ky K.A. Le, Tuan D. Phan, MOF-5 as an efficient heterogeneous catalyst for FriedelCrafts alkylation react ions, Elsevier, 2010 [27] U. Mueller,* M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt and J. Pastre Metal organic frameworksprospective industrial applications, Journal of Materials Chemistry, 2005

57

[28] Frank Stallmach, S.G., Volker Kunzel, Jorg Karger, O. M. Yaghi, Michael Hesse, Ulrich Muller, Angew. Chem. Int. Ed., 2006. 45: p. 2123 -2126 [29] Zhenqiang Wang and Seth M. Cohen Tandem Modification of MetalOrganic Frameworks via a Postsynthetic Approach Supporting Information Wiley-VCH 2008 [30] Mingyan Ma, Denise Zacher, Xiaoning Zhang, Roland A. Fischer, and

Nils Metzler-Nolte A Method for the Preparation of Highly Porous, Nanosized Crystals of Isoreticular Metal-Organic Frameworks Crystal growth design article., 2011,Vol 11, P. 185-189 [31] Jesse L. C. Rowsell and Omar M. Yaghi* Effects of Functionalization, Catenation, and Variation of the Metal-Oxide and Organic Linking Units on the Low Pressure Hydrogen Adsorption Properties of Metal-Organic Frameworks (SupportingInformation) [32] Yaghi et al. Isoreticular metal-organic frameworks, process for forming the same, and systematic design of pore size and functionality therein, with application for gas storage. US Patent Publication. 2005 [33] Yaoqi Li, Lei Xie, Yang Liu, Rong Yang, and Xingguo Li Favorable Hydrogen Storage Properties of M(HBTC)(4,4 -bipy) 3DMF Inorg. Chem. 2008, 47, 10372 10377 [34] Jun Kim, Seung-Tae Yang, Sang-Beom Choi, Jaeung Sim, Jaheon Kim, and Wha-Seung Ahn Control of Catenation in CuTATB-n Metal-Organic Frameworks by Sonochemical Synthesis and its Effect on CO2 Adsorption Supplementary Material (ESI) for Journal of Materials Chemistry 2011. [35] [36] [37] Minh Operation manual novawin series version 10.0,Quantachrome instrument Mai H u Khim, Gio trnh ha keo, i Hc Quc Gia TP.H Ch Minh Nguyn Ngc Hnh, Th nghim Ha L, i Hc Bch Khoa TP.H Ch

[38] Lm Ngc Thm, Trn Hip Hi, Nguyn Th Thu, Ha L C S, Nh xut bn khoa hc k thut.

58

[39] 2009. [40] 2010.

Lun. T.V Lu v T S B Mn Ha Hu C, BK. Tp. CM Hnh. N.T.N Lu v T S B Mn Ha Hu C, BK. Tp. CM