Luan Van MOF Thao

LI CAM N
Em xin gi li cm n su sc n thy L Ngc Thch v thy on L Hong Tn

tn tnh hng dn, ch bo v gip em trong sut thi gian thc hin ti cung nh
trong qua trnh hon thnh v bo v lu n vn.
Em xin by t lng bit n i vi Ban Giam Hiu, khoa Ha hc trng i hc Khoa
hc t nhin TPHCM v Trung Tm Nghin Cu Vt Liu Cu Trc Nano V Phn T
(trung tm MANAR) to iu kin thun li cho em trong sut qua trnh hc tp v
nghin cu ti.
Xin chn thnh cm n i ngu can b lm vic ti trung tm MANAR, TS. Nguyn Thai
Hong, TS. Nguyn Th L Anh, TS. Nguyn Tn Ti, cac anh ch nghin cu sinh: anh
Thch, anh Bo, anh H, anh Bnh, anh Long v cac anh ch khac: anh Bn, ch Linh
nhit tnh gip v a ra nhng kin ng gp qu bau trong qua trnh em thc hin
ti.
Con xin by t lng bit n su sc n b m v gia nh, cam n mi ngi lun tin
tng v l ch da tinh thn mi khi con gp kh khn, lun ng vin, khuyn khch
con t tin tip tc thc hin cho n khi hon thnh lun vn.
Mc d c gng hon thnh lun vn trong phm vi v kh nng ca mnh, nhng v
nng lc bn thn cn nhiu hn ch nn chc chn s khng tranh khi nhng thiu st,
em rt mong nhn c s cm thng v gp ca qu thy c, anh ch v cac bn.
SVTH: L Hunh Thanh Tho
Trang 1
MUC LUC
MUC LUC
LI CAM N...................................................................................................................1
DANH MUC HINH VE...................................................................................................5
DANH MUC BANG BIU..............................................................................................8
DANH MUC T VIT TT...........................................................................................9
LI M U.................................................................................................................11
CHNG 1 TNG QUAN...........................................................................................12
1.1.
KHI QUT MOF..................................................................................................12
1.1.1.
Khai nim.....................................................................................................12
1.1.1.1. Phn kim loi............................................................................................15

1.1.1.2. Phn linker hu c....................................................................................15
1.1.1.3. Khai ni m khi cu trc th cp (secondary building unit, SBU).............17
1.1.2.
Cac th h MOF v ang c nghin cu..............................................18
1.1.3.
M t s phng phap tng hp MOF v cac yu t nh hng.....................19
1.1.3.1. Phng phap nhit dung mi (solvothermal)............................................19

1.1.3.2. Phng phap thuy nhit (hydrothermal)...................................................20
1.1.3.3. Phng phap khng dung mi (solvent-free)............................................20
1.1.3.4. Phng phap ion nhit (ionothermal).......................................................20
1.1.3.5. Phng phap i n ha...............................................................................20
1.1.3.6. Phng phap vi sng................................................................................20
1.1.3.7. Cac yu t nh hng...............................................................................21
1.1.4.
Cac phng phap kim tra c tnh..............................................................22
1.1.5.
ng dng ca MOF.....................................................................................23
1.1.5.1. Kh nng hp ph kh...............................................................................23

1.1.5.2. Lu tr kh................................................................................................26
1.1.5.3. Kh nng xc tac......................................................................................27
1.1.5.4. ng dng sinh hc....................................................................................28
1.1.5.5. Kh nng tach...........................................................................................29
1.1.6.
Nhng hn ch ca MOF.............................................................................29
Trang 2
MUC LUC
1.2.
GII THIU V ZR-MOF.......................................................................................30
1.2.1.
M t s loi v t li u MOF s dng Zr

...........................................................32
1.2.1.1. UiO-n........................................................................................................32
1.2.1.2. PIZOF.......................................................................................................34
1.2.1.3. MOF-525, MOF-535, MOF-545...............................................................35
1.2.1.4. Zr-fum.......................................................................................................35
1.2.2.
Vai tr ca cht iu hng (modulator) trong Zr-MOF..............................36
1.2.3.
M t s ng dng ca Zr-MOF.....................................................................37
1.3.
KHAI QUAT V CAC PHAN NG TRONG QUY TRINH TNG HP LINKER
HOOC[PEP(CONH2)EP]COOH, (P-PHENILEN, E-ETINILEN)........................................38

1.3.1.
Phn ng iu ch clorur acid......................................................................38
1.3.2.
Phn ng amin gii.......................................................................................39
1.3.3.
Phn ng ghep c p Sonogashira...................................................................39
1.3.4.
Phn ng thy gii.......................................................................................41
CHNG 2 KT QUA VA BIN LUN ...................................................................42

2.1.
TNG HP ACID 4,4'-(2-CARBAMOIL-1,4-PHENILEN)BIS(ETIN-1,2-DIIL)DIBENZOIC
(ACPEB)........................................................................................................................42
2.1.1.
Phn ng tng hp 2,5-diiodobenzamid.......................................................42
(a) Phn tch FT-IR.................................................................................................43

(b) Phn tch 1H NMR............................................................................................43
2.1.2.
Phn ng Sonogashira..................................................................................44
(a) Phn tch FT-IR.................................................................................................45

(b) Phn tch 1H NMR............................................................................................45
(c) Phn tch 13C NMR...........................................................................................45
(d) Phn tch MS....................................................................................................45
2.1.3.
Phn ng thy gii.......................................................................................46
(a) Phn tch FT-IR.................................................................................................46

(b) Phn tch 1H NMR............................................................................................46
(c) Phn tch 13C NMR...........................................................................................47
(d) Phn tch MS....................................................................................................47
2.2.
TNG HP ZR-MOF.............................................................................................47
Trang 3
MUC LUC
2.2.1.
Kho sat iu kin tng hp Zr-ACPEB......................................................47
2.2.1.1. Kho sat tng hp theo nng ...............................................................47

2.2.1.2. Kho sat tng hp theo ng lng acid acetic (khng nc)................48
2.2.1.3. Kho sat tng hp theo ng lng acid acetic (thm nc)..................49
2.2.1.4. Kho sat tng hp theo lng nc..........................................................51
2.2.1.5. Kho sat tng hp theo nhi t ...............................................................52
2.2.1.6. Kho sat tng hp theo thi gian..............................................................53

2.2.2.
Kt qu phn tch c tnh cu trc ca Zr-ACPEB.....................................53
2.2.2.1. Phn tch FT-IR.........................................................................................53

2.2.2.2. Phn tch nhi t trng lng (TGA)...........................................................54
2.2.2.3. Di n tch b m .t.......................................................................................56
CHNG 3 THC NGHIM......................................................................................57
3.1.
DUNG CU, HOA CHT, THIT BI. ...........................................................................57
3.1.1.
Dng c........................................................................................................57
3.1.2.
Ha cht.......................................................................................................57
3.1.3.
Thit b.........................................................................................................58
3.2.
THC NGHIM.......................................................................................................58
3.2.1.
Quy trnh iu ch linker HO2C[PEP(CONH2)EP]CO2H.............................58
3.2.1.1. Phn ng iu ch benzamid....................................................................58

3.2.1.2. Phn ng Sonogashira...............................................................................58
3.2.1.3. Phn ng thy gii....................................................................................59
3.2.2.
Tng hp Zr-MOF vi linker HO2C[PEP(CONH2)EP]CO2H......................59
3.2.2.1. Quy trnh tng hp....................................................................................59

3.2.2.2. Quy trnh trao i dung mi......................................................................59
3.2.2.3. Quy trnh hot hoa....................................................................................60
CHNG 4 KT LUN...............................................................................................61
TAI LIU THAM KHAO.............................................................................................62
CHNG 5 PHU LUC..................................................................................................67
Trang 4
DANH MUC HINH VE
DANH MUC HINH VE

Hnh 1-1: Minh ha cu to ca MOF [2]........................................................................12
Hnh 1-2: Minh ha m t s cu trc ca MOF.................................................................13
Hnh 1-3: Cu trc tng quat dng 3D ca MOF: linker hu c vi hai nhm chc kt
hp vi ion kim loi.........................................................................................................16
Hnh 1-4: Tng hp MOF c linker mang nhm chc bng hai phng phap: tin tng
hp v h u tng hp.........................................................................................................17
Hnh 1-5: (a) m t SBU bat di n ca MOF-5, (b) cac SBU lin kt vi cac n v benzen
to thnh m t mng li nguyn khi.........................................................................18
Hnh 1-6: Qua trnh hydrat hoa v dehydrat hoa din ra trong MIL-53 (Al, Cr)..............19
Hnh 1-7: Kho sat kh nng hp ph CO2 ca mt s loi MOF nhit phng. [16] 24
Hnh 1-8: Minh ha kh nng lu tr kh CO2 ca MOF-177. [17].................................24
Hnh 1-9: Hnh minh ha lin kt gia nhm chc CONH2 ca MOF vi CO2..............25
Hnh 1-10: Cu trc tinh th ca MOF-5. (khi t di n ZnO4-tm, C-xam, O-xanh).......26
Hnh 1-11: Phn ng ngng t aldol s dng xc tac d th UiO-66-NH2........................28
Hnh 1-12: Cu trc ca MIL-53 gm AlO6 cu trc bat di n gn vi benzen dicarboxilat.
......................................................................................................................................... 29
Hnh 1-13: Cluster dng hidrat hoa Zr 6O4(OH)4 v dehidrat hoa Zr6O6. (Zr-, O-xanh,
C-xam, H-trng)...............................................................................................................31
Hnh 1-14: Cluster hon chnh cho thy s thay i trong s phi tr ca zirconium t 8
thnh 7 do s kh H2O. (Zr-, O-xanh, C-xam, H-trng)...............................................31
Hnh 1-15: Cu trc ca cluster Zr6(3-O)4(3-OH)4(COO)12. (Zr-xanh, O-, C-en) [36]
......................................................................................................................................... 31
Hnh 1-16: Cu trc SBU m r ng ca cluster Zr-O, gn vi 12 linker hu c. (Zr-xanh,
C-xam, O-) [37]............................................................................................................ 31
Hnh 1-17: Cu trc tng quat th hi n di dng a di n. (Zr-lc lam, O-, C-xam)
[37]................................................................................................................................... 32
Hnh 1-18: (a) Cu trc bat di n ca Zr-MOF, (b) Zr-MOF vi 1,4-benzen dicarboxilat
(BDC) lm linker, UiO-66, (c) Zr-MOF vi 4,4-biphenil dicarboxilat (BPDC) lm linker,
UiO-67, (d) Zr-MOF vi terphenil dicarboxilat (TPDC) lm linker, UiO-68. (Zr-, Oxanh, C-xam, H-trng) [35]..............................................................................................32
Trang 5
DANH MUC HINH VE

Hnh 1-19: Cac linker vi di m r ng c s dng trong tng hp Zr-MOF. [39]
......................................................................................................................................... 33
Hnh 1-20: S thay th cac nhm chc khac nhau t UiO-66-NH2..................................33
Hnh 1-21: SBU ca PIZOF-1. [41].................................................................................34
Hnh 1-22: Cu trc PEPEP..............................................................................................34
Hnh 1-23: Tng hp PIZOF. [41]....................................................................................34
Hnh 1-24: Cu trc ca (a) MOF-525, (b) MOF-535, (c) MOF-545...............................35
Hnh 1-25: (a) Cu trc ca linker fumarat khng tuyn tnh, (b) v (c) M hnh cu trc
ca Zr-fum MOF. (b) mng c s hnh l p phng. (c) Cu trc bat di n ca m t
mng c s. [43]............................................................................................................... 35
Hnh 1-26: nh hng ca vi c s dng acid benzoic ln hnh thai v kch thc ca tinh
th UiO-66....................................................................................................................... 36
Hnh 1-27: Minh ha kh nng hnh thnh ht nhn nh hng bi nng modulator.
(ion kim loi-khi cu xanh la, linker-g y xam, ht nhn-khi cu tm, tinh th-khi
vung )......................................................................................................................... 37
Hnh 1-28: Phn ng gia acid carboxilic vi SOCl2.......................................................38
Hnh 1-29: C ch phn ng vi SOCl2 xc tac DMF......................................................38
Hnh 1-30: Phn ng gia clorur acid vi NH3................................................................39
Hnh 1-31: Phn ng ghep c p Sonogashira.....................................................................39
Hnh 1-32: C ch d oan ca phn ng Sonogashira vi xc tac paladium v Cu(I). . .40
Hnh 1-33: Phn ng thy gii.........................................................................................41
Hnh 1-34: C ch phn ng thy gii ester trong mi trng baz...................................41
Hnh 2-1: Quy trnh tng quat iu ch linker diacid HOOC[PEP(CONH2)EP]COOH...42
Hnh 2-2: Quy trnh phn ng iu ch benzamid............................................................42
Hnh 2-3: Quy trnh phn ng ghep c p alkinil-aril.........................................................44
Hnh 2-4: Quy trnh phn ng thy gii...........................................................................46
Hnh 2-5: Tng hp MOF vi linker ACPEB...................................................................47
Hnh 2-6: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo nng ....................48
Hnh 2-7: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo ng lng AcOH
(khng nc).................................................................................................................... 49
Trang 6
DANH MUC HINH VE

(thm nc)...................................................................................................................... 50
Hnh 2-9: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo lng nc thm vo.
......................................................................................................................................... 51
Hnh 2-10: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo nhi t . ................52
Hnh 2-11: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo thi gian.................53
Hnh 2-13: Gin phn tch nhi t TGA ca tinh th MOF va tng hp.......................54
Hnh 2-14: Gin phn tch nhi t TGA ca tinh th MOF sau khi hot hoa..................55
Trang 7
DANH MUC T VIT TT
DANH MUC BANG BIU

Bng 1-1: C cu ca m t s ion kim loi v linker hu c dng trong tng hp MOF.. 12
Bng 1-2: M t s loi MOF c kim tra kh nng lu tr kh hidrogen.................24
Bng 2-1: Kho sat nh hng ca xc tac n hi u sut phn ng vi SOCl2................41
Bng 2-2: Kho sat nh hng ca nhi t ti hi u sut phn ng vi NH3...................41
Bng 2-3: D li u t ph 1H NMR (300 MHz, DMSO-d6)..............................................41
Bng 2-4: Kho sat phn ng theo nhi t . ...................................................................42
Bng 2-5: Kho sat phn ng theo thi gian....................................................................42
Bng 2-6: D li u t ph 1HNMR (500MHz, DMSO d6)...............................................43
Bng 2-7: D li u t ph 13CNMR (500MHz, DMSO d6)..............................................43
Bng 2-8: D li u t ph 1HNMR (500MHz, DMSO d6)...............................................44
Bng 2-9: D li u t ph 13CNMR (500MHz, DMSO d6)..............................................45
Bng 2-10: Kho sat tng hp Zr-ACPEB theo nng ..................................................46
Bng 2-11: Kho sat tng hp Zr-ACPEB theo ng lng AcOH (khng nc).........47
Bng 2-12: Kho sat tng hp Zr-ACPEB theo ng lng AcOH (thm nc)...........48
Bng 2-13: Kho sat tng hp Zr-ACPEB theo lng nc thm vo.............................49
Bng 2-14: Kho sat tng hp Zr-ACPEB theo nhi t . ................................................50
Bng 2-15: Kho sat tng hp Zr-ACPEB theo thi gian................................................51
Trang 8
DANH MUC T VIT TT
DANH MUC T VIT TT

UiO
University of Oslo (in Norway)
UCLA
University of California, Los Angeles
MOF
Metal Organic Frameworks
MIL
Materials of the Institut Lavoisier
IRMOF
Isoreticular
HKUST
Hong Kong University of Science and Technology
PIZOP
Porous Interpenetrated Zirconium Organic framework
SBU
Secondary Building Unit
PSM
Post-Synthesis Modification
NMR
Nuclear Magnetic Resonance spectroscopy
MS
Mass Spectrometry
P-XRD
Powder X-Ray Diffraction
SC-XRD
Single crystal X-Ray Diffraction
FT-IR
Fourier Transform Infrared Spectroscopy
TGA
Thermogravimetric Analysis
BET
Brunauer - Emmett - Teller
DMF
N, N-Dimethylformamide
DEF
Diethylformamide
TEA
Triethylamine
THF
Tetrahydrofuran
Otf
triflat hay trifluorometansulfonat
bdc
benzen 1, 4-dicarboxilat
bpdc
biphenyldicarboxilat
ndc
napthalen-2,6-dicarboxilat
hpdc
4,5,9,10-tetrahidropyren-2,7-dicarboxilat
tmbdc
2,3,5,6-tetramethilbenzen-1,4-dicarboxilat
btb
benzen-1,3,5-tribenzoat
Trang 9
DANH MUC T VIT TT

dabco
1,4-diazabiciclo[2.2.2]octan
btc
benzen-1,3,5-tricarboxilat
3-pic
3-picolin
pd
1,2-propanediol
ttdc
thieno[3,2-b]thiophen-2,5-dicarboxilat
Trang 10
LI M U
LI M U
S phat trin vt bc ca khoa hc k thut to tin cho ngnh khoa hc vt liu
v ha hc phat trin. T , rt nhiu vt liu mi c ra i. V t liu xp ang thu
ht c nhiu s quan tm bi nhng ng dng a dng v phong ph trong cng
nghi p (xc tac, ly trch, v.v). Hi n nay cac hng nghin cu v ng dng t p trung
kha nhiu vo zeolit, metalophosphat, carbon hot tnh ho c cac v t li u mesoporous
(covalent 2 50 nm). Gn y, c thm s ch trng n m t loi v t li u c cu trc
khung, l v t li u lai ha c to thnh t cac thnh phn hu c v v c c gi
l vt liu khung hu c-kim loi (Metal organic framework, MOF) c phat trin bi
nhm nghin cu ca Omar Yaghi vi xp, ng knh v th tch l xp ln vt
b c so vi v t li u zeolit m t thi tng c xem l c xp cao nht.
K t khi vt liu MOF c cng b bi Yaghi v nhm nghin cu trng i hc
UCLA vo nm 1997, s lng MOF c tng hp hi n ang tng u n da vo s
a dng ca ngnh ha hc hu c, cung nh s phong ph ca cac kim loi trong bng
tun hon vi kch thc l xp, hnh dng v chc nng hu c hon ton khac bi t
nhau. V t li u ny c kh nng ng dng v cng phong ph trong nhiu linh vc bao
gm chuyn hoa nng lng m t tri thnh i n nng, xc tac, lu tr cac kh dng cho
nng lng nh hidrogen v metan, tach cac kh thi c hi cho mi trng nh CO2,
CO v H2S
Mc tiu nghin cu ca lun vn ny l trnh by nghin cu v quy trnh tng hp
linker c mang nhm chc CONH2, ng vai tr l mt linker hu c trong tng hp
MOF, nhm nng cao kh nng hp ph CO 2 ca loi vt liu ny. ng thi, kho sat
kh nng hnh thnh MOF ca linker, s dng Zr lm phn kim loi.
Trang 11
TNG QUAN
Chng 1
TNG QUAN
1.1. Khi qut MOF

1.1.1.
Khi nim
MOF l loi v t li u dng tinh th, c c cu khung, l mt chui cu trc m rng c

cu thnh t cac n v ion kim loi lin kt vi nhau thng qua cac linker hu c a
chc. Trong , linker hu c ng vai tr lm cu ni, phn kim loi l cac khp ni ca
khung. T , hnh thnh nn mt mng li cu trc khng gian ba chiu c din tch b
mt ln v cac l xp c kch thc nano [1]. Kt cu ny c thit k nhm tng ti a
din tch b mt, nhng vn m bo cho cu trc bn c th s dng vt liu MOF
trong cac iu kin khac nhau.
Ion kim loi / cluster kim loi
Linker hu c
Hnh 1-1: Minh ha cu to ca MOF [2].
Trang 12
TNG QUAN
Khac vi cac v t li u cu trc xp truyn thng nh zeolit hay cac loi silica nh SBA15, MCM-41, MOF c cac l xp c ngn cach vi nhau bng nhng cu trc phn t
ch khng phi bng nhng vach ngn dy. Do MOFs c di n tch b m t ring v
th tch l xp cao hn nhiu so vi cac v t li u cu trc xp truyn thng .
M t tnh cht c bi t ca MOF l isorecticular c nghia l vi c gia tng di ca
linker hu c ng thi vn gi nguyn kiu cu trc vi MOF to bi linker m ban
u, nhm to ra cac th h MOF c cng cu trc nhng di n tch b m t v kch thc
l xp c ci thi n hn.
Da vo kh nng phi tr hnh hc a dng ca cac ion kim loi, nhiu loi MOF vi kt
cu khac nhau c thit k v phat trin: dng t ong, mng li bat din, t di n,
dng l p phng
Hnh 1-2: Minh ha m t s cu trc ca MOF.
Trang 13
TNG QUAN
Bng 1-1: C cu ca m t s ion kim loi v linker hu c dng trong tng hp MOF.
Ion
kim
loi/
cluster
Li+, Na+ , Cu+, Ag+, Ni2+, Mg2+, Zn2+, Cd2+, Cu2+, Fe2+, Mo2+, Rh2+,
Ru2+, Al3+, V3+, Cr3+, Zr4+, ZnO4+
kim
loi
Linke
r hu
c
Acid tereptalic
Acid 1,3,5benzentricarboxilic
4,4-dipiridin
4,4,4-benzen-1,3,5-
4,4',4''-(benzen-1,3,5-triil-tris (benzen-4,1-
triilbenzoat (BTB)
diil)tribenzoat (BBC)
Trang 14
TNG QUAN
Acid hexacarboxilic (LH6)

bn ca MOF ph thuc ch yu vo cluster kim loi v bn lin kt gia cluster
kim loi v linker hu c. Do , vi c tm ra nhng kiu cluster kim loi mi bn v linh
hot l mc tiu quan trng tng hp cac MOF mi c kh nng ng dng trong iu
kin thc t.
1.1.1.1.
Phn kim loi
Phn kim loi thng l cation kim loi hoc cluster kim loi (nhm kim loi a nhn).
Phn kim loi ca MOF thng c tin cht l mui (halogenur, nitrat, perclorat hoc
hidroxid) nhng c th l chnh kim loi c oxid ha sau trong qua trnh phn ng
bng cach thm vo cac tac nhn oxid ha nh l nitric hoc acid percloric.
1.1.1.2.
Phn linker hu c
Linker hu c thng l cac linker di-, tri- hoc tetradentat, gm mt hoc nhiu vng
benzen c cha cac nhm to phc (carboxilat, phosphat, sulfonat hay cac dn xut ca
nitrogen nh pyridin, imidazol). Trong , cac linker c cha nhm carboxilat c s
dng nhiu nht do c kh nng to nhiu kiu ni phi tr khac nhau, v gip gia tng
cng cho cu trc da vo hiu ng cng ha bn cnh hai ni mnh: [kim loi oxigen
carbon], nh cac ion kim loi c c nh mt cach chc chn s to ra c m t
nhm nguyn t c s nh hng ro rng. [2]
Trang 15
TNG QUAN
Hnh 1-3: Cu trc tng quat dng 3D ca MOF: linker hu c vi hai nhm chc kt
hp vi ion kim loi.
Kch thc ca linker c th iu chnh d dng bng cach m rng khung sn carbon.
Trong nhng nm gn y, vic thay th cac vng benzen trong cu trc linker bng cac
nhm alkin ang c nghin cu nhm ci thin din tch b mt ring ca vt liu
MOF.
Ngoi ra, tnh cht ca MOF c th c ty chnh thng qua vi c s dng cac linker vi
cac nhm chc hu c khac nhau, c th l phn cc, tnh acid-baz v kh nng chonh n i n t s thay i ty thu c vo cac nhm chc hu c nh hidrogen, amin,
hidroxil gn trn linker, nhng linker c gc t do s to nn cac v t li u c t tnh. Nh
v y nhng ng dng ca MOF c th bin i a dng.
Linker mang nhm chc c th c gn ln MOF bng hai cach:
Tin tng hp (pre-synthesis): linker c tng hp vi y nhm chc, sau
em i tng hp MOF.
H u tng hp (post-synthetic modification): nhm chc chnh ca linker c b
sung sau khi linker c gn vi phn kim loi v to thnh MOF.
Trang 16
TNG QUAN
Hnh 1-4: Tng hp MOF c linker mang nhm chc bng hai phng phap: tin tng
hp v h u tng hp.
1.1.1.3.
Khi ni m khi cu truc th cp (secondary building unit, SBU)
SBU l m t quan im m c s dng trong vi c miu t cac mnh ca zeolit.
Trong quan im ca ha hc mng li, SBU dng m t m t cach n gin dng
hnh hc ca m t n v thng qua cac im m ca n v (v d nh nguyn t
carbon trong nhm carboxilat- thng thy trong hu ht cac loi MOF c linker mang
nhm carboxilat). SBU l m t cng c hu ch trong vi c m t s lc cu trc ca
MOF. [3]
Trong vi c d oan v gii thch cu trc MOF, SBU c coi l khp, cn cac cu ni
hu c (hay ligand) c coi l thanh chng ca mng li c bn. Khi xem xet cac
thu c tnh hnh hc v ha hc ca SBU v ca cac ligand c th d oan c cu trc
lin kt ca v t li u MOF. Do , cu trc ligand v SBU c nh hng quyt nh n
cu trc MOF.
Trang 17
TNG QUAN
n v v c
SBU
n v hu c
SBU
Hnh 1-3: Minh ha cac SBU t MOF carboxilat.

(cluster kim loi-khi a di n mu xanh, O-, C-en) [2]
Hnh 1-5: (a) m t SBU bat di n ca MOF-5, (b) cac SBU lin kt vi cac n v benzen
to thnh m t mng li nguyn khi.
Trang 18
TNG QUAN
1.1.2.
Cc th h MOF a va ang c nghin cu
Da vo linh hot v n nh, MOF c th c chia thnh ba th h :

Th h u tin s dng linker to ni yu: 4, 4-bipiridin do tinh th c th
chuyn thnh dng v nh hnh nu gia tng nhi t .
Th h th hai bn hn bng cach s dng nhng nhm chc mnh trn linker
nh acid dicarboxilic v tinh th c th duy tr c cu trc sau khi loi b cac
phn t cn nm trong l xp m vn gi c di n tch b m t v th tch l xp
cao.
Th h th ba s hu kh nng bin i linh hot m vn gi nguyn c cu
trc. Tinh th khng ngng thay i do cac ni hidrogen trong cu trc lm cu
trc khung khng ngng thay i dn n s ng-m ca h thng l xp. y
l m t tnh cht c bi t gy ra do s loi b v hp ph cac phn t ngoi lai vo
l xp m khng pha huy cu trc ca v t li u. Bn cht ca cac phn t ngoi lai
gy nh hng n s thu hp v m r ng ca th tch l xp (breathing). Ni
hidrogen c th c hnh thnh gia hidrogen ca phn t nc, nguyn t
oxigen ca nhm carboxilat v nhm hydroxyl ca kim loi trung tm. [4]
Hnh 1-6: Qua trnh hydrat hoa v dehydrat hoa din ra trong MIL-53 (Al, Cr).
1.1.3.
M t s phng php tng hp MOF va cc yu t nh hng
MOF c th c tng hp t nhiu phng phap khac nhau nh nhit dung mi, tng
hp ion nhi t v vi sng. Trong , phng phap tng hp nhit dung mi l phng
phap thng c s dng do thao tac k thut n gin, tuy thi gian phn ng kha lu
nhng cho tinh th c kch thc ln v din tch b mt ring cao.
Trang 19
TNG QUAN
1.1.3.1.
Phng php nhit dung mi (solvothermal)
K thut ny da vo bn cht kt tinh t dung mi nhit cao v ap sut cao.

Phng phap c thc hin trong h kn, bng cach nung nng hn hp gm mui c
cha ion kim loi v nhng phn t hu c trong mt h dung mi ph hp ti nhi t
cao hn nhi t si ca dung mi, ion kim loi s to phi tr vi cac linker hu c sao
cho t c tnh i xng cao nht. [5]
1.1.3.2.
Phng php thuy nhit (hydrothermal)
Dung mi s dng l nc, tin hnh nhi t cao (180oC-220 oC), ap sut cao. Trong
m t s trng hp c th thm vo cac cht khoang hoa tng kh nng ho tan.
1.1.3.3.
Phng php khng dung mi (solvent-free)
Tin hnh m t cach n gin l nghin v tr n cac tac cht li, phn ng trong iu ki n
khng dung mi. Phng phap ny nhanh, d dng thc hi n v thn thi n vi mi
trng cho vi c tng hp MOF v rt hu dng khi tng hp MOF vi cac linker ln
kh tan.
Tng hp khng dung mi thng dng tng hp tinh th kep v cht rn i phn t.
Phng phap ny c m r ng ra i vi cac polimer phc v cac cht microporous
3D ho c 1D. [6, 7, 8]
1.1.3.4.
Phng php ion nhit (ionothermal)
Cht lng ion (vi u im nh bn nhi t cao, khng c ap sut hi) c tac dng rt
tt trong vi c tng hp cac cht rn xp. Cht lng ion ln u tin c ng dng vo
iu ch cac zeolit, phostphate, v gn y l cac polimer phc cht (coordination
polimer) v cac mng li 3D. [9]
Da vo anion c s dng (cation m c nh l cac dn xut ca imidazolium), ta hon
ton c th iu khin cu trc ca cht rn. [10]
1.1.3.5.
Phng php i n hoa
Mueller v cac ng nghi p ca mnh tin hnh tng hp ng trimesate HKUST-1

bng phng phap i n ha hc thay v phng phap nhi t dung mi nh trc. Qua
trnh i n phn ca dia kim loi ng cng vi s c m t ca acid trimesic hnh thnh
v t rn tng ng nhanh chng. S th v ca phng phap ny nm kh nng tng
Trang 20
TNG QUAN
lng cht iu ch (scale-up), v n tc phn ng, cung nh tinh khit cao do khng
h c s nh hng ca i ion ca tin cht kim loi trong sut qua trnh phn ng. [11]
1.1.3.6.
Phng php vi song
Vi sng c c tnh l re tin v thi gian phn ng nhanh. Vi sng ng thi cung l
m t phng phap rt tt iu kch thc v hnh dng ca cac tiu phn sn phm.
Chnh v l do ny, ngi ta ng dng vi sng vo vi c tng hp MOF. Phng phap
vi sng cho phep tng hp trong vng vi pht rt nhiu loi pha xp ni ting nh
cac IRMOF, nickel glutarat hay cac l xp ln MIL-101. Phng phap vi sng gn y
dc kt hp vi phng phap nhi t ion tng hp nickel trimesate. [12, 13, 14, 15]
1.1.3.7.
Cc yu t nh hng
C nhiu yu t gy nh hng trc tip n cht lng tinh th, hiu sut kt tinh hay
kh nng to ra pha mi trong qua trnh tng hp MOF nh:
T l mol tac cht
Nng tac cht
Nng cht iu chnh (modulator): iu khin tc kt tinh, nh hng n
kh nng hnh thnh tinh th ca MOF.
Dung mi: phi c kh nng ha tan c hai tin cht hu c v v c, ho c t nht
l m t phn cac tin cht. Tng hp thy nhit l mt trng hp c bit khi
dung mi s dng l nc, ngoi ra ngi ta c th s dng cac alcol (MeOH,
EtOH, propanol), acetonitril ho c hn hp nhiu loi dung mi. Thng thng,
nhng dn xut ca formamid nh: DMF v DEF thng c dng lm dung
mi v c kh nng ho tan tt nhiu cht hu c ln v c. Tuy nhin, cac dung
mi ny c hi nn trong qua trnh s dng cn lu tranh nguy him.
Nhit : ph thuc vo tnh cht vt l, ha hc ca tac cht (nhit nng chy,
nhit si, nhit phn hy), thng nm gia nhi t phng v 250oC.
Thi gian phn ng: c th keo di t vi gi n vi ngy.
Vt cha: ty thu c vo s la chn nhit v dung mi (vial, autoclave, ng
nghim hn kn).
Ngoi ra, th tch l xp v di n tch b m t ca MOF cung chu nh hng ca qua
trnh x l, hot hoa sau khi tng hp:
Trang 21
TNG QUAN
Trong c cu ca MOF c rt nhiu l xp nn sau qua trnh tng hp, cac phn t
ngoi lai (cac phn t dung mi ho c modulator) thng nm li trong nhng l
xp ca sn phm MOF di dng t do, ho c phi tr vi cac tm kim loi, iu
ny c th nh hng n kch thc, th tch l xp v di n tch b m t ca v t
li u. Cac phn t ny c th c loi b nh vo vi c trao i dung mi sau
ht chn khng phi hp vi vi c gia nhi t nu cn. Mc ch ca qua trnh trao
i dung mi chnh l thay th dung mi DMF c nhit bay hi cao (153 oC)
bng cac dung mi khac c nhit bay hi thp hn nh CH 2Cl2 (40 oC), CH3Cl
(61,2 oC), EtOH (78 oC).
Trong vi c iu khin thnh phn v cu trc l xp ca cac MOF, ngoi vi c s
dng cac linker hu c ln th hot ha MOF bng cht lng siu ti hn cung
c xem l m t la chn cho vi c tng di n tch b m t v th tch l xp. Hot
ha siu ti hn c kh nng tri t tiu sc cng b m t ca dung mi ti nhng
nhi t v ap sut ti im ti hn m c th lm s p cu trc ca tinh th nu
hot ha gia nhi t theo cach thng thng. [16]
1.1.4.
Cc phng php kim tra c tnh
Trng thai, cu trc, di n tch b m t, th tch l xp v bn nhi t ca v t li u MOF

c xac nh bng nhng phng phap nh:
Ph nhiu x tia X (XRD): c th cho bit cac thng tin t:
V tr cac mui (peak) cho bit thng tin v thng s mng, xac nh c kch
thc mng, bit c thnh phn pha to thnh, t c th xac nh tn
khoang cht, vt liu, ho c tn hp cht nu c cac ph chun so sanh.
Da vo cng cac peak c th tnh c mt electron bn trong
mng, xac nh c v tr ca cac nguyn t trong mng.
Hnh dng v b rng peak ni ln mc tinh th ha, khim khuyt do bin
dng cu trc v kch thc ht.
ng nn ni ln mc tinh th ha.
Phng phap phn tch nhit trng lng (TGA): c th ghi nhn trc tip s thay
i khi lng theo thng s nhit v tc nng nhi t, c dng kho
sat bn nhit v s b xp ca vt liu. Mi trng nung nng c th l kh
tr (nh nit) hoc kh phn ng (khng kh hay oxi).
Din tch b mt ring ca vt liu c xac nh bng cach hp th kh N 2 nhit
N2 lng (-195.8 oC hay 77 K), ho c kh Ar nhi t Ar lng (185.9C,
Trang 22
TNG QUAN
87 K) v da theo phng trnh hp ph ca ng hp ph ng nhit theo m
hnh BET v m hnh Langmuir x l s liu.
Ph hng ngoi (FT-IR): nhm kim tra nhm chc c trng ca linker trong
phn t cht xac nh s b xem c s hnh thnh lin kt gia linker vi
kim loi hay cha, v kim tra s c m t ca cac nhm chc ca phn t dung
mi v tac cht cha phn ng ht.
1.1.5.
ng dng ca MOF
Kh nng ng dng ca MOF rt rng ri nh hp ph v lu tr kh, lm cht xc tac,

b phn cm bin, v ng dng lm in cc cho pin. Ty thuc vo cu trc khung kim
loi v cu t hu c m kh nng ng dng ca MOF cung thay i a dng.
1.1.5.1.
Kh nng hp ph kh
Carbon dioxid v metan l hai kh chnh trong cac kh nh knh thi ra hi n nay. Cac v t
liu MOF hay cac phc polimer kim loi hi n ang c quan tm nh cht thay th cho
zeolit v cac cht hp ph da trn carbon do c kh nng hp ph cao hn.
MOF l loi vt liu c kh nng hp ph chn lc, mi loi MOF khac nhau cho kh
nng hp ph chn lc i vi tng loi kh khac nhau. c tnh ny khin cho MOF c
tim nng ng dng ln trong vic phn tach cac hn hp kh vi c tnh la chn cao,
kh nng lu tr ln. [17]
Nhin liu ha thch (than, du m, kh t nhin) hin chim 85% ngun nng lng
ang c s dng trn ton th gii. S t chay nhin liu sinh ra mt lng ln kh
thi CO2 c c tnh vo khong 30 t tn mi nm. Vn bt gi v c lp CO 2 hin
ang thu ht s quan tm ca khng ch gii khoa hc m y cn l vn ca ton x
hi trong vic bo v mi trng nhm m bo s phat trin bn vng bi l CO 2 ln
trong nhin liu l mt yu t lm gim tinh khit v nh hng n kh nng cung
cp nng lng ca nhin liu v CO 2 cn l mt trong nhng nguyn nhn chnh gy ra
hiu ng nh knh trn trai t. Hin nay, bin phap chn CO 2 ang c ng dng trn
th gii nhng hiu qu khng cao. MOF ra i da trn tng mt vt liu xp c kh
nng phn tach v lu gi kh CO2 thu ht s quan tm ca nhiu nh nghin cu trn
th gii.
Trang 23
TNG QUAN
Hnh 1-7: Kho sat kh nng hp ph CO2 ca mt s loi MOF nhit phng. [16]
Hnh 1-8: Minh ha kh nng lu tr kh CO2 ca MOF-177. [17]

Bnh cha c thm MOF-177 c kh nng tr lng kh CO2 gp 9 ln so vi bnh cha
thng thng.
C hai ng dng trong vi c tach kh CO2 bng MOF ang c quan tm l: tach CO2
khi cac ging kh t nhin c tnh acid v tach kh CO2 khi kh thi t cac nh may
i n. i vi ng dng th 2 cn lu rng ap sut ring phn ca CO2 kha thp so vi
ap sut kh quyn, chnh v v y nghin cu v s hp ph CO2 ln MOF ti ap sut thp
(sub-atmospheric) l rt quan trng. [16]
Nhng yu t nh hng n kh nng hp ph CO 2 l kch thc l xp v din tch
b mt. Bn cnh , cac tng tac ha hc nh tng tac hidrogen gia proton c tnh
acid ca COOH, -SO3H vi nguyn t oxigen ca CO2 hoc tng tac cho-nhn in t
Trang 24
TNG QUAN
gia phn t CO2 vi MOF c linker cha cac nhm chc nh OH,
-NH2, -CONH2 cung c nh hng n kh nng ca MOF trong hp ph CO 2. [16] Vic
tng s nhm chc cung c nh hng nht nh n kh nng hp ph kh.
V d: Nhm chc NH2 trn linker ca MOF c th lm tng kh nng hp ph CO 2
bng phn ng ca NH2 vi CO2 to thnh carbamat:
c bi t khi linker ca MOF c nhm CONH2, nhm -CONH2 s ng vai tr baz

Lewis cung cp electron cho carbon thiu i n t trn CO2 khin cho nguyn t oxigen
trn CO2 tr nn giu i n t hn, t d dng hnh thnh lin kt hidrogen lin phn
t mnh hn vi linker hu c. [18]
Hnh 1-9: Hnh minh ha lin kt gia nhm chc CONH2 ca MOF vi CO2.
(C-en, O-, N-xanh, H-trng) [18]
Ngoi ra, cac loi MOF c kch thc l xp khac nhau cung c ng dng trong vi c
hp ph chn lc theo kch thc i vi cac phn t kh nh N2, O2, CO. [19]
Trang 25
TNG QUAN
1.1.5.2.
Lu tr kh
1.1.1.1.1 Lu tr kh hidrogen
Hidrogen c coi nh m t loi nng lng xanh, cung cp nng lng hi u qu m sn
phm ph ch l nc. M c d v y , c m t tr ngi i vi vi c ng dng r ng ri
nhin li u hidrogen l s thiu an ton v kh khn trong vi c lu tr loi kh ny.
Nhiu phng phap v ang c s dng lu tr kh hidrogen nh cha kh trong
cac xy-lanh kh ap sut cao, cac b ng lnh cha hidrogen lng, hp ph trong cac ng
nano carbon ho c zeolit.
Nm 2003, Yaghi v nhm cng s ca ng tng hp thnh cng trong tng hp
MOF5 c cng thc Zn4O(BDC) c din tch b mt ring ln khong 3000 m 2/g, c kh
nng lu tr 4,5 wt% H2 770 K, ap sut thp hn 1 atm v 1,0 wt% H 2 nhit phng
v 20 bar. [20]
Hnh 1-10: Cu trc tinh th ca MOF-5. (khi t di n ZnO4-tm, C-xam, O-xanh)

Bng 1-2: M t s loi MOF c kim tra kh nng lu tr kh hidrogen.
Di n tch
MOF
b m t
Ni3(btc)2(3-pic)6(pd)3
Sc2(bdc)3
Al(OH)(bdc), MIL-53(Al)
Cr(OH)(bdc), MIL-53(Cr
Al3O(OH)(btc)3, MIL-96(Al)
(m2g-1)
721
1590
1500
Trang 26
H2 lu gi
iu ki n p
(wt.%)
sut lu tr
2.10
1.50
3.80
3.20
1.70
14 bar
0.8 bar
16 bar
16 bar
10 bar
TNG QUAN
Cr3OF(btc)2, MIL-100(Cr)
Cr3OF(bdc)3, MIL-101(Cr)
Cr3OF(ntc)1.5, MIL-102(Cr)
Cu3(btc)2, HKUST-1
Zn4O(bdc)3, MOF-5 ho c IRMOF-1
Zn4O(cbbdc)3, IRMOF-6
Zn4O(ndc)3, IRMOF-8
Zn4O(hpdc)3, IRMOF-11
Zn4O(tmbdc)3, IRMOF-18
Zn4O(ttdc)3, IRMOF-20
Zn4O(BTB)2, MOF-177
2800
5500
42
1958
2296
3300
1466
2340
1501
4590
5640
3.30
6.10
0.90
3.60
4.70
4.80
1.50
3.50
0.89
6.70
7.50
25 bar
60 bar
10 bar
50 bar
50 bar
50 bar
40 bar
35 bar
40 bar
70 bar
70 bar
1.1.1.1.2 Lu tr kh metan
Metan thng c s dng trong cac t bo nng lng. Carbon hot tnh v zeolit
c s dng lu tr kh metan nhng vn cn tn ti nhng m t hn ch nht nh.
M t s loi MOF nh IRMOF-6, MIL-101 th hi n tim nng cao trong hp ph kh
metan m c d y l m t loi phn t kh khng phn cc.
Nhiu nghin cu cho rng cac khong kim loi phi tr bt bo ho (open metal site) c
th tng tac vi metan nh lc coulomb (lc tinh i n) v kch thc l xp ph hp s
gia tng lc ht van der Waal gip tng kh nng lu gi kh metan. [21]
1.1.5.3.
Kh nng xuc tc
c nhiu bao cao v kh nng xc tac d th ca MOF c cng b. So vi cac zeolit

v cac silica mesoporous bin tnh th u im ca MOF nm kh nng kt hp trc
tip ca cac tm xc tac hot tnh kim loi v kh nng bin tnh d dng khu vc xung
quanh vng xc tac nh vo cac nhm chc trn cac linker.
Nhiu nghin cu cho thy MOF c th tai s dng li nhiu ln m khng nh hng
n kh nng xc tac ch bng cach n gin l cho vo may ly tm, ra sch v lm kh
bng cach ht chn khng. [22]
V d:
MOF-5 mang tnh cht nh mt acid Lewis nh c cation kim loi (Zn 2+) nn c
kh nng ng dng lm xc tac trong cac phn ng hu c nh: phn ng
Mukaiyama-aldol, phn ng Knoevenagel, phn ng ester ha, phn ng alkol
ha, phn ng Diels-Alder, phn ng hidrogen ha cho hiu sut cao.
Trang 27
TNG QUAN
MOF ng vai tr xc tac baz Lewis cung c bao cao bi nhm ca Kitagawa,
vng xc tac nm trn nhm amid ca linker h tr cho phn ng
Knoevenagel. [23] Ngoi ra, MOF vi cac nhm chc piridin, amin c th h tr
phn ng transester ha, phn ng aza-Michael.
UiO-66-NH2 c s dng lm xc tac d th cho phn ng ngng t aldol.
Hnh 1-11: Phn ng ngng t aldol s dng xc tac d th UiO-66-NH2.

Zr(IV) ng vai tr l cac tm acid Lewis tng tac vi nhm carbonil ca
benzaldehid, lm tng tnh phn cc, trong khi nhm amin c m t trong linker c
kh nng hot ha aliphatic aldehid chi phng. Phn ng ny c chn lc
cao, trn 82%. [24]
MOF vi Cu(I) s dng phn hy hay kh NO. [25]
MOF vi Fe(III) dng trong phn ng benzil ha Friedel-Craft. [26]
1.1.5.4.
ng dng sinh hoc
C rt nhiu kh nng trong vi c s dng lng NO ngoi sinh trong qua trnh phng v
cha b nh i vi vi cac thit b chng to huyt khi (chng ng mau trong mch
mau), chng so cho cac vt thng v loet [27]. S cung cp kh NO t cac xylanh bnh
thng khng th hi n s ti u trong vi c cha b nh nnvi c kham pha ra m t loi v t
li u c kh nng sn xut, cha v v n chuyn NO l rt cn thit. Morris chng
minh rng kh NO c th c tr v v n chuyn trong MOF-199 vi cac tm kim loi
bt bo ha phi tr (open metal site) khng nh kh nng chng li s ng t ca cac
tiu cu. [28, 29]
1.1.5.5.
Kh nng tch
a) M t s bi bao c p n vi c tach cac hn hp dung mi phn cc s dng

MOF.
V d:
Trang 28
TNG QUAN
Eddaoudi v cac ng nghi p s dng MOF-4 tach MeOH khi acetonitril.
[30]
Nhm ca Chen s dng MOF vi cac l xp nh chn lc kch thc v tach
MeOH khi dietileter. [31]
b) Ngoi ra, kh nng tach cn c ng dng i vi cac olefin.
V d:
Nhm nghin cu ca Huang bao cao tnh cht chn lc ca qua trnh tach pxilen v o-xilen vi cac bin th ca MOF-5. [32]
Devos v cac c ng s ca mnh s dng MIL-47 v MIL-53(Al) cho qua trnh ly
trch cac ng phn ca xilen [33].
Nhm ca Ernst bao cao kt qu s dng MOF-199 tach propan v propen
vi kh nng chn lc rt ang k d cho nhi t hp ph ca mi ng phn gn
nh nhau. [34]
1.1.6.
Nhng hn ch ca MOF
Chi ph v cac phng phap hi u qu tng hp ra cac linker s dng trong MOF l
vn lun c quan tm.
Qua trnh trao i dung mi thng tiu tn m t lng dung mi ang k.
Hnh 1-12: Cu trc ca MIL-53 gm AlO6 cu trc bat di n gn vi benzen

dicarboxilat.
Tuy nhin gii hn chnh ca MOF, c bit l nhng vt liu c n v th cp l Zncarboxilat, l bn ha hc thp trong iu kin khng kh m v cac dung mi hu c.
Chnh iu ny lm gii hn kh nng ng dng ca MOF.
Trang 29
TNG QUAN
1.2. Gii thi u v Zr-MOF

a s cac vt liu MOF kem bn trong mt s dung mi hu c v nhy m. Trong khi
, cac MOF c cha zirconium (Zr) li bn trong iu kin khng kh, nc, benzen,
etanol v mt s dung mi hu c khac cho nn tim nng ng dng ca loi vt liu ny
trong tng lai rt ln.
Zr l kim loi thu c nhm IV, tng tac mnh vi oxigen hnh thnh lin kt mnh Zr-O
trong SBU (Zr c s oxi ha cao +4). Thm vo , nh vo cu trc xp ch t ca cac
SBU, cu trc ca cac Zr-MOF c duy tr tng i bn vng.
Cu trc ca Zr-MOF bao gm m t chm nguyn t (cluster) c cng thc Zr6O4(OH)4
trong cac m t tam giac ca bat di n Zr6 c gn vi 3-O and 3-OH (Hnh 1-13a) v
cac cnh ca bat di n Zr6 ny ni li bi 12 cu ni carboxilat (-COO -) ca acid
dicarboxilic hnh thnh nn cluster Zr6O4(OH)4(COO)12. Cac nguyn t oxigen lin kt
dng 3-O s to nn m t hnh t di n lng bn trong bat di n Zr6, tng t vi cac
nguyn t oxigen lin kt dng 3-OH (Hnh 1-13a). Mi nguyn t zirconium to phi
tr vi 8 nguyn t oxigen to thnh dng hnh hc i lng tr vung (squareantiprismatic). M t m t vung to thnh bi nguyn t oxigen ca carboxilat, m t
vung th hai to thnh do nguyn t oxigen n t 3-O and 3-OH (Hnh 1-15).
Bi v bn kem ca 3-OH, SBU c th bin i thu n nghch gia hai dng. SBU
Zr6(O)4(OH)4(COO)12 c th kh H2O tr thnh Zr6O6(COO)12 vi khong cach gia
Zr(IV)-Zr(IV) khac nhau v hnh thnh nn Zr(IV) trung tm c s phi tr 7 (Hnh 114b). Tuy v y, cu trc chung ca v t li u khng thay i d cho bin i dng SBU
no. Qua trnh kh H2O ca cluster bt u t 250 oC n 300 oC. Hai trong s bn nhm
3-OH tach ra cng vi hidrogen ca hai nhm 3-OH cn li, a n kt qu l cluster
Zr6O6(COO)12 (Hnh 1-13b). [35]
Hnh 1-13: Cluster dng hidrat hoa Zr6O4(OH)4 v dehidrat hoa Zr6O6.
(Zr-, O-xanh, C-xam, H-trng)
Trang 30
TNG QUAN
Hnh 1-14: Cluster hon chnh cho thy s thay i trong s phi tr ca zirconium t 8
thnh 7 do s kh H2O. (Zr-, O-xanh, C-xam, H-trng)
Hnh 1-15: Cu trc ca cluster Zr6(3-O)4(3-OH)4(COO)12.

(Zr-xanh, O-, C-en) [36]
Hnh 1-16: Cu trc SBU m r ng ca cluster Zr-O, gn vi 12 linker hu c.

(Zr-xanh, C-xam, O-) [37]
Trang 31
TNG QUAN
Hnh 1-17: Cu trc tng quat th hi n di dng a di n .

(Zr-lc lam, O-, C-xam) [37]
1.2.1.
M t s loi v t li u MOF s dng Zr
1.2.1.1.
UiO-n
Nm 2008, Lillerud v c ng s tng hp c nhm cac vt liu xp UiO-66, UiO67, UiO-68 t Zr(IV) dicarboxilat. Loi vt liu Zr-MOF ny bn trong nhiu loi
dung mi v cac iu kin ap sut khac nhau. [38]
Hnh 1-18: (a) Cu trc bat di n ca Zr-MOF, (b) Zr-MOF vi 1,4-benzen dicarboxilat
(BDC) lm linker, UiO-66, (c) Zr-MOF vi 4,4-biphenil dicarboxilat (BPDC) lm linker,
UiO-67, (d) Zr-MOF vi terphenil dicarboxilat (TPDC) lm linker, UiO-68.
(Zr-, O-xanh, C-xam, H-trng) [35]
Trang 32
TNG QUAN
Hnh 1-19: Cac linker vi di m r ng c s dng trong tng hp Zr-MOF.

[39]
S kt hp ca cac nhm chc c mt trong cu trc c th thu c kt qu l nhng
v t li u MOF c cu trc v tnh cht a dng, c ao, gp phn vo vi c m r ng
tim nng ng dng ca cac vt liu ny. Do , xut phat t cu trc c bn l UiO-66,
Cohen v ng nghip nghin cu thnh cng nhiu loi UiO c cu trc tng t
UiO-66 bng cach dng nhng cu ni hu c c gn nhm chc khac nhau nh -NH 2,
-Br, -NO2. T nhm chc NH2 c mt trong cu ni, nhiu nhm chc khac nhau c
thay th hnh thnh nn s a dng ca vt liu Zr-MOF (Hnh 1-17) [40].
Trang 33
TNG QUAN
Hnh 1-20: S thay th cac nhm chc khac nhau t UiO-66-NH2.

1.2.1.2.
PIZOF
a s cac cu ni hu c dng trong tng hp vt liu Zr-MOF c kch thc tng i

ngn nn khng dn n hin tng thm nhp vo nhau trong cu trc (cn gi
l interpenetrated). Cn khi s dng cac linker c kch thc di hn, c th xy ra
hin tng thm nhp vo nhau trong mng tinh th. Tuy nhin, cac vt liu Zr -MOF ny
cung c din tch b mt ring kha cao nn gi l vt liu PIZOP (Porous
interpenetrated zirconium organic frameworks). [41]
Hnh 1-21: SBU ca PIZOF-1. [41]

Cac PIZOF c cu to t ZrCl4 v acid dicarboxilic cu trc thng di HO 2C[PEP(R1,R2)-EP]CO2H. Cac nhm chc R1,R2 c th thay i a dng: alkil, O-alkil, oligo
(etilen glycol), amino, alkin, furan [41]
Trang 34
TNG QUAN
Hnh 1-22: Cu trc PEPEP.
Hnh 1-23: Tng hp PIZOF. [41]

1.2.1.3.
MOF-525, MOF-535, MOF-545
Mi y, Yaghi v cac cng s tng hp thnh cng ba loi Zr-MOF khac nhau t
mui zirconium v linker porpirin H4-TCPP-H2 = (C48H24O8N4) v cruciform H4-XF
= (C42O8H22)] c din tch b mt ring ln hn 1000 m 2/g. Cac vt liu ny cung
bn trong dung mi nc, MeOH v hn hp acid acetic/nc (v/v=1:1) trong 12 gi.
[42]
Hnh 1-24: Cu trc ca (a) MOF-525, (b) MOF-535, (c) MOF-545.
Trang 35
TNG QUAN
1.2.1.4.
Zr-fum
Zr-MOF s dng linker fumarat dianion tng hp. Acid fumaric (acid trans-buten-1,4dicarboxilic) l m t acid dicarboxilic bt bo ho. Linker ny c la chn nh kt cu
n gin v an ton v m t sinh hc v c s dng nh ph gia thc phm. V y
nn mc tiu ch to loi MOF ny l ng dng trong y hc. [43]
Hnh 1-25: (a) Cu trc ca linker fumarat khng tuyn tnh, (b) v (c) M hnh cu trc
ca Zr-fum MOF. (b) mng c s hnh l p phng. (c) Cu trc bat di n ca m t
mng c s. [43]
1.2.2.
Vai tro ca cht iu hng (modulator) trong Zr-MOF
S thm vo ligand vi ch m t vng kt hp, cnh tranh vi linker trong qua trnh lin
kt vi cation kim loi gi l phng phap s dng cht iu hng (modulator). Phng
phap ny c bao cao gn y vi quy trnh tng hp [Cu 2(ndc)2(dabco)] (ndc2-=1,4naphthalene dicarboxilat, dabco=diazabicyclo[2.2.2]octane) s dng acid acetic lm
modulator.
S dng modulator c u im l c th iu chnh c kch thc v hnh thai ca v t
li u, rt ngn thi gian phn ng. Tuy nhin, vi c lm ny cung c hn ch nh kh ra
sch modulator khi sn phm cui cng, gy nh hng n bn nhi t ca MOF.
M t s cac modulator c nghin cu s dng trong tng hp Zr-MOF thng l cac
mono acid nh: HCOOH, AcOH, acid benzoic ho c H2O.
Trang 36
TNG QUAN
Hnh 1-26: nh hng ca vi c s dng acid benzoic ln hnh thai v kch thc ca
tinh th UiO-66.
S hi n di n ca modulator s hn ch kh nng hnh thnh tinh th v nh hnh. Cng
vi s gia tng nng modulator, qua trnh to phc c s cnh tranh gia phn t
linker kh proton v ion carboxilat ca modulator trong lin kt vi cation Zr lm gim
s lng ht nhn hnh thnh (s lng cac SBU c hnh thnh), nh lm ch m
qua
trnh kt tinh, hnh thnh nn nhng tinh th ln hn.
Trang 37
TNG QUAN
Hnh 1-27: Minh ha kh nng hnh thnh ht nhn nh hng bi nng modulator.
(ion kim loi-khi cu xanh la, linker-g y xam, ht nhn-khi cu tm, tinh th-khi
vung )
Nc cung c nh hng n qua trnh tng hp MOF. L do l nc rt cn thit cho s
thuy phn ca tin cht mui Zr v cho s cung cp nguyn t oxigen cho s hnh thnh
ca SBU Zr6O4(OH)4(COO)12. [43]
1.2.3.
M t s ng dng ca Zr-MOF
UiO-66, UiO-67, UiO-68, t c bn ln n 450 oC trong khng kh, khng thay

i kh nng hp ph sau khi ngm trong nc v ap sut, hp ph chn lc hn hp
CO2-CH4.
UiO-66 and UiO-66-NH2 c nghin cu ng dng xc tac trong phn ng quang
hoa.
UiO-66-NH2 xc tac cho phn ng aldol hoa cheo.
Ngoi bn nhit v bn hoa hc cao, Zr-MOF cn c din tch b mt cao v c kch
thc ht nh (khong vi trm nanometer) nn Zr-MOF rt thch hp lm mng
mng v dn truyn thuc. V d: Zr-fum.
Trang 38
TNG QUAN
1.3. Khi qut v cc phn ng trong quy trnh tng hp linker

HOOC[PEP(CONH2)EP]COOH, (P-phenilen, E-etinilen)
1.3.1.
Phn ng iu ch clorur acid
Hnh 1-28: Phn ng gia acid carboxilic vi SOCl2.

Phn ng trn c s sinh ra kh SO 2 v HCl c nn cn lm trong t ht v h phn ng
cn lp h thng phng b hp th kh HCl.
Phn ng gia acid carboxilic vi SOCl2 s dng DMF lm xc tac cho phn ng nhanh
v hi u qu hn. DMF s phn ng vi SOCl2 to thnh hp cht trung gian lm tng kh
nng phn ng vi acid carboxilic, gip phn ng t hi u sut cao. [44]
Trang 39
TNG QUAN
Hnh 1-29: C ch phn ng vi SOCl2 xc tac DMF.
1.3.2.
Phn ng amin gii
Hnh 1-30: Phn ng gia clorur acid vi NH3

Clorur acid tac dng rt nhanh vi amoniac cho ra amid vi hi u sut cao. Phn ng cn
dng hai phn t amin cho m t phn t clorur acid, m t phn t tac dng nh cht thn
hch i vi clorur acid, m t phn t ng vai tr baz kt hp vi sn phm ph HCl
sinh ra mui amonium clorur. Trong m t s trng hp, m t ng lng amin cung c
th c thay bng m t ng lng NaOH. [45]
Trang 40
TNG QUAN
1.3.3.
Phn ng ghep c p Sonogashira
Phn ng ghep c p nhm xy dng b khung carbon ln t nhng phn t n gin nh

vo xc tac kim loi chuyn tip v ang thu ht s quan tm ca c ng ng cac nh
khoa hc trong nhiu nm qua. Trong s , phn ng ghep c p vi xc tac paladium sp2sp gia aril ho c halogenur alkenil ho c triflat vi alkin u dy vi s c m t ca cht
h tr xc tac Cu(I) tr thnh m t phn ng quan trng cho tng hp arilalkin v enin
tip cach, l tin cht cho cac sn phm t nhin, dc phm, v t li u hu c phn t.
Trong giai on u nghin cu (1975), phn ng ch s dng xc tac paladium, tuy
nhin, i hi nhi t cao (> 100oC). Sau , Sonogashira v Hagihara nghin cu
v b sung thm CuI h tr xc tac, gip rt ngn thi gian phn ng cung nh gim bt
nhi t phn ng. Tuy v y, s thm vo CuI cung c nhng khuyt im nh khng
thn thi n vi mi trng v kh thu hi tai s dng.
Hnh 1-31: Phn ng ghep c p Sonogashira.

Phn ng Sonogashira thng s dng phc Pd vi ligand phosphan lm xc tac cng
vi s c m t ca mui Cu(I) v m t amin (va l baz, va l dung mi v c s dng
vi lng d) ho c c th s dng thm DMF, THF, toluen ng vai tr dung mi. Xc
tac truyn thng l phc c cha triphenilphosphan nh Pd(PPh 3)4, Pd(PPh3)2Cl2. Tuy
nhin, phc Pd(II) nh Pd(PPh3)2Cl2 thng c s dng hn Pd(0) do c n nh v
kh nng ha tan cao hn.
Trang 41
TNG QUAN
L= phosphan, baz, dung mi ho c alkin

Hnh 1-32: C ch d oan ca phn ng Sonogashira vi xc tac paladium v Cu(I)
C ch chnh xac ca phn ng Sonogashira vi xc tac Cu(I) vn cn nhiu im cha
c lm ro. M c d bng m t s phan oan v t l th c ch phn ng c d oan
da trn s nh n di n cac sn phm trung gian hnh thnh trong qua trnh phn ng. C
ch bao gm 2 chu trnh:
Chu trnh Pd:
u tin, c s kh phc Pd(II) ban u thnh xc tac Pd(0) hot tnh nh nhng
linker ho c baz c kh nng cho i n t nh phosphan, amin ho c ether thng qua
chui phn ng to phc loi H+ gim cp. Sau , s oxid ha gia R-X vi
phc cht Pd0L2 c 14 electron hnh thnh sn phm trung gian sn phm ny trao
Trang 42
TNG QUAN
i (transmetallation) vi alkinil ng (hnh thnh t alkin u dy, baz v CuI).
Trong bc oxid ha, R-X ng vai tr quan trng. Bc phn ng ny s c thm
thu n li nu X = I ho c Otf (triflat hay trifluorometansulfonat) v nu m t i n
tch c gim xung trn ni CX nh s c m t ca nhm rt i n t. Tip theo,
din ra s gim cp cng vi s ghep c p ca hai linker hu c a n sn phm v
tai hnh thnh xc tac Pd(0).
Chu trnh Cu:
Vn cn ang c tm hiu. Baz (thng l amin) ly proton acetilen ca alkin
u dy, t to thnh acetilur ng trong s hi n di n ca mui Cu(I). m t vn
quan trng l amin thng khng c tnh baz kh proton alkyn to
ra anion thn hch t to thnh acetilur ng. Do , m t phc -alkin Cu
c th tham gia vo chu trnh, lm tng tnh acid ca proton alkin nh s kh
proton d dng din ra hn. [46]
1.3.4.
Phn ng thy gii
Hnh 1-33: Phn ng thy gii

S thy gii ester c th s dng xc tac acid ho c baz. Thy gii xc tac acid l cn
bng ngc ca s ester ha Fischer. Xc tac baz cho phn ng khng thu n nghch nn
thng c s dng trong phn ng ny, y cn c gi l s savon ha (x phng
ha).
Amid cung thy gii ra c acid carboxilic v amin khi un nng trong dung dch acid
ho c baz. Tuy nhin, iu ki n phn ng thy gii amid kh khn hn rt nhiu so vi
cac dn xut khac ca acid carboxilic. [45]
Hnh 1-34: C ch phn ng thy gii ester trong mi trng baz.

Trang 43
KT QUA VA BIN LUN
Chng 2
Kt qu va bi n lu n
Trong phn ny, c tnh ca linker v MOF s c m t li. Linker tng hp ra s

c nhn danh thng qua phn tch NMR (1H, 13C), MS, IR v c s dng kho sat
kh nng hnh thnh Zr-MOF.
2.1. Tng hp acid 4,4'-(2-carbamoil-1,4-phenilen)bis(etin-1,2diil)dibenzoic (ACPEB)
Hnh 2-35: Quy trnh tng quat iu ch linker diacid HOOC[PEP(CONH2)EP]COOH
2.1.1.
Phn ng tng hp 2,5-diiodobenzamid
Hnh 2-36: Quy trnh phn ng iu ch benzamid.
Trang 44
KT QUA VA BIN LUN

Acid 2,5-diiodobenzoic v xc tac DMF phn ng vi SOCl2 trong 2 gi. Sau , tip tc
phn ng vi NaOH 15% v NH3 trong 15.
Bng 2-3: Kho sat nh hng ca xc tac n hi u sut phn ng vi SOCl2.
Xuc tc
Hiu sut (%)
Khng s dng
20
C s dng
86-88
Kt qu cho thy phn ng nn c s gp m t ca xc tac DMF thu c hi u sut
cao.
Bng 2-4: Kho sat nh hng ca nhi t ti hi u sut phn ng vi NH3.
Nhit (oC)
nhi t phng
50 oC
60 oC
Hiu sut (%)

86
82
82
Kt qu cho thy hi u sut phn ng nhi t phng l tt nht cho phn ng (8688%).
(a) Phn tch FT-IR
Ph cho thy vng 3200-3400 cm-1 xut hi n 2 peak ca ni N-H ca amid nht cp.
Peak hp thu 1649 cm-1 l tn hi u ca C=O ca amid. (Ph lc 1)
(b) Phn tch 1H NMR
Bng 2-5: D li u t ph 1H NMR (300 MHz, DMSO-d6).

STT
H2
H6
H3
7.46, dd
7.61, d
7.61, d
(Ph lc 5)
Trang 45
J (Hz)
2.1, 8.2
2.1
8.2
KT QUA VA BIN LUN
2.1.2.
Phn ng Sonogashira
Hnh 2-37: Quy trnh phn ng ghep c p alkinil-aril.

Hn hp 2,5-diiodobenzamid v 4-etinilbenzoat metil t l 1:2, cng vi h xc tac
Pd(PPh3)2Cl2 v CuI c thc hi n trong mi trng kh N2, s dng dung mi THF v
Et3N. Phn ng c thc hi n trong 6 gi, thay i nhi t kho sat hi u sut phn
ng.
Bng 2-6: Kho sat phn ng theo nhi t .
Nhit (oC)
Thi gian (gi) Hiu sut (%)
nhi t phng
6
80
o
50 C
6
58
o
60 C
6
53
Theo kt qu cho thy, phn ng thc hi n nhi t phng cho hi u sut tt nht.
Chn nhi t ny kho sat tip.
Phn ng c thc hi n nh trn vi nhi t phng v thi gian phn ng thay i.
Bng 2-7: Kho sat phn ng theo thi gian.
Nhit (oC)
nhi t phng
nhi t phng
nhi t phng
Thi gian (gi)

6
16
24
Trang 46
Hiu sut (%)

78
90
91
KT QUA VA BIN LUN

Phn ng nhi t phng v thi gian 16 gi cho hi u sut tt (88-90%) nn c
chn lm iu ki n phn ng sau ny.
(a) Phn tch FT-IR
Vng 3200-3400 cm-1 c hai peak ca N-H ca amid nht cp. Tuy nhin, hai peak ny b
che m t phn bi cac peak xut hi n vng 2800-3500 cm-1 do O-H ca KBr ht m.
Peak 1659 cm-1 l peak ca C=O ca amid. Peak 1723 cm-1 l peak ca C=O ca
ester. (Ph lc 2)
(b) Phn tch 1H NMR
Bng 2-8: D li u t ph 1HNMR (500MHz, DMSO d6).
STT
ppm)
Hn
H29, H33 (6H)
H18, H22
NH
H4 , H 5
H13, H17
H14
H14, H16, H19, H21
NH
J (Hz)
3.89, s
7.67, d
7.67
7.71, s
7.74, d
7.77, s
8.02, dd
8.02
8.55
8.55
1.65, 8.45
(Ph lc 6)
(c) Phn tch 13C NMR
Bng 2-9: D li u t ph 13CNMR (500MHz, DMSO d6).
STT
Cn
CONH2
(C23)
COOH
(C26, C30)
C trn vng benzen
C C
(C7, C8, C9, C10)
CH3
(C29, C33)
(Ph lc 7)
(d) Phn tch MS
Tnh toan: M= 437
Thc nghi m: m/z = 438 [M+], 460, 413
Trang 47
ppm
165.64
168.04
120-140
90.67-93.77
90.67-93.76
KT QUA VA BIN LUN

(Ph lc 10)
2.1.3.
Phn ng thy gii
Hnh 2-38: Quy trnh phn ng thy gii.

Hn hp tac cht (5), KOH (615 mg), MeOH, THF v H 2O c un n 50 oC trong 19
gi. Sau ho tan trong nc ri acid hoa thu c san phm. Hi u sut trung bnh
78-80%.
(a) Phn tch FT-IR
Vng 3000-3500 cm-1 c mui r ng ca O-H ca acid carboxilic, peak ca N-H ca amid
b che khut . Peak 1657 cm-1 l peak ca C=O ca amid. (Ph lc 3)
(b) Phn tch 1H NMR
Bng 2-10: D li u t ph 1HNMR (500MHz, DMSO d6).
STT
(ppm)
RCOOH
NH
H18, H22
H13, H17
H4
H1
H19,H21
H14, H16
H5
11.0, s
6.92, s
7.74, d
7.76, d
7.92, d
7.95, s
7.97, d
8.00, d
8.18, d
(Ph lc 8)
Trang 48
J (Hz)
8.5
8.5
8.0
8.3
8.3
8.1
KT QUA VA BIN LUN
(c) Phn tch 13C NMR

Bng 2-11: D li u t ph 13CNMR (500MHz, DMSO d6).
STT
(ppm)
RCOOH
RCONH2
C trn vng benzen
C C
168.19
166.64, 166.98
121.28-138.78
90-106.23
(Ph lc 9)
(d) Phn tch MS
Tnh toan: M= 409
Thc nghi m: m/z = 410 [M+], 341
(Ph lc 11)
2.2. Tng hp Zr-MOF
Hnh 2-39: Tng hp MOF vi linker ACPEB.
2.2.1.
Kho st iu kin tng hp Zr-ACPEB
Cac yu t c la chn kho sat bao gm: nng , lng acid acetic, lng nc
thm vo, nhi t v thi gian phn ng.
2.2.1.1.
Kho st tng hp theo nng
Hn hp mui ZrCl4 v linker ACPEB theo ty l 1:1 cng vi dung dch acid acetic (30
eq) c ho tan trong DMF. Hn hp phn ng c un trong l sy nhit 120 oC
Trang 49
KT QUA VA BIN LUN

trong 2 ngy. Sau khi phn ng kt thc, hn hp phn ng c lc ly cht rn.
kt tinh ca vt liu c phn tch bng gin nhiu x tia X trn mu bt (P-XRD).
Bng 2-12: Kho sat tng hp Zr-ACPEB theo nng .
[ACPEB]
(mol/L)
[ZrCl4]
(mol/L)
AcOH
(eq)
Kt qu
0.005
0.005
30
V nh hnh
0.0085
0.0085
30
V nh hnh
0.010
0.010
30
V nh hnh
0.015
0.015
30
V nh hnh
0.020
0.020
30
V nh hnh
Hnh 2-40: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo nng .

Cac kt qu P-XRD hnh 2-5 u cho thy c mui v tr 2 theta = 4 o, chng t cac
mu c s tng ng v mt cu trc.
Trang 50
KT QUA VA BIN LUN

Ngoi ra, nng linker ACPEB v ZrCl 4 = 15x10-3 l tt nht do c mui c trng pha
v c thm peak xut hi n vng 2 theta = 8o. Do , chn nng linker v Zr l
15x10-3 mol/L cho cac kho sat tip theo.
2.2.1.2.
Kho st tng hp theo ng lng acid acetic (khng nc)
Da theo cac kt qu kho sat trc, trong DMF, t l Zr/ACPEB 1:1 v nng ACPEB
v Zr l 15x10-3 mol/L c chn kho sat tip. ng lng acid acetic thay i t 0
n 90 eq. Hn hp phn ng c un nng 120 oC trong 2 ngy.
Bng 2-13: Kho sat tng hp Zr-ACPEB theo ng lng AcOH (khng nc).
[ACPEB]
[ZrCl4]
AcOH
(mol/L)
0.015
(mol/L)
0.015
(eq)
0
V nh hnh
0.015
0.015
20
V nh hnh
0.015
0.015
30
V nh hnh
0.015
0.015
50
0.015
0.015
70
V nh hnh
V nh hnh
0.015
0.015
90
V nh hnh
Kt qu
(khng nc).
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KT QUA VA BIN LUN

Khi tng ng lng AcOH th tinh th hoa ca vt liu MOF tng. Qua trnh kt
tinh c tin trin bt u t nng AcOH 30 eq. Tuy nhin, m c d tip tc tng lng
AcOH ln n 90 eq th kh nng kt tinh vn khng c s thay i.
1.1.1.1.
Kho st tng hp theo ng lng acid acetic (thm nc)
Da theo kt qu kho sat trc, t l Zr/ACPEB 1:1 v nng ACPEB v Zr l 15x10 -3

mol/L c chn kho sat tip. ng lng acid acetic thay i t 30 n 90 eq, 0.10
mL H2O c thm vo trong DMF. Hn hp phn ng c un nng 120 oC trong 2
ngy.
Bng 2-14: Kho sat tng hp Zr-ACPEB theo ng lng AcOH (thm nc).
[ACPEB]
[ZrCl4]
AcOH
H2O
(mol/L)
0.015
(mol/L)
0.015
(eq)
30
(mL)
0.10
0.015
0.015
50
0.10
0.015
0.015
70
0.10
V nh hnh
Tinh th nh
0.015
0.015
90
0.10
Tinh th nh
Kt qu
V nh hnh
(thm nc).
Trang 52
KT QUA VA BIN LUN

Kt qu P-XRD cho thy, khi c nh nng linker, mui v lng nc thm vo, tng
ng lng AcOH s t c tinh th hoa tt hn, peak 2 theta = 3.6o thon nhn
hn, c thm peak xut hi n 2 theta = 6.3o, 7.3o v 9.7o v ng nn bng phng hn.
Lng AcOH 90 eq v lng H2O 0.10 mL c xem l iu ki n tt nht cho nhng
kho sat tip theo.
1.1.1.2.
Kho st tng hp theo lng nc
Trong DMF, Zr/ACPEB t l 1:1 v nng ACPEB v Zr l 15x10-3 mol/L, ng lng

acid acetic 90 eq c chn tip tc kho sat vi lng H 2O thay i dn t 0.06 mL
n 1.000 mL. Hn hp phn ng c un nng 120 oC trong 2 ngy.
Bng 2-15: Kho sat tng hp Zr-ACPEB theo lng nc thm vo.
[ACPEB]
[ZrCl4]
AcOH
H2O
(mol/L)
0.015
(mol/L)
0.015
(eq)
90
(mL)
0.06
Tinh th nh
0.015
0.015
90
0.10
Tinh th nh
0.015
0.015
90
0.14
Tinh th nh
0.015
0.015
90
0.20
Tinh th nh
0.015
0.015
90
0.30
V nh hnh
0.015
0.015
90
0.60
V nh hnh
0.015
0.015
90
1.00
V nh hnh
Trang 53
Kt qu
KT QUA VA BIN LUN
Hnh 2-43: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo lng nc thm vo.
Hnh 2-9 cho thy c s thay i ca gin P-XRD khi thm vo th tch nc khac
nhau. T khong 0.20 mL tr i, qua trnh hnh thnh tinh th bt u b cn tr, c cac
peak l xut hi n. Khi lng nc thm vo nhiu hn 0.30 mL, ta thy c s mt i ca
nhng peak 2 theta < 10, nh v y , qua trnh kt tinh b cn tr mnh.
T kt qu trn cho thy nh hng ca modulator v nc n s to thnh cung nh
thnh phn cu trc ca Zr-ACPEB. Thm 0.10 ml H2O vo diu kin tng hp trn c
chn lm iu kin ti u cho kho sat tng hp vt liu Zr-ACPEB.
2.2.1.3.
Kho st tng hp theo nhi t
T l Zr/ACPEB 1:1 v nng ACPEB v Zr l 15x10 -3 mol/L, ng lng acid acetic
90 eq, lng H2O 0.100 mL trong DMF. Hn hp phn ng c un nng 85 oC, 100
o
C v 120 oC trong 2 ngy.

Bng 2-16: Kho sat tng hp Zr-ACPEB theo nhi t .
[ACPEB]
[ZrCl4]
AcOH
(mol/L)
0.015
(mol/L)
0.015
(eq)
90
(mL)
0.10
(oC)
120
Tinh th nh
0.015
0.015
90
0.10
100
Tinh th nh
0.015
0.015
90
0.10
85
Tinh th nh
H2O Nhi t
Trang 54
Kt qu
KT QUA VA BIN LUN
Hnh 2-44: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo nhi t .

Kt qu P-XRD cho thy nhi t 120 oC, cac peak xut hi n ro net hn, chiu r ng
chn peak nh hn v ng nn cho thy kt tinh tt hn so vi nhi t 85oC v
100 oC.
1.1.1.3.
Kho st tng hp theo thi gian
T l Zr/ACPEB 1:1 v nng ACPEB v Zr l 15x10 -3 mol/L, ng lng acid acetic
90 eq, lng H2O 0.100 mL trong DMF. Hn hp phn ng c un nng 120 oC
trong 1 ngy, 2 ngy, 3 ngy.
Bng 2-17: Kho sat tng hp Zr-ACPEB theo thi gian.
[ACPEB]
[ZrCl4]
AcOH
(mol/L)
0.015
(mol/L)
0.015
(eq)
90
(mL)
0.10
(oC)
120
(ngay)
1
Tinh th nh
0.015
0.015
90
0.10
100
Tinh th nh
0.015
0.015
90
0.10
85
Tinh th nh
H2O Nhi t Thi gian
Trang 55
Kt qu
KT QUA VA BIN LUN
Hnh 2-45: Kt qu P-XRD ca kho sat tng hp Zr-ACPEB theo thi gian.
Hnh 2-11 cho thy thi gian un khng thay i thnh phn pha. Hn na, ng nn
phng cho thy kt tinh ca vt liu tng dn v n nh theo thi gian.
2.2.2.
Kt qu phn tch c tnh cu truc ca Zr-ACPEB
2.2.2.1.
Phn tch FT-IR
Qua ph , nhn thy c nhng mui xut hin trong vng 2800-3500 cm -1 (l mui ca
OH ca nc do KBr ht m). Ti vng xung quanh 1650-1700 cm -1 c s xut hin ca
cac mui ca C=O v mui ca vng benzen ti vng 1580-1600 cm -1. So sanh vi kt qu
FT-IR ca linker ACPEB cho thy c s tn ti ca cac nhm chc c trng ca linker
trong MOF to thnh. (Ph lc 4)
2.2.2.2.
Phn tch nhi t trong lng (TGA)
Mu Zr-ACPEB ([ZrCl4]:[ACPEB] = 0.015M : 0.015M, 90 eq AcOH, 0.10 mL H 2O) l

tinh th dng bt, mu vng tng hp theo iu kin ti u c dng xac nh bn
nhit. Gin phn tch nhit TGA c ghi trn may TGA Q500 vi tc gia nhit l
5 C/ pht trong mi trng khng kh, khong nhit t nhit phng n 600 C.
Trang 56
KT QUA VA BIN LUN
Hnh 2-46: Gin phn tch nhi t TGA ca tinh th MOF va tng hp.
Hnh 2-13 th hi n gin TGA ca v t li u MOF va tng hp (as-synthesized), cha
trao i dung mi. Ta quan sat thy c 3 bc gim khi lng: i) t nhi t phng n
100 oC c th l khi lng t s hp ph nc, ii) t 100 oC n 225 oC khi lng gim
c th l do s thoat ra ca cac phn t dung mi DMF trn b m t v trong l xp ca
v t li u, iii) trong khong t 425oC v 500 oC, khi lng gim mnh (> 50%), y l
giai on khung sn ca v t li u ang b pha huy. Nhi t t 500oC tr i, khi lng
sn phm hu nh khng thay i chng t tinh th b phn huy hon ton thnh ZrO2.
Trang 57
KT QUA VA BIN LUN
Hnh 2-47: Gin phn tch nhi t TGA ca tinh th MOF sau khi hot hoa.
Hnh 2-14, ng cong TGA ca tinh th MOF sau khi c hot hoa trong 24 gi 120
o
C. Ta quan sat thy c 2 bc gim khi lng: i) t nhi t phng n 100 oC khi
lng gim c th l do hp ph hi m ca mi trng, ii) trong khong t 425 oC v

500 oC, khi lng gim mnh (65%), y l giai on khung sn ca v t li u ang b
pha huy. Nhi t t 500oC tr i, khi lng sn phm hu nh khng thay i chng
t tinh th b phn huy hon ton thnh ZrO2.
Nh n xet: ng cong TGA ca tinh th MOF sau khi c hot hoa (hnh 2-14) tng t
nh ng cong TGA ca v t li u MOF va tng hp (hnh 2-13). Tuy nhin, trong
khong nhi t phng n 200 oC, phn khi lng gim do phn t ngoi lai cn li
trn MOF ch chim khong 8% so vi 26% khi lng nh trc lc hot hoa.
Bng khao sat TGA cho thy: bn nhi t ca v t li u Zr-ACPEB cao, b phn huy
nhi t trn 400oC. Qua trnh hot hoa cha hon ton, cac phn t dung mi vn cn
nm trong l xp ca MOF.
Trang 58
KT QUA VA BIN LUN

2.2.2.3.
Di n tch b m t
Din tch b mt ring ca vt liu Zr-ACPEB nghin cu c xac nh theo m hnh

Langmuir l 748.645 m2/g (ph lc 14) v theo m hnh BET l 573.524 m 2/g (ph lc
15).
Trang 59
THC NGHIM
Chng 3
Thc nghi m
3.1. Dng c, hoa cht, thit b

3.1.1.
Dng c
Bnh cu (50 mL, 100 mL), Schlenk flask, Schlenk tube, kim tim, ca t (1 cm, 2 cm),
pipet (5 mL, 10 mL, 25 mL), pasteur pipet, becher (100 mL, 250 mL), erlen (100mL, 250
mL), nhi t k thy ngn (200 oC), h thng sinh hn, phu lc Bchner, giy lc, vi qun,
bp cao su, kp, v gia , vial (8 mL), micropipet (100-1000 L, 5-50 L).
3.1.2.
Acid 2,5-diiodobenzoic
4-etinilbenzoat metil
SOCl2
N,NDimethylformamid (DMF)
Amoniac (NH3)
Acetat etil (EtOAc)
n-Hexan
Trietilamin (TEA)
Tetrahidrofuran (THF)
Iodur ng (I) (CuI)
Pd(PPh3)2Cl2
MeOH
Hidroxid kalium (KOH)
Hidroxid natrium(NaOH)
Clorur Amonium (NH4Cl)
Sulfat natrium(Na2SO4)
Etanol (EtOH)
Acid acetic (AcOH)
Zirconium (IV) clorur (ZrCl4)
Diclorometan (CH2Cl2)
Nc kh ion
3.1.3.
Hoa cht
Sigma-Aldrich
Sigma-Aldrich
Trung Quc
Acros, Trung Quc
Sigma-Aldrich
Trung Quc
Trung Quc
Fisher
Merck, Trung Quc
Sigma-Aldrich
Sigma-Aldrich
Trung Quc
Trung Quc
Sigma-Aldrich
Fisher
Trung Quc
Trung Quc
Merck
Acros
Sigma-Aldrich
Thit b
May c quay Buchi

Cn phn tch
May siu m Cole-Parmer
May li tm Hettich
May khuy t c gia nhi t Arec
T sy Thermo scientific
Trang 60
THC NGHIM
H Schlenk line Chemglass
FT-IR, P-XRD, TGA
H thng hot ha Masteprep-vacuum
May o din tch b mt Nova3200e
3.2. Thc nghi m
3.2.1.
Quy trnh iu ch linker HO2C[PEP(CONH2)EP]CO2H
3.2.1.1.
Phn ng iu ch benzamid
Cho acid 2,5-diiodobenzoic (1 mmol, 374 mg) vo bnh cu 3 c 25 mL, thm vo 2 git
DMF (ch : phi thm DMF trc khi cho SOCl 2 vo bnh phn ng). H phn ng
c lp vo ng hon lu c h thng hp thu kh HCl, t ln bp. 3mL SOCl2 c
cho vo v un hon lu 80 oC. Sau 2 gi, hn hp c lm ngu i v lm lnh xung
0-5 oC. Trong thi gian , hn hp (A) 5 mL NaOH 15% v 5 mL NH 3 cung c lm
lnh. Cho t t hn hp ban u vo erlen cha hn hp (A), va cho va khuy u,
thy xut hi n tinh th trng. yn trong 15 phn ng xy ra hon ton. Cht rn
c ho tan trong 40 mL hn hp H 2O/ EtOAc (v/v=1/1). Ly lp EtOAc v ly trch lp
H2O bng EtOAc (3 ln). G p phn hu c li, lm khan bng Na2SO4 sau em i c
quay, lm kh, thu c sn phm (3) mu trng. [47]
3.2.1.2.
Phn ng Sonogashira
Trong mi trng kh N2, hn hp 2,5-diiodobenzamid (0.5 mmol, 186.5 mg), 4etinilbenzoat metil (1.3 mmol, 208 mg), Pd(PPh 3)2Cl2 (17.5 mg) v CuI (1 mg) c ho
tan trong 14 mL THF/ Et3N (v/v= 1/1). Phn ng c thc hi n nhi t phng,
khuy u trong 16 gi.
Sau khi phn ng kt thc, dung mi c thu hi bng h thng c quay v phn cht
rn cn li c ra ln lt vi 30 mL n-hexan, 30 mL EtOAc, 10 mL NH4Cl bo ho,
10 mL H2O, sau kh, thu c sn phm (5) mu vng nht. [41]
3.2.1.3.
Phn ng thy gii
Trong bnh cu 25mL cho vo cht (5) (0.3 mmol, 131 mg), KOH (615 mg), 6mL MeOH,
6mL THF v 4 mL H2O. Phn ng din ra 50 oC trong 19 gi. Dung mi hu c c
thu hi bng h thng c quay v phn cn li c ho tan trong nc ri acid hoa bng
Trang 61
THC NGHIM
HCl n khi khng cn xut hi n thm kt ta. Kt ta xut hi n c lc ra vi nc,
sau lm kh thu c sn phm (6) mu vng. [48]
3.2.2.
Tng hp Zr-MOF vi linker HO2C[PEP(CONH2)EP]CO2H
3.2.2.1.
Quy trnh tng hp
Hn hp gm ZrCl4, acid acetic 99%, v nc c ho tan vo DMF trong vial 8 mL.
Tng th tch hn hp l 4 mL. Hn hp sau c chiu x siu m trong 30 pht v
yn khong 4 gi. Linker ACPEB c thm vo hn hp. Phn ng c nhi t t
1 ngy n 3 ngy.
iu kin ti u sau khi a khao sat: Hn hp gm ZrCl4 (0.015 mmol), acid acetic 99%
(90 eq), v nc (100 L) c ho tan vo DMF trong vial 8 mL. Tng th tch hn hp
l 4 mL. Hn hp sau c chiu x siu m trong 30 pht v yn khong 4 gi.
Linker ACPEB (0.015 mmol) c thm vo hn hp. Phn ng c tin hnh 120 oC
trong 3 ngy.
Sau khong thi gian gia nhit, mu cht c ly ra khi t sy, ngui. Thc hin
tinh ch li sn phm bng cach lc ra. u tin dng dung mi DMF loi b phn
linker cha phn ng v dung mi phn hy. Sau , phn DMF tha trn b mt vt liu
c loi b bng cach lc ra vi EtOH.
3.2.2.2.
Quy trnh trao i dung mi
Tinh th MOF sau khi tng hp c ngm trong DMF (4 gi). Sau , ngm trong
EtOH (24 gi), cach 2 gi lc m t ln. Tip theo, ngm trong dung mi CH2Cl2 (24 gi),
cach 2 gi lc m t ln, sau 12 gi thay dung mi m t ln.
3.2.2.3.
Quy trnh hot ho
Sau khi trao i dung mi, MOF s tip tc c hot ha bng bng h thng
Masterprep vacuum 120 oC trong 24 gi. Mu c cho vo cell chuyn dng, chy
chng trnh nhit v rt chn khng bng may NOVA.
Trang 62
KT LUN
Chng 4
Kt lu n
KT QUA
Linker ACPEB ln u tin c nghin cu tng hp v s dng kt hp vi ZrCl 4
kho sat kh nng hnh thnh vt liu Zr-MOF mi.
T kt qu phn tch P-XRD, d oan c kh nng hnh thnh c v t li u MOF bng
phng phap nhit dung mi. Tuy nhin, tinh th hoa cn cha cao.
MOF to thnh c di n tch b m t ring theo m hnh Langmuir l 748.645 m2/g v theo
m hnh BET l 573.524 m2/g.
Theo kt qu phn tch nhi t trng lng TGA, MOF tng hp c bn nhi t tng
i cao (> 400 oC). Tuy nhin, qua trnh hot hoa cha hon ton, vn cn cac phn t
ngoi lai trong l xp ca MOF, nh hng n kt qu o di n tch b m t v th tch l
xp ca v t li u.
NGHI
Cac iu ki n tng hp linker cn c ti u hoa thm tit ki m thi gian v chi
ph tng hp, cung nh mang li sn phm vi tinh khit cao.
Cac iu kin tng hp vt liu Zr-MOF mi cn c tip tc nghin cu tng kh
nng tinh th hoa, t phn tch c cu trc ca v t li u bng phng phap nhiu x
n tinh th (SC-XRD). ng thi tm ra dung mi trao i v nhit hot ha thch
hp xac nh chnh xac din tch b mt ring v kch thc l xp ca vt liu. Trn
c s , thm d tim nng ng dng ca v t li u ny trong linh vc hp ph, lu tr
kh v cac linh vc khac.
Trang 63
TAI LIU THAM KHAO
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Trang 68
PHU LUC
Chng 5
Ph lc
Ph lc 1: Ph IR ca 2,5-diiodobenzamid.
Ph lc 2: Ph IR ca diester MeOOC[PEP(CONH2)EP]COOMe.
Trang 69
PHU LUC
Ph lc 3: Ph IR ca diacid HOOC[PEP(CONH2)EP]COOH.
Ph lc 4: FT-IR ca Zr-ACPEB.
Trang 70
PHU LUC
Ph lc 5: Ph 1H NMR ca 2,5-diiodobenzamid.
Trang 71
PHU LUC
Trang 72
PHU LUC
Ph lc 6: Ph 1H NMR ca diester MeOOC[PEP(CONH2)EP]COOMe.
Trang 73
PHU LUC
Ph lc 7: Ph 13C NMR ca diester MeOOC[PEP(CONH2)EP]COOMe.
Ph lc 8: Ph 1H NMR ca diacid HOOC[PEP(CONH2)EP]COOH.

Trang 74
PHU LUC
Trang 75
PHU LUC
Ph lc 9: Ph 13C NMR ca diacid HOOC[PEP(CONH2)EP]COOH.
Trang 76
PHU LUC
Ph lc 10: Ph MS ca diester
MeOOC[PEP(CONH2)EP]COOMe.
Ph lc 11: Ph MS ca diacid HOOC[PEP(CONH2)EP]COOH.
Trang 77
PHU LUC
Ph lc 12: ng phn tch nhit trng lng ca Zr-ACPEB va tng hp.
Ph lc 13: ng phn tch nhit trng lng ca Zr-ACPEB sau khi hot hoa.
Trang 78
PHU LUC
Ph lc 14: Di n tch b m t xac nh theo Langmuir.
Trang 79
PHU LUC
Ph lc 15: Di n tch b m t xac nh theo BET.
Trang 80
PHU LUC
Trang 81
PHU LUC
Ph lc 16: Thit b o P-XRD D8 Advance Bruker.
Ph lc 17: Thit b o TGA Q500.
Ph lc 18: H thng hot hoa chn khng Masterprep vacuum (trai) v May o din
tch b mt Nova3200e (phi).
Trang 82
PHU LUC
Ph lc 19: H thng Schlenk line.
Ph lc 20: Schlenk flask (trai) v Schlenk tube (phi).

Trang 83

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LI CAM N

Em xin gi li cm n su sc n thy L Ngc Thch v thy on L Hong Tn

SVTH: L Hunh Thanh Tho

KHI QUT MOF..................................................................................................12

1.1.1.1. Phn kim loi............................................................................................15

Cac th h MOF v ang c nghin cu..............................................18

M t s phng phap tng hp MOF v cac yu t nh hng.....................19

1.1.3.1. Phng phap nhit dung mi (solvothermal)............................................19

Cac phng phap kim tra c tnh..............................................................22

1.1.5.1. Kh nng hp ph kh...............................................................................23

SVTH: L Hunh Thanh Tho

GII THIU V ZR-MOF.......................................................................................30

M t s loi v t li u MOF s dng Zr

Vai tr ca cht iu hng (modulator) trong Zr-MOF..............................36

KHAI QUAT V CAC PHAN NG TRONG QUY TRINH TNG HP LINKER

HOOC[PEP(CONH2)EP]COOH, (P-PHENILEN, E-ETINILEN)........................................38

Phn ng iu ch clorur acid......................................................................38

Phn ng amin gii.......................................................................................39

Phn ng ghep c p Sonogashira...................................................................39

Phn ng thy gii.......................................................................................41

CHNG 2 KT QUA VA BIN LUN ...................................................................42

TNG HP ACID 4,4'-(2-CARBAMOIL-1,4-PHENILEN)BIS(ETIN-1,2-DIIL)DIBENZOIC

Phn ng tng hp 2,5-diiodobenzamid.......................................................42

(a) Phn tch FT-IR.................................................................................................43

(a) Phn tch FT-IR.................................................................................................45

Phn ng thy gii.......................................................................................46

(a) Phn tch FT-IR.................................................................................................46

SVTH: L Hunh Thanh Tho

Kho sat iu kin tng hp Zr-ACPEB......................................................47

2.2.1.1. Kho sat tng hp theo nng ...............................................................47

2.2.1.6. Kho sat tng hp theo thi gian..............................................................53

Kt qu phn tch c tnh cu trc ca Zr-ACPEB.....................................53

2.2.2.1. Phn tch FT-IR.........................................................................................53

DUNG CU, HOA CHT, THIT BI. ...........................................................................57

Quy trnh iu ch linker HO2C[PEP(CONH2)EP]CO2H.............................58

3.2.1.1. Phn ng iu ch benzamid....................................................................58

Tng hp Zr-MOF vi linker HO2C[PEP(CONH2)EP]CO2H......................59

3.2.2.1. Quy trnh tng hp....................................................................................59

SVTH: L Hunh Thanh Tho

DANH MUC HINH VE

DANH MUC HINH VE

DANH MUC HINH VE

SVTH: L Hunh Thanh Tho

DANH MUC HINH VE

SVTH: L Hunh Thanh Tho

DANH MUC T VIT TT

DANH MUC BANG BIU

SVTH: L Hunh Thanh Tho

DANH MUC T VIT TT

DANH MUC T VIT TT

University of Oslo (in Norway)

University of California, Los Angeles

Metal Organic Frameworks

Materials of the Institut Lavoisier

Hong Kong University of Science and Technology

Porous Interpenetrated Zirconium Organic framework

Secondary Building Unit

Nuclear Magnetic Resonance spectroscopy

Powder X-Ray Diffraction

Single crystal X-Ray Diffraction

Fourier Transform Infrared Spectroscopy

Brunauer - Emmett - Teller

triflat hay trifluorometansulfonat

SVTH: L Hunh Thanh Tho