Tp ch Ha hc, T. 41, s 4, Tr.

77 - 82, 2003

Nghin cu hot tnh xc tc baz ca hydrotanxit

bng ph ng php ha l ng t
n Ta son 24-3-2003
Mai Tuyn1, ng nh Bch2, Nguyn Quang Tng2, Nguyn Th Anh Sn2
1

Vin Ha hc cng nghip

Tr#ng i hc S# phm H' Ni
summary

A study of base property of hydrotalcite was carried out using quantum - chemical
calculation method. The basicity is evaluated by using Proton Affinity. In general the
basicity of magnesium - aluminium hydrotalcite is stronger than that of NaOH and KOH.
On increasing Al/(Al+Mg) ratio to 0.33 the basicity is rapidly increased. The center in
which hydroxyl group is attached to aluminium is tronger than that in which hydroxyl
group is attached to magesium. The acetone molecules adsorbed on the surface of
hydrotalcite must overcome a energy barried equal to 9.88 kcal/mol to reach activated
state of base - catalyzed processes.
I - M u
Hydrotanxit l khong st t nhin c cu
trc lp v c cng thc ca t b o nguyn t
Mg6Al2(OH)16CO34H2O [1]. Cu trc tinh th
ca hydrotanxit7c xem nh7 t7ng t vi cu
trc ca khong bruxit Mg(OH)2, trong
Mg2+ lin kt phi tr vi 6 nhm hydroxyl. Khi
cc ion Al3+ thay th cho mt s Mg2+ trong
mng l7i to th nh hydrotanxit, th trn cc
lp c d7 in tch d7ng. in tch d7ng
7c b tr bng cc anion, thng th7ng l
CO 23 . Gia cc lp 7c lp y bng cc
anion v n7c. Ng y nay, th7ng dng
hydrotanxit tng hp, i vi hydrotanxit
magi - nhm, th nh phn hp thc c th
l [Mg1-xAlx]x-. A nx/n .mH2O, trong , x = Al/
(Al+Mg), An- l anion c ha tr -n v m l s
phn t n7c kt tinh gia cc lp. Khi x l
nhit n 200oC th n7c thot ra. Nng nhit
cao hn, nh7ng khng qu 500oC, th CO2
7c gii phng v b mt b dehydroxyl ha

mt phn, khi thu 7c dng oxit hn hp

Al-Mg, v d: Mg6Al2O8(OH)2 [1, 2]. Nh nhng
tnh cht , hydrotanxit c nhiu ng dng
quan trng, nh7 7c dng l m cht trao i
anion, tc nhn gim axit trong y t cha
mt s bnh 7ng tiu ha, cht mang xc tc,
v nht l l m cht xc tc tt cho nhiu phn
ng xc tc baz trong tng hp hu c tinh vi,
nh7 phn ng ng7ng t aldol [3], ng7ng t
Knoevennagel [4], ng7ng t Clasen Schmidt
[5], thy phn este [6]...
Kt qu nghin cu bng cc ph7ng php
vt l v ha l cho php 7a ra gi thuyt rng
trung tm baz l nhm hydroxyl b mt -OH
[2]. Khi nghin cu ph IR ca CO2 hp ph
trn b mt hydrotanxitcho thy to th nh ion
bicacbonat [7]. Reichle [8], t kt qu nghin
cu NMR, d 7a ra gi thuyt l trung tm
hot ng xc tc baz trn b mt cha nhm
Al-O-H.
hydroxyl gn vi nhm t din
C7ng baz ca nhng nhm n y thay i
theo t l s Al/Mg trong mng l7i [8, 9]. i
77

vi oxit magi, trung tm hot ng xc tc

baz l nhng nhm hydroxyl gn vi Mg trn
cc cnh hoc nh ca tinh th v c cu trc Mg-O-H [10], cn trong mng l7i hydrotanxit,
c7ng baz ca nhm n y rt c th cng
chu nh h7ng ca Al ln cn. 7ng nhin,
trn b mt hydrotanxit c th c mt c hai
kiu trung tm ni trn.
Nh7 d bit, trong xc tc d th, t7ng tc
gia phn t phn ng v trung tm hot ng
th7ng c vai tr quan trng quyt nh tc
v chiu h7ng qu trnh phn ng. Da trn c
s , trong cc nghin cu ha l7ng t,
phn nh tinh cht b mt cht rn nh h7ng
n trung tm hot ng, th nhng t7ng tc
gn c ngha ln hn, cn nhng t7ng tc xa
c nh h7ng khng ng k v c th b qua.
V vy, ph7ng php "cm cu trc b mt"
(cluster) 7c ng dng rng rdi trong nghin
cu ha l7ng t tnh cht b mt ca cht xc
tc rn [11].
Trong b i bo n y, chng ti 7a ra cc kt
qu nghin cu bng ph7ng php ha l7ng t
tnh cht baz ca hydrotanxittrn c s nh
gi i lc proton ca trung tm hot ng v
kh nng ca nhng trung tm baz trong
qu trnh hot ha phn t cacbonyl c nguyn

H
O

Al

Al

II - M hnh v' ph)ng php

i vi nhm hydroxyl gn lin vi Al trn
b mt, cc php tnh 7c thc hin vi cc
cm cu trc (H3AlOH) v [Hm(HMg)n
AlOH], trong m = 2, 1, 0, cn n = 1, 2, 3, 4
(s 1). Trong tr7ng hp nhm hydroxyl gn
vi Mg, cc php tnh 7c thc hin vi cu
trc HMgOH, H3AlOMgOH v H3AlOHMg
OH (s 2). Trong cc cu trc trn, cc
nguyn t hiro 7c dng ng ha tr
cui cc cu hnh.
Nng l7ng 7c tnh bng cch ti 7u ha
hnh hc khi s dng trong ch7ng trnh
Gaussian 98 [12] theo chun RHF/3-21G. Trn
c s kt qu thu 7c t tnh ton theo cc b
c s khc nhau, tc gi [13] thy rng vi b
c s 3 - 21 G, vic d on nng l7ng l
chnh xc i vi mc ch so snh. Cc php
tnh tn s theo cng chun trn 7c thc hin
xc nh cu trc t trng thi bn to n cc
khi gi tr Nimag = 0, hay cu trc chuyn tip
khi gi tr Nimag = 1.

O
H

t hiro v tr alpha i vi nhm cacbonyl,

l nhng phn t c kh nng tham gia v o
cc phn ng xc tc baz.

Mg

O
H
H

Mg

Al

Al

Mg

Mg
H

(Mg3AlOH)

O Mg
O Mg

Mg
H

(Mg4AlOH)

S 1: Cu trc trung tm baz gn vi Al

78

Mg

Mg

(Mg2AlOH)

Mg

(MgAlOH)

(AlOH)

Al

H
H

H
H

Mg

Mg

O
Mg
H

Al

Al

O H
H
(AlOHMgOH)

(MgOH)

(AlMgOH)

S 2: Cu trc trung tm baz gn vi Mg

i lc proton 7c tnh theo h thc sau y:
PA = (E - ZPE) - (EH - ZPEH),
trong , E v EH t7ng ng l nng l7ng ca
cu trc khng v c proton ha, cn ZPE v
ZPEH l gi tr hiu chnh nng l7ng im
khng t7ng ng vi cu trc khng v c
proton ha. Vi mc ch so snh, cc php
tnh i lc proton cng 7c thc hin vi
NaOH v KOH, nhng baz mnh th7ng 7c
s dng i vi cc phn ng xc tc baz ng
th (cc mu 5 v 6 bng 2).
xt kh nng hot ha phn t cacbonyl,
trong cng trnh n y, phn t axeton 7c kho
st kh nng tham gia phn ng xc tc baz.
Qu trnh t7ng tc b mt 7c tnh trn cc
cu trc ca phc hp ph b mt gia phn t

axeton v trung tm baz. gim thi gian

tnh ton, trung tm baz 7c dng l nhm
hydroxyl gn vi Mg. Cc php tnh 7c thc
hin cng bng ph7ng php t7ng t ni trn.
Trng thi chuyn tip 7c nh v bng
ph7ng php QST2, sau tnh tn s xc
nh cu trc chuyn tip (TS) khi thu 7c gi
tr Nimag = 1. Cu trc chuyn tip cn 7c
khng nh bng tnh IRC v t y c th tnh
nng l7ng hot ha phn t axeton bng trung
tm baz trn hydrotanxit.
III - Kt qu v' tho lun
Nhng kt qu thu 7c v baz vi
nhng trung tm loi I (nhm hydroxyl gn vi
nhm trn b mt) 7c nu trong bng 1.

Bng 1: baz ca cc trung tm

No

Xc tc

EHF (hartree)

AlOH trong hydrotanxit

ZPE (hartree)

Etotal (hartree)

PA
(kcal/mol)

AlOH
AlOHH+

-317,3860885
-317,9316034

0,033127
0,046902

-317,3529615
-317,8847014

333,67

MgAlOH
MgAlOHH+

-590,41076779
-590,9646425

0,037316
0,051258

-590,3734519
-590,9133835

338,81

Mg2AlOH
Mg2AlOHH+

-863,5479891
-864,1381057

0,044577
0,057251

-863,5034121
-864,0808547

362,35

Mg3AlOH
Mg3AlOHH+

-1136,5905279
-1137,1899007

0,048081
0,060783

-1136,5424469
-1137,1291177

368,14

Mg4AlOH
Mg4AlOHH+

-1410,0357848
-1410,5725146

0,058431
0,068592

-1409,9773538
-1410,5039226

330,43

79

T bng 1, c th nhn thy rng, khi

chuyn t mu s 1 sang mu s 2, tc l khi
nhm Al-OH gn v o mng l7i vi Mg, th
baz tng ln, tuy nhin, mc tng
baz ch7a ln (t 333,67 ln 338,81 kcal/mol).
Nh7ng khi chuyn t mu s 2 sang mu s 3,
th baz tng ln r rt (t 338,81 ln 362,35
kcal/mol). Cn khi chuyn t mu s 3 sang
mu s 4, mc tng baz cng li khng
nhiu (t 362,35 ln 368,14 kcal/mol). Ti mu
s 3, gi tr ca i l7ng x (x = Al/(Al+Mg))
bng 0,33. Nh7 vy kt qu n y ho n to n ph
hp vi thc nghim [14], rng khi trong mng
l7i hydrotanxit, vic thay th Mg bng Al n
gi tr x = 0,33 l gii hn, ti y th hin tnh

cht y ca hydrotanxit.
i vi cc trung tm baz loi II, trong ,
nhm hydroxyl gn lin vi Mg trn b mt
(bng 2), cng nhn thy nh h7ng ca
nguyn t nhm ln cn l m tng baz r
rt. T mu 1 sang mu 2, i lc proton tng t
218,79 ln 350,39 kcal/mol. Tuy nhin, trong
tr7ng hp c nhm hydroxyl gn c v o
nguyn t nhm ln cn, th i lc proton ca
trung tm -MgOH li gim i (mu 3), trong
khi i lc proton ca trung tm H3AlOH ln
cn cao hn (mu 4). Trong [15] cng nhn
thy rng khi tng t s Mg/Al trong
hydrotanxit, th s trung tm baz yu hn
tng.

Bng 2. Tnh cht baz ca cc trung tm -MgOH trong hydrotanxit

No

Xc tc

EHF (hartree)

ZPE (hartree)

PA
(kcal/mol)

MgOH
MgOHH+

-274,0928979
-274,4550587

0,017778
0,031280

-274,0751199
-274,4237787

218,79

AlMgOH
AlMgOHH+

-590,3951557
-590,9666101

0,037195
0,050273

-590,3579607
-590,9163371

350,39

AlOHMgOH
AlOHMgOHH+

-664,9352716
-665,4723737

0,046167
0,059304

-664,8891046
-665,4130697

328,79

AlOHMgOH
AlOHH+MgOH

-664,9352716
-665,4930319

0,046167
0,058069

-664,8891046
-665,4349629

342,53

NaOH
NaOHH+

-235,8688788
-236,3254602

0,011302
0,025315

-235,8575768
-236,3001452

277,72

KOH
KOHH+

-671,1380285
-671,636052

0,010524
0,024669

-671,127504
-671,611383

303,64

Khi so snh vi cc i lc proton ca NaOH

v KOH (mu 5 v 6, bng 2), thy rng, tr
mu 1 bng 2, tt c cc trung tm baz
nghin cu trong cc bng 1 v 2 u c i lc
proton cao hn, tc l baz ln hn.
Nhng kt qu thu 7c trn y chng t
rng cc trung tm baz trn b mt hydrotanxit l nhng nhm hydroxyl gn lin vi
nguyn t nhm hay magi trn b mt,
baz ca nhng trung tm t7ng i ln so
vi cc baz in hnh, trong trung tm baz
gn vi nguyn t nhm mnh hn. C th l
80

Etotal (hartree)

trung tm n y d d ng 7c pht hin bng

ph7ng php chun . Nh7 vy, kt qu tnh
ton l7ng t ho n to n ph hp vi thc nghim.
Kt qu nghin cu ha l7ng t i vi
trng thi hp ph axeton trn b mt
hydrotanxit 7c m hnh ha nh7 trn s 3.
Nh7 c th nhn thy trn s 3, trng thi
hp ph ban u (CT1), cu trc ca phn t
axeton cn 7c gi gn nh7 trong phn t
axeton t do (xem cu trc phn t axeton). Tuy
nhin, khi chuyn n trng thi hot ha (CT2),
d i ca lin kt C-H ca nhm metyl lin

kt vi b mt d b gidn d i ra (t 1,085 n
3,364 ) v tin gn n nguyn t oxi trn
b mt (t 5,274 n 0,982 ). Ho n to n
c th tin rng trng thi n y phn t

axeton d sn s ng tch ra th nh cacbanion

CH3COCH2(-) tip tc qu trnh tc dng vi
phn t cacbonyl th hai trong qu trnh kiu
ng7ng t aldol.

H
H

H
C

1,085

H
H

C
C

3,363

(CT1)

H
5,274

0,928

Mg
1,797

(CT2)

O1,956 Mg

EHF = -465,0351244
ZPE = 0,110684
Etotal = -464,9244404
Nimag = 0

EHF = -465,0303142
ZPE = 0,111764
Etotal = -464,9185502
Nimag = 0

S 3: Trng thi hp ph vt l v ha hc axeton trn hydrotanxit

H
H

C
C

H
H

1,386

1,0851

1,0851

1,080
H 1,0851 C
1,5148
H
C

1,0802
1,085

1,5149

1,211

1,252

O - - - -Mg

1,886

(TS)

(axeton)

EHF = -465,0159672
ZPE = 0,107275
Etotal = -464,9086922
Nimag = 1

S 4: Cu trc TS ca qu trnh hot ha axeton trn hydrotanxit

-464,90869
TS
9,88 kcal/mol
-464,92444
CT1

6,18 kcal/mol
-464,91855
CT2

S 5: H ng r o nng l7ng hot ha phn t

axeton trn HT

Qu trnh chuyn ha t cu trc CT1 n

CT2 phi i qua trng thi chuyn tip, tc l
phi tiu tn mt nng l7ng. Cu trc ca
trng thi chuyn tip 7c m hnh ha bng
cu trc TS (s 4). T s 4, c th nhn
thy cu trc TS l trng thi trung gian gia
CT1 v CT2 v cng khc vi cu trc ca phn
t axeton t do.
T nng l7ng to n phn ca cc cu trc
CT1, CT2 v TS, c th tnh 7c nng l7ng
hot ha ca cc qu trnh thun v nghch
(xem s 5). T s 5 c th nhn thy
rng nng l7ng hot ng ca qu trnh
chuyn phn t axeton t trng thi hp ph vt
l (CT1) sang trng thi chuyn tip (TS) l
81

9,88 kcal/mol, cn t trng thi TS n trng

thi hp ph ha hc (CT2), tc l trng thi
sn s ng to th nh cacbanion tham gia v o
cc qu trnh ng7ng t 7c xc tc bng cc
trung tm baz trn b mt hydrotanxit, c th
gii phng mt nng l7ng bng 6,18 kcal/mol,
nh , cacbanion 7c bn ha.
Li cm n: Cng trnh #c ho'n th'nh vi
s h tr t'i chnh ca Ch#ng trnh Nghin
cu c bn trong lnh vc Khoa hc t nhin.
T'i liu tham kho
1. T. Lopez, O. Bosch. E. Ramos, P. Gomez,
O. Novaro, D. Acosta, F. Figueras.
Langmuir, Vol. 12, P. 1889 (1996).
2. M. Rajamathi, G. S. Thomas, P. V. Kamath.
Pro. Indian, Acad. Sci. (Chem. Sci), Vol.
133 (5 & 6), P. 671 (2001).
3. E. Suzuki, Y. Ono. Bull. Chem. Soc. Jpn,
Vol. 61, P. 1008 (1988).
4. A. Corma, S. Iborra, J. Primo, F. Rey. Appl.
Catal. A: General, Vol. 114, P. 215 (1994).
5. A. Guida, M. H. Lhouty, D. Tichit, F.
Figueras, P. Geneste. Appl. Catal. A. General,

82

Vol. 3944, P. 1 - 17 (1997).

6. A. Corma, S. Iborra, S. Miquel. J. Primo,
J. Catal., Vol. 173, P. 315 (1998).
7. W. T. Reicchle. US Pat. 4, 458, 026 (1984).
8. W. T. Reichle. J. Catal., Vol. 94, P. 457
(1985); J. C. A. A. Roelfs, Thesis, 2001.
9. J. Wang, A. G. Kalinichev, R. J. Kirkpatrick,
X. Q. Hou. Chem. Mater., Vol. 13, No. 1, P.
145 (2001).
10. K. Tanabe, M. Misono, Y. Ono, H. Hattori.
New solid acids and basses, Their catlytic
properties. Hodansha (Tokyo), Elsevier
(Amsterdam - Oxdord - New York - Tokyo),
P. 38 (1989).
11. R. Shah, M. C. Payne, M. H. Lee, J. D.
Gale. Science, Vol 271, P. 1395 (1996).
12. M. J. Frisch et al. Gaussian 98, Revision A
3. Gaussian Inc., Pittsburgh PA (1998).
13. D. Margetic, M. R. Jhonson, R. N.
Warrener, Molecules, Vol. 5, P. 1417 (2001).
14. M. J. Climent, A. Corma, S. Iborra, J.
Primo. J. Catal., Vol. 151, P. 60 (1995).
15. A. Corma, V. Fornes, R. M. Martin - Aranda,
F. Rey. J. Catal., Vol. 134, P. 58 (1992).