Catalysis Communications 5 (2004) 643–646

www.elsevier.com/locate/catcom

Silica immobilized ruthenium catalyst used for carbon

dioxide hydrogenation to formic acid (I): the effect of
functionalizing group and additive on the catalyst performance
a,b
Yiping Zhang , Jinhua Fei a, Yingmin Yu a, Xiaoming Zheng a,*

a
Department of Chemistry, Institute of Catalysis, Xixi Campus, Zhejiang University, Hangzhou 310028, PR China
b
Department of Chemistry, Zhejiang Education Institute, Hangzhou 310012, PR China

Received 6 June 2003; accepted 9 August 2004

Available online 11 September 2004

Abstract

The amine functionalized silica immobilized ruthenium complexes used for CO2 hydrogenation to formic acid were prepared in
an in situ synthesis way. The formic acid turnover frequency of 1384 h 1 at 100% selectivity has been obtained in CO2-expanded
ethanol over Si–(CH2)3–NH(CH2)3CH3–Ru, while NEt3 used as base, which was significantly higher than homogeneous ones.

2004 Elsevier B.V. All rights reserved.

Keywords: Immobilized; Ruthenium; Silica; Formic acid; CO2-expanded solvent

1. Introduction DMF could be reached 1860 h 1. The catalyst was pre-

Recently, the atom economic reaction of formic acid
synthesis from carbon dioxide hydrogenation has at-
tracted much attention. The effective catalysts used for
this reaction were homogeneous ruthenium complexes
in published papers [1–3]. It was also reported [4–6] that
the formic acid production rate reaches turnover fre-
quency (TOF) of 1400 h 1 with PH2/CO2(atm) = 80/130
when scCO2 (supercritical CO2) was used as both a reac-
tant and a solvent. But the separation and recovery of
the catalyst is a major problem in homogeneous cataly-
sis. The immobilization of homogeneous catalyst at the
surface of a support may be a favourable way to solve
this problem. The group of Baiker [7–9] employed
RuCl2[P(CH3)3]4 supported on sol–gel derived silica ma-
trix as catalyst for the synthesis of N,N-dimethylforma-
mide (DMF) from CO2, H2 and NH(CH3)2, the TOF of
* with the general formula (EtO)3Si(CH2)3–X, where X is
Corresponding author. Tel.: +86 571 882 73417; fax: +86 571 882
73283.
E-mail address: xmzheng@dial.zju.edu.cn (X. Zheng).
pared by the co-condensation of RuCl2[P(CH3)2(CH2)2
Si(OC2H5)3]3 with Si(OC2H5)4.
In this paper, the ruthenium immobilized on func-
tionalized silica was used as a new catalyst precursor,
and then ruthenium complexes catalysts were formed
in situ at the reaction process of formic acid syntheses
from CO2 hydrogenation by the catalyst precursor and
triphenylphosphine ligand in CO2-expanded solvent.
This approach offers the following advantages: (1) easy
separation from products; (2) reusability; (3) high activ-
ity and selectivity; (4) simplification of the process, no
need for preparing ruthenium complexes beforehand.
2. Experimental
The preparation of catalysts is as follows: firstly, a
mixture of 6 g silica and 20 mmol functionalizing agents,
a Cl atom, or an NH2 group, in refluxing toluene was
stirred for 8 h, then 25 ml H2O was added, and stirred

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2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2004.08.001
644 Y. Zhang et al. / Catalysis Communications 5 (2004) 643–646
for 4 h. The mixture was filtered and washed several
times with toluene, then dried at 200 C in vacuum.
The functionalized solid was denoted as ‘‘Si’’–(CH2)3–
X. Secondly a mixture of ‘‘Si’’–(CH2)3–Cl, amine (n-
butylamine, diethylamine, respectively), was refluxed in
toluene for 4 h, then filtered, washed and dried at 200
C. Three types of amine functionalized support, de-
scribed as ‘‘Si’’–(CH2)3–NH2, ‘‘Si’’–(CH2)3–NH(CH2)3
CH3 and ‘‘Si’’–(CH2)3–N(CH2CH3)2 were obtained.
Thirdly, an ethanol solution of RuCl3 was mixed with
‘‘Si’’–(CH2)3–NH2, ‘‘Si’’–(CH2)3–NH(CH2)3CH3 or
‘‘Si’’–(CH2)3–N(CH2CH3)2 under stirring. Then, fil-
tered, washed several times with ethanol, and dried at
60 C in vacuum, which was denoted as A–Ru, B–Ru,
or C–Ru in turn. The Ru content measured by ICP-
AES was 0.380 · 10 2, 0.258 · 10 2, 0.290 · 10 2 g/g
catalyst, respectively.
The reactions were performed in a stainless-steel 100
ml autoclave. In a typical run, 0.6 g A–Ru (or B–Ru,
C–Ru), 20 ml solvent, triphenylphosphine ligand, base
were successively introduced. H2 (4.0 MPa pressure)
and then liquid CO2 was pumped into the autoclave
using a syringe pump, the reaction was normally pro-
ceeded at 80 C for 1 h, the total pressure is 16.0 MPa
at reaction temperature. At the end of the reaction,
the reactor was cooled rapidly at first and then depressu-
rized very slowly. The reaction solution collected was
acidified by 10% HCl and the formic acid was esterified
completely for analysis [10]. The esterified sample was
analyzed both by GC–MS equipped with TC-wax col-
umn and GC equipped with poropak QS column and
FID detector. The two results were consistent with each
other.
3. Results and discussion
The activity, expressed as HCOOH TOF of various
Ru catalyst precursors is summarized in Table 1.
Although the reaction conditions were above critical
point of CO2 (Tc: 31.3 C, Pc: 7.39 MPa), the reaction
system was a multi-component and multiphase system,
Table 1
Catalytic results of CO2 hydrogenation with various ruthenium
immobilized catalysts
Entry Catalyst PPh3/Ru HCOOH
(mol ratio)
TOF (h 1)a Selectivity (%)
1 RuCl3 + PPh3 10:1 462 100
2 A–Ru + PPh3 10:1 656 100
3 B–Ru + PPh3 10:1 1384 100
4 C–Ru + PPh3 10:1 868 100
Reaction conditions: reaction temperature, 80 C; H2 pressure, 4.0
MPa; total pressure, 16.0 MPa; reaction time, 1 h; ligand, PPh3; sol-
vent, 20 ml ethanol; base, 5 ml NEt3; stirring rate, 250 r/min.
a
TOF: turnover frequency, mol of HCOOH/mol of Ru/h.
which contained such components: the solid catalyst, a
vapor and a liquid phase (see Fig. 1). A large amount
of CO2 was present in the lower phase, so the volume
of the lower phase was larger than the amount of liquid
solvent added [6,11]. The lower phase could be intro-
duced as CO2-expanded solvent as B. Subramaniam
et al. [12–14] term it. It is likely that the large amount
of CO2 in the lower phase increased the solubility of
H2 in that phase compared to the solubility of H2 in liq-
uid organic solvent, Thus making CO2-expanded solvent
a good medium for CO2 hydrogenation.
From Table 1, HCOOH selectivity of 100% was at-
tained in all of the catalysts, which means that no
byproducts formation under the conditions employed.
Comparison with the homogeneous system (entry 1),
the activity of the immobilized catalyst was greatly en-
hanced (entry 2, 3, 4), which can be ascribed to so-called
site-isolation [15]. Since attaching a catalyst to a support
in such a way, catalytic sites were dispersed and pre-
cluded their dimerization or oligomerization to less reac-
tive species and can, therefore, endowed them with
unique activities compared to their homogeneous
counterparts.
The best catalytic performance was achieved over B–
Ru as catalyst precursor, and the HCOOH TOF reached
1384 h 1, which is almost three times higher than that of
homogeneous system with RuCl3 as precursor. The
activity order of three types of immobilized ruthenium
was as follows: A–Ru < C–Ru < B–Ru. The possible
reason for the different activity of catalyst may be that
the electron donating character of alkyl group bound
to N atom. The ability of electron-donating increased
as the sequence of H (in A), –(CH2CH3)2 (in C) and
–(CH2)3CH3 (in B), leading to an increase in the density
of electron cloud around N atom, this helps to stabilize
the Ru–N bond in accordance with the above sequence.
Consequently, the activity of three types of immobilized
ruthenium increased in proper sequence.
Table 2 shows the comparison of the results on A–Ru
catalyst precursor in different bases.
As shown in Table 2, the production rate of HCOOH
was high in the presence of NEt3, while in the absence of
base, no HCOOH was obtained. The reaction
CO2(g) + H2(g) M HCOOH(1) occurs with DG298 =
Fig. 1. Schematic diagram of the phase behavior of reaction system
using immobilized catalyst in CO2-expanded ethanol.
 Y. Zhang et al. / Catalysis Communications 5 (2004) 643–646 645

Table 2 Table 3
The catalytic results on A–Ru precursor in different bases The catalytic results on A–Ru precursor in different solvents
Entry Catalyst Base HCOOH Entry Catalyst Solventa HCOOH
1
TOF (h ) Selectivity (%) TOF (h 1) Selectivity (%)
1a A–Ru + PPh3 – 0 0 1 A–Ru + PPh3 Methanol 933 100
2a,b A–Ru + PPh3 NEt3 656 100 2 A–Ru + PPh3 Ethanol 656 100
3c,d A–Ru + PPh3 NH2CONH2 523 100 3 A–Ru + PPh3 Isopropanol 74 100
4c,d A–Ru + PPh3 Na2CO3 227 100 4 A–Ru + PPh3 DMSOb 93 100
5c A–Ru + PPh3 C2H5ONa 68.5 100 5 A–Ru + PPh3 THFc 0 0
6c,d A–Ru + PPh3 CH3COONa 93 100 6 A–Ru + PPh3 toluene 0 0
Reaction conditions: reaction temperature, 80 C; H2 pressure, 4.0 Reaction conditions: reaction temperature, 80 C; H2 pressure, 4.0
MPa; total pressure, 16.0 MPa; reaction time, 1 h; ligand, PPh3; PPh3/ MPa; total pressure, 16.0 MPa; reaction time, 1 h; ligand, PPh3; PPh3/
Ru mol ratio, 10:1; stirring rate, 250 r/min. Ru mol ratio, 10:1; base, 5 ml NEt3; stirring rate, 250 r/min.
a a
Solvent: 20 ml ethanol. Solvent: 20 ml.
b b
NEt3: 5 ml. DMSO: dimethylsulphoxide.
c c
Wbase: 1.8 g. THF: tetrahydrofuran.
d
Solvent: 16.7 ml ethanol + 3.3 ml H2O.

+32.9 KJ mol 1, which is thermodynamically unfavour-
able, and the equilibrium conversion of CO2 at 3.0 MPa,
100 C and 6.0 MPa, 100 C is 0.72 · 10 5 and
0.14 · 10 4, respectively [16]. The equilibrium can be
shifted to the right by the addition of a base. The formic
acid and formate ester could be detected when the reac-
tion solution collected was acidified and esterified com-
pletely. But neither formic acid nor formate ester could
be detected in the reaction solution before being acidi-
fied to all of the reactions in which base was added. It
suggested that the product formic acid was converted
to a formate salt in the presence of a base.
The purpose of adding water in entry 3, 4 and 6 was
to cause the base dissolve in the solution. Table 2 shows
that the use of organic bases (entry 2) resulted in much
higher activity as compared to that of inorganic bases
(entry 3, 4, 5, 6). The activity was in the order of
NEt3 > NH2CONH2 > Na2CO3 > CH3COONa > C2H5
ONa, which was independent on the order of basicity.
These results suggest that the presence of base was not
only served to neutralize HCOOH, but also played a
crucial role in the catalytic performance of reaction.
NEt3, the most efficient base we tested, may be also used
as reducing agent for the ruthenium complex formed in
situ [17].
Table 3 shows the comparison of the results on A–Ru
catalyst precursor in different solvents.
As shown in Table 3, no HCOOH could be observed
in non-protonic solvent, such as THF and toluene (entry
5, 6). But the hydrogenation of CO2 to formic acid can
occur in a non-protonic DMSO solution (entry 4). The
reason may be that the strong polarity of DMSO, these
solvents dissolved extremely large amounts of CO2 than
other apolar solvents [18]. Addition of protonic solvent
accelerated the reaction. The highest HCOOH TOF (933
h 1) was achieved in methanol, the catalytic activity de-
creased in the order of methanol, ethanol and isopropa-
nol (entry 1, 2, 3), consistent with the order of steric
hindrance effect of alkyl group in ROH molecular.
The smallest steric bulk of methanol made it the most
efficient alcohol for CO2 hydrogenation, while isopropa-
nol with large steric bulk resulted in only 93 h 1 of TOF.
After the reaction was completed, the catalyst can
readily be recovered by filtration, hence, the catalyst

Table 4
The catalytic results of formic acid production with reused catalysts
Entry Catalyst PPh3/Ru (mol ratio) HCOOH
TOF (h 1)a Selectivity (%)
1 A–Ru 0 0 0
2 A–Ru + PPh3 10:1 656 100
3 Recycle-1b 0 612 100
4 Recycle-2b 0 600 100
5 B–Ru 0 0 0
6 B–Ru + PPh3 10:1 1384 100
7 Recycle-1b 0 1263 100
8 Recycle-2b 0 1239 100
Reaction conditions: reaction temperature, 80 C; H2 pressure, 4.0 MPa; total pressure,16.0 MPa; reaction time, 1 h; ligand, PPh3; solvent, 20 ml
ethanol; base, 5 ml NEt3; stirring rate, 250 r/min.
a
TOF: turnover frequency, mol of HCOOH/mol of Ru.
b
The recycled catalyst was the catalyst in the above entry.
646 Y. Zhang et al. / Catalysis Communications 5 (2004) 643–646
can be reused (see Table 4). A worthy noting detail
was that no formic acid was formed in the absence
of triphenylphosphine ligand (entry 1, 5), while the
synthesis of formic acid only occurred with the addi-
tion of triphenylphosphine (entry 2, 6). The reused
catalysts, formic acid could be obtained while the
recycle was performed in the absence of triphenyl-
phosphine ligand (entry 3, 4, 7, 8). It was attributed
to the formation of the catalytic active species from
the immobilized ruthenium and triphenylphosphine
ligand under reaction conditions in the first run.
Therefore, besides the high activity of the catalyst, it
is also a new, clean, simple and highly efficient
method for the synthesis of complexes catalyst.
From Table 4, it can be found that 600 and 1239 h 1
of HCOOH TOF was maintained after catalyst A–Ru
and B–Ru was used three times, respectively.
The moderate loss of activity was due to the inevita-
bly loss of catalyst in the process of filtration. Because
we used the filtrate in the further reaction as Sheldon
noted [19], and the filtrate exhibited no activity, indicat-
ing that the leaching of ruthenium from amine-modified
silica in each run was almost negligible, hence the recy-
cling of the catalyst was possible.
4. Conclusion
In conclusion, amine functionalized silica immobi-
lized ruthenium complexes for the formation of formic
acid in CO2-expanded solvent have been developed
with an in situ synthesis way. The functionalizing
group, the additives such as the base, the solvent,
influenced the performance of the catalyst. And the
immobilized catalysts were superior to the homogene-
ous catalysts, not only exhibiting higher activity, but
also offer the practical advantages such as ease separa-
tion and recycling.
Acknowledgements
This work was financially supported by the Natural
Science Foundation of China (No. 20173048) and the
specialized research fund for the Doctoral program of
higher education (No. 20030335068).
References
[1] D.J. Darensbourg, C. Ovalles, M. Pala, J. Am. Chem. Soc. 105
(1983) 5937.
[2] D.J. Darensbourg, C. Ovalles, J. Am. Chem. Soc. 106 (1984)
3750.
[3] D.A. Palmer, R.V. Eldik, Chem. Rev. 83 (1983) 651.
[4] P.G. Jessop, T. Ikariya, R. Noyori, Nature 368 (1994) 231.
[5] P.G. Jessop, T. Ikariya, R. Noyori, Science 269 (1995) 1065.
[6] P.G Jessop, Y. Hsiao, T. Ikariya, R. Noyori, J. Am. Chem. Soc.
118 (1996) 344.
[7] O. Kröcher, R.A. Köppel, A. Baiker, J. Chem. Soc., Chem.
Commun. (1997) 453.
[8] O. Kröcher, R.A. Köppel, M. Fröba, A. Baiker, J. Catal. 178
(1998) 284.
[9] O. Kröcher, R.A. Köppel, A. Baiker, J. Mol. Catal. 140 (1999)
185.
[10] J.Z. Zhang, Z. Li, H. Wang, C.Y. Wang, J. Mol. Catal. 112
(1996) 9.
[11] P.E. Savage, S. Gopalan, T.I. Mizan, C.J. Martino, E.E. Brock,
AIChE J. 41 (1995) 1723.
[12] G. Music, M. Wei, B. Subramaniam, D.H. Busch, Coord. Chem.
Rev. 219 (2001) 789.
[13] B. Kerler, R.E. Robinson, A.S. Borovik, B. Subramaniam, Appl.
Catal. B: Environ. 49 (2004) 91.
[14] B. Subramaniam, C.J. Lyon, V. Arunajatesan, Appl. Catal. B:
Environ. 37 (2002) 279.
[15] B. Pugin, M. Müller, Stud. Surf. Sci. Catal. 78 (1993) 107.
[16] F.H. Cao, D.H. Liu, Q.S. Hou, D.Y. Fang, J. Nat. Gas. Chem.
10 (2001) 24.
[17] J.Z. Zhang, Z. Li, H. Wang, C.Y. Wang, J. Mol. Catal. 112
(1996) 9.
[18] W. Leitner, E. Dinjus, F. Gaßner, J. Organometal. Chem. 475
(1994) 257.
[19] R.A. Sheldon, M. Wallau, I.W.C.E. Arends, U. Schuchardt, Acc.
Chem. Res. 31 (1998) 485.