2

C : C N H

hng 1
TNG QUAN V VT IU KHUNG HU C KIM
OI (MOFs) V CC IGAND CACBOATE H
PYRIDINIUM S DNG TNG HP MOFs
.. TNG QUAN V KHUNG HU C KIM OI (MOFs)
1.1.1. Lch s pht trin

Nhng nm trc y cc nh h hc nghin cu v s dng nhng loi
vt liu c cu trc xp nh entonite zeolite ng dng trong cng nghip nh
hp ph kh xc tc... Tuy nhin, nhng vt liu ny c cu trc mng l xp khng
ng u v din tch mt cn thp. V vy cc nh khoa hc c gng nghin
cu ra nhng cu trc xp ng u hn v din tch mt ln hn.
Trong nhng nm u thp k 90 c th k XX nhm nghin cu c tc
gi Yghi ti trng i hc UCLA M tm phng php kin to c kim sot
cc l xp mt cch chnh xc trn c s khung hu c-c kim gi l vt liu
MOFs
[1]
.
Nm 1995 tc gi Yghi cng tng hp thnh cng vt liu c khng gin
n trong ln hnh ch nht ng phng php tng hp Hydrotherml t
Cu(NO3)
2
vi 44-Bipyridine v 1,3,5-Trazine
[2]
.
Nm 1996 tc gi Yghi cng cu trc c nhng vt liu rn xp tng
hp t phc kim loi Con Niken Zine vi cid 135-BTC dng lu tr
Hydrogen
[3]
.
Nm 1997 nhm nghin cu c GS. Omr M.Yghi tm r loi vt liu
c cu trc xp v mt ring ln l vt liu c xy dng trn c s
khung hu c kim loi (Metl Orgnic Frmeworks) vit tt l MOFs nhm c
ng c nhiu cng trnh nghin cu c ng trn cc tp ch uy tn nh:
Nture Science Journl of Americn Cc cng trnh nghin cu tp trung vo
cc vn thit k tng hp vt liu MOFs c mt ring ln c ng dng
lu tr kh hp th kh tch kh
3

C : C N H

Nm 2004 Yghi v cc ng nghip tng hp, nghin cu ng dng lu tr
kh H
2
c cc IRMOF-1, IRMOF-8, IRMOF-18, IRMOF-11 v MOF-177.

Hnh 1.1. Cu trc khng gian ca cc vt liu MOFs vi cc lin kt hu c trn
c s carboxylic acid kt ni cc tm kim loi vi nhau, do nhm nghin cu ca
GS Omar M. Yaghi tng hp ra. Hnh cu trong mi cu trc minh ha cho khng
gian ln nht c trong l xp m khng b nh hng ca cc tng tc van der
Waals vi khung hu c kim loi
[4]
Nm 2005 Yghi v cc ng nghip tng hp MOF-69A C, MOF-70
80 d trn cu ni croxylic cid v cc kim loi nh Zn P Co Mn v T. Nm
2006 nhm tng hp c MOF-500 c cng thc
(Fe
3
O)
4
(SO
4
).12(BPDC)
6
(BPE)
6
. Cc vt liu MOFs tng hp c c mt ring
ln c th t n 5640 m
2
/g cho vt liu MOF-177 c hnh thnh trn c s
Zn
4
O(COO)
6
vi lin kt hu c l 135-benzenetribenzoic acid, c kh nng hp
th lng cron dioxide ln hn trong lng c n 150% nhit trong phng
v p sut ph hp (35 r)
[5]
.
Nhm nghin cu c gio s Yghi c th thy i thnh phn ca cc
nhm kim loi - hu c ty nhm to ra nhng cu trc vt liu mi c tnh nng
vt tri hn nhng vt liu nghin cu trc : nh bn nhit, din tch b
mt ring ln, cu trc l xp vng chcnhm p ng nhiu ng dng rng ri,
4

C : C N H

y ha hn ca nhng loi vt liu xp ny trong cc lnh vc nh: xc tc, phn
tch hn hp lu tr kh


nh 1.2. u trc MO-5
[6]

Khung hu c kim loi (MOFs) l nhm vt liu lai mi c cu trc xp
m rng c cc l nh li ti ging nh hnh t ong c hnh thnh da trn s lin
kt ca cc ion ca kim loi chuyn tip v cc cu ni hu c. Cu trc c n c
MOF thuc loi vt liu tinh th cu to t nhng ction kim loi hy nhm ction
kim loi lin kt vi cc phn t hu c (lignd) hnh thnh cu trc c khng
gin chiu xp v c mt ring ln
[7]
.
MOFs gm nhng nhm cation kim loi vi cc nhm carboxylate, mt cu
ni dicroxylte c dng lm tc nhn phn ng hnh thnh mt khi t din vi
mi nh l mt nhm carboxylate kim loi. Tnh cht ca cc cu ni hu c khc
nhau l khc nhau v l nht bin, chng cho php qu trnh lp ghp cc cu ni
vo b khung khng gian ba chiu ca vt liu MOFs l duy nht, cu trc vng
chc ny c din tch b mt ring ln v th tch mao qun co hn hu ht cc loi
cu trc xp khc. MOFs l mt tim nng v tn lu tr kh cng nh nh
hng nghin cu vt liu composite mi
[8]
.
5

C : C N H

..2. N i MOFs
[1]
Vt liu MOFs gm nhng tm ion kim loi lin kt vi cc cu ni hu c
to nn b khung hu c - kim loi vng chc nh nhng gin gio xy dng, bn
trong b khung l nhng l trng to nn mt h thng xp vi nhng vch ngn
ch l nhng phn t hoc nguyn t.
1.1.2.1. C io ki oi
Cc tm ion kim loi thng l cc cation Zn
2+
, Cu
2+
, Co
2+
, Pb
2+
cc mui
kim loi thng dng tng hp l loi ngm nc nh: Zn(NO
3
)
2
.6H
2
O,
Co(NO
3
).6H
2
O, Cu(NO
3
).4H
2
O, Co(CH
3
COO)
2
.4H
2
O

nh 1.3. c thnh phn ca MO-5
1.1.2.2. C i
Cc phn t hu c s dng trong qu trnh tng hp MOFs s to ra cc lin
kt hu c Ccoxylte vi tm kim loi.
Cc phn t hu c thng l diacid hu c cha hai nhm COOH. Ngoi
ra cn c cc nhm chc khc nh: nitrile sufte mine photphtehy cng
cha cc nhm chc khc nhu cng c s dng lm cu ni.
Vic la chn cc n v cu trc tng hp nn vt liu MOFs phi c
la chn mt cch cn thn cc tnh cht c cc n v cu trc ny phi c
bo ton v sn phm MOFs phi c c nhng tnh cht . Khc vi cc vt liu
copolymer hu c trong n cht v nng ca cc monomer trong polymer
6

C : C N H

quyt nh cc c tnh vt l v c tnh quang hc cng nh kh nng c th gia
cng hay x l chng; i vi vt liu MOFs, cch b tr mng li lin kt cc n
v cu trc trong sn phm MOFs li quyt nh ch yu ln tnh cht ca MOFs.
Qu trnh tng hp vt liu MOFs khng ch yu cu vic la chn v iu ch ra
cc module mong mun, m cn yu cu phi d on trc c chnh xc cch
sp xp cc module ny trong sn phm vt liu dng rn sau cng
[9]
.
..3. C MOFs
1.1.3.1. v x (SBUs)
Vic m t cc cu trc ca MOFs l mt vn kh khn v kh c s gii
thch hp l mt khi ch phn loi n mt cch r rng. Nhm nghin cu ca
gio s Yghi cng cng s pht trin khi nim SBUs. Da vo n v xy
dng th cp (SBUs) m c th tin on c cu trc hnh hc ca cc vt liu
tng hp, t thit k v tng hp cc loi vt liu xp mi c cu trc v trng
thi xp cao. Phn v c ca MOFs c gi l n v xy dng c n (SBU), c
th c m t bi cc cu trc lin kt chung cho mt s cu trc. Mi cu trc
lin kt cn c gi l mt mng li c ch nh mt biu tng, gm ba ch
thng c in m. S r i c n v xy dng c n SBU to iu kin thun
li cho qu trnh nghin cu hin ti v trong tng li.

nh 1.4. Mt s s ca cc MO-31, MOF-32, MOF-33
[10]