DOI: 10.1002/cphc.
201200115
Mechanisms of Silicon Alkoxide Hydrolysis–
Oligomerization Reactions: A DFT Investigation
Xueli Cheng,[a, b] Dairong Chen,[a] and Yongjun Liu*[a]
Silica aerogels possess a variety of unique and remarkable
properties, but the mechanisms of silicon alkoxide, Si(OR)4, hy-
drolyses and oligomerization in the initial stage of sol–gel pro-
cesses are still not well understood. On the basis of density
functional theory calculations at the B3LYP/6-31G(d,p)//B3LYP/
6-311 + + G(d,p) basis set level, the hydrolysis and oligomeriza-
tion reactions of Si(OR)4 in neutral, acidic, and alkaline solu-
tions were systematically investigated and we found that in
1. Introduction
Silica aerogels are low-density, high-porosity materials and pos-
sess desirable physical properties, such as extremely low ther-
mal conductivity, high acoustic impedance, large specific sur-
face area, and low relative dielectric constants.[1–7] Because of
these remarkable properties, experimental and theoretical in-
vestigations involving aerogels are mostly focused on silicon
compounds.[8] Silica aerogels are ideal candidates for various
applications, such as thermal superinsulators, adsorbents, sen-
sors, catalyst carriers, and inorganic fillers.[3, 9–11]
The fabrication, morphologies, and applications of silica aero-
gels have received sustained attention in recent years in both
chemistry and physics.[12–17] The hydrolysis and condensation of
the precursor silicon alkoxide, Si(OR)4, is the initial step to pre-
pare silica aquasols. The Si atoms in Si(OR)4 carry a reduced par-
tial positive charge [e.g. d +  0.32 ppm in Si(OEt)4], so the hy-
drolysis and condensation reactions of Si alkoxides may be very
slow and therefore need to be catalyzed, either with bases that
carry strong negative charges (e.g. OH and strong Lewis bases
such as F ions) or with acids that carry a strong positive charge
and are able to attack the O (d ) atoms of the alkoxy groups.[8]
Zerda and Hoang proved that the transition-state silicon atoms
in the hydrolysis reactions of tetramethylorthosilicate were pen-
tavalent.[18] Aelion et al. proved experimentally that the hydroly-
sis of tetraethylorthosilicate (TEOS) occurred readily in the pres-
ence of acidic or basic catalysts.[19] Brochier Salon and Belgacem
carried out 29Si NMR spectroscopy studies on the competition
between hydrolysis and condensation reactions of trialkoxysi-
lanes in water/ethanol solutions and selected acidic conditions
to enhance the formation of hydrolyzed alkoxysilane molecules
and to slow down the consecutive self-condensation reac-
tions.[20] Moreover, 29Si NMR spectroscopy was employed widely
to investigate the reaction kinetics and the quantitative study of
organosilicate hydrolysis and condensation.[21–32]
With regard to theoretical studies on the hydrolysis and oli-
gomerization of silica, in 2005 Mora-Fonz et al.[33] investigated
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acidic solutions the precursor Si(OCH3)4 was inclined to hydro-
lyze rather than to condense and the hydrolysis processes
were energetically more favorable than the neutral ones. In al-
kaline solutions, the hydrolysis products oligomerize through
an SN1 dimerization mechanism and the condensation rates
are fast to form denser colloidal aerogels. Our calculations also
testify that the subsequent cyclization reactions are energeti-
cally unfavorable.
the oligomerization and cyclization processes in the nucleation
of microporous orthosilicic acid, Si(OH)4, by using DMOL3 with
a numeric DNP basis set; in 2006 Trinh et al.[34] studied the
anionic and neutral mechanisms of oligomerization reactions
of silica by using DFT calculations for various structures of sili-
cate oligomers with the continuum solvation (COSMO) method
and the activation energies for di- and trimer formation were
estimated. In 2009 Trinh and co-workers[35–37] reported a DFT-
based molecular dynamics simulation of silica oligomerization,
providing thermodynamics, kinetics, and the mechanism of the
reaction pathway for the anionic bond formation of siliceous
oligomers. Recently, an off-lattice kinetic Monte Carlo (kMC) ap-
proach called continuum kMC was used to model silicate oli-
gomerization from Si(OH)4 in water and the evolution of sili-
cate oligomers as well as their role in the oligomerization pro-
cess were reported.[38, 39] Although there are plenty of experi-
mental reports regarding the silica sol–gel process, theoretical
investigations are mostly focused on the condensation of
Si(OH)4 and it is difficult to extract information from experi-
mental data because of the multitude of reactions that occur
simultaneously in solution.[8, 11, 19, 33–49] Does the hydrolysis or oli-
gomerization of Si(OR)4 predominate at all stages during the
sol–gel process? How does the oligomer form in various solu-
[a] X. Cheng, Prof. Dr. D. Chen, Prof. Dr. Y. Liu
Key Lab of Colloid and Interface Chemistry
Ministry of Education
School of Chemistry and Chemical Engineering
Shandong University
Jinan, Shandong 250100 (China)
E-mail: yongjunliu_1@sdu.edu.cn
[b] X. Cheng
Department of Chemistry and Environmental Sciences
Taishan University
Tai’an, Shandong 271021 (China)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cphc.202000115.
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tions? The fundamental chemistry of the hydrolysis and oligo-
merization mechanism is still unknown. Herein, we describe
a DFT investigation carried out to obtain the activation ener-
gies and structural parameters for the elucidation of the hy-
drolysis and oligomerization mechanisms of Si(OR)4. The pres-
ent work allows insight into the condensation of silica aero-
gels.
Computational Details
All species involving the hydrolysis and oligomerization of the
Si(OR)4 precursor were fully optimized with the Gaussian 03 pro-
gram package[50] at the B3LYP/6-31G(d,p) basis set level of hybrid
DFT. The B3LYP method has been employed successfully to eluci-
date the oligomerization mechanism of silicic acid[34] to optimize
structures of silicon clusters[51] and compounds,[52] and to model
the adsorption of molecules on the surface of amorphous silica.[53]
Because the hydrolysis and oligomerization processes involve hy-
drogen transfer, it is essential to employ a basis set possessing suf-
ficient polarization functions to describe noncovalent interac-
tions.[54] Frequency calculations in the gas phase have also been
performed at the same level of theory to obtain the zero-point en-
ergies and to identify whether the stationary point is a local mini-
mum or a transition state. Furthermore, the displacement vectors
of the imaginary vibrational modes were used to identify real tran-
sition states and their connections.[55] Some significant transition
states were further checked by intrinsic reaction coordinate (IRC)
calculations to confirm their connections between the correspond-
ing intermediates.
The liquid environment was modeled by using a conductor-like
screening model (CPCM)[56, 57] in which water was represented as
a dielectric continuum. Most of the parameters employed were de-
fault settings. Considering the computational time requirement,
the CPCM single-point energy (SPE) calculations with the gas-
phase equilibrium geometries were carried out throughout the
present work at the more rigorous B3LYP/6-311 + + G(d,p) basis set
level of theory without frequency calculations. The CPCM SPE cal-
culations were also performed with the Gaussian 09 package[58] at
the M06-2X/6-311 + + G(d,p) level to compare the reactivity of
methyl- and ethyl-substituted species because of the good perfor-
mance of the M06-2X functional in main-group thermochemis-
try.[59, 60] The M06-2X CPCM energies were scaled with thermal cor-
rections to Gibbs free energies in the gas phase.
In the SPE calculations, because diffuse functions were employed,
to improve the accuracy, we used the SCF = Tight keyword to re-
quest tight SCF convergence criteria. The SphereOnH = N keyword
was also selected to describe the shifting hydrogen atoms in tran-
sition states and the unbonded hydrogen atoms in ionic species
for which the default calculation cannot be performed. Then the
single-point Gibbs free energies were scaled with zero-point
energy (ZPE) in the gas phase to draw the potential energy surface
(PES) profiles.
2. Results and Discussion
Since silicon alkoxides do not have a hydroxy hydrogen atom
to form hydrogen bonds with the alkoxy oxygen to facilitate
condensation, the precursor is hydrolyzed before condensation
when mixed with water. The initial pH value of the hydrolysis–
oligomerization system is the main factor to affect the particle
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Y. Liu et al.
size,[44] so the neutral, acidic, and alkaline solutions is consid-
ered. Herein, we describe extensive investigations into the
first-, second-, third-, and fourth-order hydrolyses of the pre-
cursor Si(OR)4 in the neutral, acidic, and alkaline solutions, and
then the condensation mechanisms at various stages. The hy-
drolysis and condensation reactions studied are illustrated in
Schemes 1 and 2.
Different alkoxy groups influence the hydrolysis and oligo-
merization processes. Herein, we selected R = CH3 and C2H5 to
compare their hydrolysis character and carried out SPE calcula-
tions by using the M06-2X/B3LYP method at the 6-311 + +
G(d,p) level to compare the reliability of these two approaches,
as shown in Figures 1 and 2 and Tables 1 and 2. The M06-2X
results are comparable with the B3LYP ones: for the first-,
second-, third-, and fourth-order hydrolyses, their M06-2X free
energy barriers are 117, 120, 119, and 117 kJ mol 1 and 121,
114, 121, and 115 kJ mol 1, respectively. Our calculations esti-
mate that both the free energy barriers and total barriers at
the M06-2X/6-311 + + G(d,p) level are unfeatured and B3LYP
may be better in this reaction system. We employed the B3LYP
method to analyze the hydrolysis–oligomerization mecha-
nisms.
2.1. Si(OR)4 Hydrolyses
2.1.1. Neutral Hydrolysis of Si(OCH3)4
The optimized structural parameters and the PES profile of the
first-order neutral hydrolysis of Si(OCH3)4 are depicted in
Figure 1, and the Gibbs free energies as well as the lowest vi-
brational frequencies are listed in Table 1. In combination reac-
tions, when reactants are chemically bonded, the Gibbs free
energies may increase because the entropy effect plays a signif-
icant role. A water molecule forms two hydrogen bonds with
Si(OCH3)4 to generate C1-1-IM1, increasing the free energy by
15 kJ mol 1. Then a hydrogen atom on the H2O unit transfers
to the adjacent methoxy oxygen via C1-1-TS with a free
energy barrier of 104 kJ mol 1, generating C1-1-IM2. In C1-1-
IM2, the methanol unit links to the Si atom through a hydrogen
bond 1.934  long. The departure of the methanol unit does
not increase the free energy and the products of this channel,
C1-1-P + CH3OH, are still more stable than Si(OCH3)4 + H2O in
the reaction coordinate. From Figure 1 it can be seen that the
first-order hydrolysis of Si(OCH3)4 has a total energy barrier of
119 kJ mol 1.
Our calculations estimate that the second-, third-, and
fourth-order hydrolyses of Si(OCH3)4 resemble the first-order
one, and therefore, only the transition states are illustrated in
Figure S1 in the Supporting Information. The Gibbs free ener-
gies and the lowest vibrational frequencies of all species are
also listed in Table 1. In these transition states, the OH moieties
attach to the central Si along with the hydrogen atoms migrat-
ing to the adjacent methoxy groups. All of the imaginary fre-
quencies are the O H O asymmetrical stretching modes re-
garding the shifting hydrogen atoms. The energy barriers are
106, 109, and 109 kJ mol 1, respectively, implying that the
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Silicon Alkoxide Hydrolysis–Oligomerization Reactions

energy barriers increase gradual-

ly with the methoxy groups hy-
drolyzed one by one.

2.1.2. Neutral Hydrolysis of

Si(OC2H5)4
To understand the effect of the
alkyl groups on the hydrolysis
and oligomerization of Si(OR)4,
the hydrolyses of Si(OC2H5)4
were also investigated. The opti-
mized structural parameters and
the PES profile of the first-order
hydrolysis of Si(OC2H5)4 are de-
picted in Figure 2, and the struc-
tural parameters of the transition
states in the second-, third-, and
fourth-order hydrolyses are
shown in Figure S2 in the Sup-
porting Information. The Gibbs
free energies and the lowest vi-
brational frequencies for all spe-
cies involving the hydrolyses of
Si(OC2H5)4 are listed in Table 2.
The ethoxyl groups are hydro-
lyzed one by one via C2-1-TS,
C2-2-TS, C2-3-TS, and C2-4-TS
with free energy barriers of 120,
106, 123, and 109 kJ mol 1, re-
spectively; these values are
Scheme 1. A schematic drawing of the hydrolysis mechanisms investigated herein. TS = transition state, IM = inter- slightly higher than those of
mediate. Si(OCH3)4. The steric effect of
alkyl groups hinders hydrolysis.[8]
Similar to the hydrolyses of
Table 1. The lowest frequencies (in cm 1), Gibbs free energies (in a. u.), and relative free energies (in kJ mol 1) Si(OCH3)4, H2O links to the
for the neutral hydrolysis of Si(OCH3)4. Relative free energies in brackets are SPE results at the M06-2X/6-311 + oxygen atoms through hydrogen
+ G(d,p) level.
bonds, then hydrogen atoms
Si(OCH3)4 Species Lowest frequencies [cm 1] Gibbs free energies [a.u.] DG [kJ mol 1] shift from H2O to the neighbor-
first-order Si(OCH3)4 + H2O 471 665 826.608280 0 ing oxygen atoms to hydrolyze
hydrolysis C1-1-IM1 40 826.602655 15 (28) the ethoxyl groups, and the
C1-1-TS i768 -826.562919 119 (145) imaginaries frequencies are all
C1-1-IM2 31 826.612883 12 (28) the O H O asymmetrical
C1-1-P + CH3OH 52 338 826.612431 11 (3)
second-order C1-1-P + H2O 521 665 787.343714 0 stretching modes. Moreover, the
hydrolysis C1-2-IM1 32 787.339314 12 (17) intermediates and products are
C1-2-TS i748 787.298844 118 (137) all more stable in energy than
C1-2-IM2 16 787.346450 7 (27) the reactants. Although the hy-
C1-2-P + CH3OH 67 338 787.347564 10 (1)
third-order C1-2-P + H2O 671 665 748.078847 0 drolysis of Si(OC2H5)4 is slightly
hydrolysis C1-3-IM1 32 748.074447 12 (17) more difficult than Si(OCH3)4,
C1-3-TS i742 748.032820 121 (136) both have similar hydrolysis
C1-3-IM2 26 748.076387 6 (23) characters. As a result, in the
C1-3-P + CH3OH 72 338 748.082628 10 (2)
fourth-order C1-3-P + H2O 721 665 708.813911 0 present work, we only investi-
hydrolysis C1-4-IM1 39 708.809672 11 (18) gated the hydrolysis and con-
C1-4-TS i770 708.768074 120 (135) densation of Si(OCH3)4. Larger
C1-4-IM2 23 708.811078 7 (23) substituents have higher hydrol-
Si(OH)4 + CH3OH 201 338 708.816802 8 (3)
ysis barriers.

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Subsequently, we consider the

Si(OCH3)4 alkaline first-order hy-
drolysis aided with a water mol-
ecule, as depicted in Figure 4.
H2O links to Si(OCH3)4 through
two hydrogen bonds rather than
a coordination bond to produce
an intermediate termed C1-
OH1w-IM1, followed by H trans-
fer from the H2O moiety to the
adjacent methoxy oxygen to hy-
drolyze CH3OH via C1-OH1w-TS,
leading to C1-OH1w-IM2, in
which hydrolyzed CH3OH con-
nects to C1-OH1w-P through
a hydrogen bond 1.740  long.
This process has a barrier of
93 kJ mol 1 and a total barrier of
77 kJ mol 1, showing a striking
contrast with Al(OC3H7)3 hydroly-
sis[54] aided by water. Therefore,
H2O may not help the Si(OCH3)4
hydrolysis in alkaline solutions.
However, the second-, third-,
and fourth-order alkaline hydrol-
yses of Si(OCH3)4 have barriers of
157, 155, and 162 kJ mol 1, re-
spectively; these values are
much higher than those of the
first-order hydrolysis of Si(OCH3)4
and the neutral hydrolyses of
Si(OCH3)4 and Si(OC2H5)4. The
lowest frequencies and free en-
ergies involving the Si(OCH3)4 al-
kaline hydrolyses are listed in
Table 3, and the optimized struc-
tural parameters and PES profiles
of the second-, third-, and
fourth-order alkaline hydrolyses
Scheme 2. A schematic of the dimerization and cyclization mechanisms under study.
are depicted in Figures S3–S5 in
the Supporting Information. In
contrast to the neutral hydroly-
2.1.3. Anionic Hydrolysis Mechanism of Si(OCH3)4 ses, the imaginary frequencies of the transition states concern-
ing the anionic hydrolyses can be assigned to the O H O and
The structural parameters and PES profiles are shown in O Si O asymmetrical stretching modes. Table 3 also shows
Figure 3. HO connects to Si(OCH3)4 through a barrierless pro- that all products are lower in energy than the corresponding
cess to form C1-OH1-IM1, decreasing the free energy by reactants. OH may initiate the oligomerization of
42 kJ mol 1. Then the hydroxyl hydrogen shifts to the neigh- Si(OCH3)4.[34, 54]
boring methoxy group and expels it from C1-OH1-IM1 via C1-
OH1-TS, leading to the formation of C1-OH1-IM2, as shown in
2.1.4. Hydrolysis Mechanism of Si(OCH3)4 in Acidic Solutions
Figure 3. This hydrolysis mode is very similar to the alkaline hy-
drolysis of Al(OC3H7)3.[54] The methanol unit links to the other In acidic solutions, we protonate one methoxy group to regu-
part of C1-OH1-IM2 through a strong hydrogen bond late charge population in Si(OCH3)4.[8, 40] The optimized geomet-
1
(1.541 ). The energy barrier is very low (37 kJ mol ), and all rical parameters and PES profile of the first-order acidic hydrol-
species of this process are much more stable in energy than ysis of Si(OCH3)4 are shown in Figure 5. H2O is bonded to
Si(OCH3)4 + HO , indicating that Si(OCH3)4 can hydrolyze the Si(OCH3)4 through a weak coordination bond (2.052 ) and
first methoxy group very easily in alkaline solutions. a hydrogen bond (2.252 ) from the opposite side of the pro-

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Silicon Alkoxide Hydrolysis–Oligomerization Reactions

Figure 2. The optimized structural parameters and the PES profile of the
Figure 1. The optimized structural parameters and the PES profile of the first-order neutral hydrolyses of Si(OC2H5)4. Relative free energies in brackets
first-order neutral hydrolysis of Si(OCH3)4. Relative energies are given in are SPE results at the M06-2X/6-311 + + G(d,p) level.
kJ mol 1, bond lengths are in , and bond angles in 8. These units are em-
ployed uniformly in all figures, including those found in the Supporting In-
formation. Relative free energies in brackets are SPE results at the M06-2X/6-
311 + + G(d,p) level. tonated methoxy group, decreasing the free energy by
25 kJ mol 1. Subsequently, H2O imparts a hydrogen atom to hy-
drolyze the methoxy group via
C1-H1-TS1, producing C1-H1-
IM2. The energy barrier is
Table 2. The Gibbs free energies and the lowest vibrational frequencies for the neutral hydrolysis of Si(OC2H5)4. 77 kJ mol 1 and the total barrier
Relative free energies in brackets are SPE results at the M06-2X/6-311 + + G(d,p) level.
is only 52 kJ mol 1, which is
Si(OC2H5)4 Species Lowest frequencies [cm ] 1
Gibbs free energies [a.u.] DG [kJ mol ]1 much lower than those of neu-
first-order Si(OC2H5)4 + H2O 171 665 983.806892 0 tral hydrolyses. From C1-H1-IM1
hydrolysis C2-1-IM1 20 983.804716 6 (24) via C1-H1-TS1 to C1-H1-IM2, the
C2-1-TS i785 983.758806 126 (145) breaking Si O bond is extended
C2-1-IM2 20 983.809430 7 (30) from 1.636 to 1.761 to 2.010 .
C2-1-P + C2H5OH 26 251 983.813883 18 (2)
second-order C2-1-P + H2O 261 665 905.243906 0 The PES profile shows that this
hydrolysis C2-2-IM1 12 905.236509 19 (28) reaction path proceeds easily.
C2-2-TS i803 905.196402 125 (142) There is another first-order
C2-2-IM2 13 905.248132 11 (17) acidic hydrolysis channel in
C2-2-P + C2H5OH 27 251 905.249422 14 (2)
third-order C2-2-P + H2O 271 665 826.679445 0 which the protonated water
hydrolysis C2-3-IM1 25 826.678184 3 (27) molecule H3O + hydrolyzes the
C2-3-TS i631 826.631288 126 (148) precursor. In the initial stage,
C2-3-IM2 15 826.677189 6 (22) H3O + protonates a methoxyl
C2-3-P + C2H5OH 23 251 826.684326 13 (1)
fourth-order C2-3-P + H2O 231 665 748.114349 0 group to form the intermediate
hydrolysis C2-4-IM1 38 748.109058 14 (22) C1-H1-IM4, where the proton,
C2-4-TS i773 748.067318 123 (137) just as the proton “in the
C2-4-IM2 18 748.111416 8 (23) middle” of H5O2 + ,[61–63] is located
Si(OH)4 + C2H5OH 201 251 748.118062 10 (4)
between H2O and the methoxy

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Figure 3. First-order hydrolysis of Si(OCH3)4 in alkaline solutions.
Figure 4. First-order hydrolysis of Si(OCH3)4 aided with a water molecule in
alkaline solutions.
oxygen,[40] and H2O links to the adjacent oxygen through
a weak hydrogen bond with distance of 2.334  (Figure 6).
Then the CH3O group is hydrolyzed via C1-H1-TS2 to generate
C1-H1-IM5. Figure 6 shows that both the energy barrier and
total barrier are higher than the process via C1-H1-TS1, sug-
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Y. Liu et al.
gesting that H2O should attack from the opposite
side of the protonated CH3O group.
The optimized structures and PES profiles of the
second- and third-order acidic hydrolysis are depicted
in Figure S6 in the Supporting Information. In both
processes, methoxy groups are hydrolyzed one by
one with H transfer and H2O attacks from the oppo-
site side of the protonated methoxyl group, and the
hydrolysis barriers via C1-H2-TS and C1-H3-TS are
only 61 and 69 kJ mol 1, respectively; these values
are much lower than those of the corresponding
second- and third-order hydrolysis processes in neu-
tral and alkaline solutions.
However, for the fourth-order acidic hydrolysis of
Si(OCH3)4, the proton blocks hydrolysis by H2O and
the direct departure or extrusion of the protonated
methoxy group can lead to an energy-rich cationic
species Si(OH)3 + . Aelion et al.[19] and Depla et al.[43]
also proved that hydrolysis was incomplete at low
acid concentrations and the last alkoxy group was
difficult to hydrolyze.
The first-, second-, and third-order hydrolyses are
energetically favorable in acidic solutions. The Gibbs
free energies and the lowest vibrational frequencies involving
the acidic hydrolysis of Si(OCH3)4 are listed in Table S1 in the
Supporting Information. Our calculation also illuminates that
the second-order hydrolysis has the lowest barrier and total
barrier in acidic solutions.
2.2. Oligomerization Reactions of Si(OCH3)4 Hydrolysis
Products
In various stages of hydrolysis, the hydrolysis products can oli-
gomerize by demethanolization or dehydration in the initial
stage of nucleation to form oligomers with oxo bridges. Now
we discuss the oligomerization mechanisms to ascertain
whether hydrolysis or oligomerization predominates in the hy-
drolysis–oligomerization processes.
2.2.1. Dimerization and Cyclization in Neutral Solutions
The Gibbs free energies and the lowest vibrational frequencies
involving the dimerization and cyclization in neutral solutions
of Si(OCH3)4 are listed in Table S2 in the Supporting Informa-
tion. Two molecules of the first-order neutral hydrolysis prod-
uct, C1-1-P, link together with hydrogen bonding (1.863 ). The
optimized geometrical parameters and the PES profile are illus-
trated in Figure 7. Then the hydroxyl hydrogen transfers to hy-
drolyze another C1-1-P molecule and the hydroxyl oxygen co-
ordinates to the Si atom via the four-membered-ring transi-
tion-state d1-TS1. The distances between the shifting hydro-
gen and the two oxygen atoms are 1.405 and 1.062 , and the
newly formed Si O bond length is 2.144 . The energy barrier
is 136 kJ mol 1, which is much higher than that of the first-
order neutral hydrolysis of Si(OCH3)4. Thus, Si(OCH3)4 may hy-
drolyze further before condensation.
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Silicon Alkoxide Hydrolysis–Oligomerization Reactions

The ring-closing process was

Table 3. The Gibbs free energies and lowest vibrational frequencies of the hydrolyses of Si(OCH3)4 in alkaline
solutions. studied after the dimerization of
the neutral first-order hydrolysis
Si(OC2H5)4 + OH Species Lowest freqencies Gibbs free energies DG product, as illustrated in
[cm 1] [a.u.] [kJ mol 1]
Figure 8. The d1-P isomerizes to
first-order hydrolysis Si(OCH3)4 + OH 473 500 826.113520 0 d1-2-IM1 via d1-2-TS1, followed
C1-OH1-IM1 49 826.129333 42
by demethanolization to form
C1-OH1-TS i195 826.115358 5
C1-OH1-IM2 20 826.148101 91 a SiO tetra-atomic ring via d1-2-
C1-OH1-P + CH3OH 18 338 826.139920 69 TS2. The imaginary frequency of
first-order hydrolysis aided C1-OH1-IM1 + H2O 491 665 902.576823 0 d1-2-TS1 at i374 cm 1 is the O H
with water C1-OH1-w-IM1 55 902.582822 16
rocking mode and the transition
C1-OH1-w-TS i607 902.547614 77
C1-OH1-w-IM2 27 902.586544 26 state has a very low barrier of
C1-OH1-w- 50 338 902.581658 13 9 kJ mol 1. The barrier to d1-2-
P + CH3OH TS2 is much higher than that of
second-order hydrolysis C1-OH1-P + H2O 181 665 786.871203 0
the dimerization process. More-
C1-OH2-IM1 19 786.869704 4
C1-OH2-TS i622 786.809751 161 over, d1-2-IM2 and the products
C1-OH2-IM2 15 786.874529 9 have high relative energies, so it
C1-OH2-P + CH3OH 34 338 786.873984 7 is energetically unfavorable.
third-order hydrolysis C1-OH2-P + H2O 341 665 747.605267 0
The dimerization and subse-
C1-OH3-IM1 27 747.604625 2
C1-OH3-TS i546 747.545409 157 quent cyclization reaction of the
C1-OH3-IM2 15 747.609340 11 second-order neutral hydrolysis
C1-OH3-P + CH3OH 66 338 747.607163 5 product are depicted in Fig-
fourth-order hydrolysis C1-OH3-P + H2O 661 665 708.338446 0
ures 9 and 10. There are two di-
C1-OH4-IM1 23 708.340312 5
C1-OH4-TS i590 708.278525 157 merization modes, namely, the
C1-OH4-IM2 24 708.343856 14 “ring (closed) mode” (Figure 9)
[SiO(OH)3] + CH3OH 165 338 708.341210 7 and the “open mode”
(Figure 10). For the ring mode,
two C1-2-P molecules link to-
gether through two hydrogen
bonds to produce the eight-
atom-ring intermediate d2-IM1-
m1. Subsequently, the Si O Si
bond forms by demethanoliza-
tion after hydrogen transfer via
d2-TS1-m1. The calculated
energy barrier is 104 kJ mol 1,
comparable with those of hy-
drolyses in neutral solutions.
Figure 11 shows that the cycliza-
tion by dehydration also has
a very high energy barrier
(174 kJ mol 1) and is energetical-
ly unfavorable, just as the pro-
cess via d1-2-TS1.
In the open mode, two C1-2-P
molecules connect through one
hydrogen bond with a distance
of 1.798 . The dimerization and
demethanolization process via
d2-TS1-m2 has a barrier of
141 kJ mol 1, higher than the
ring mode by 37 kJ mol 1. The
estimated barrier of the subse-
quent cyclization reaction is still
very high (183 kJ mol 1).
Then the dimerization and
Figure 5. First-order acidic hydrolysis of Si(OCH3)4. cyclization of the third-order

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Figure 6. First-order hydrolysis of Si(OCH3)4 by H3O + .
neutral hydrolysis product C1-3-P were investigated. The opti-
mized structural parameters and the PES profile of the ring
Figure 7. The dimerization mechanism of the neutral first-order hydrolysis of Si(OCH3)4.
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Y. Liu et al.
mode are illustrated in Figure S7 in the Supporting Informa-
tion, which shows that the dimerization barrier is 128 kJ mol 1;
slightly lower than that via d2-TS1-m1, but slightly higher than
that of the neutral hydrolyses. The cyclization processes by de-
methanolization and dehydration are also shown in Figure 12.
The energy barriers of these two cyclization channels are 177
and 166 kJ mol 1, implying that demethanolization is easier
than dehydration.
The dimerization and cyclization of the fourth-order neutral
hydrolysis product Si(OH)4 are depicted in Figure S8 in the Sup-
porting Information. The estimated dimerization barrier of the
ring mode is 94 kJ mol 1, which is much lower than the com-
putational results reported by Trinh et al.[34] Similarly, the cycli-
zation of d4-P has a large energy barrier of 177 kJ mol 1.
In neutral solutions, it can be seen from the hydrolysis–oli-
gomerization reaction mechanisms of Si(OCH3)4 that, after the
first-order hydrolysis, oligomerization can compete with hy-
drolysis, but hydrolysis predominates before the precursor is
hydrolyzed completely.
2.2.2. Dimerization in Acidic Solutions
Dimerization after the hydrolysis of a methoxy group in acidic
solutions is similar to the silanization of hydride silica with sila-
nol groups.[64] We investigated the energetically favorable ring-
mode acidic dimerization mechanism herein, in which the neu-
tral hydrolysis products link to the corresponding acidic hydrol-
ysis products through two hydrogen bonds. The
lowest frequencies and Gibbs free energies in the
acidic dimerization of Si(OCH3)4 are listed in Table S3
in the Supporting Information. The acidic dimeriza-
tion of first-order neutral hydrolysis product C1-1-P
and first-order acidic product C1-H1-P is depicted in
Figure 11. The hydrolysis products are bonded to-
gether by two hydrogen bonds with distances of
1.823 and 1.521 , respectively, decreasing the free
energy by 13 kJ mol 1. Then the hydroxyl oxygen
adds to Si via hydrogen-transfer transition-state dH1-
1-TS1 to form dH1-1-IM2. The total energy barrier is
90 kJ mol 1, which is slightly lower than those of first-
order neutral dimerization, but higher than acidic hy-
drolyses of Si(OCH3)4. In this ring mode, the proton
lies between two oxygen atoms to form a ring and
prevents the dimer from further cyclization.
The second-order acidic dimerization is similar to
the above-mentioned first-order one, as shown in
Figure S9 in the Supporting Information. The second-
order dimerization has a potential energy of
109 kJ mol 1 and a total barrier of 98 kJ mol 1. This
barrier is also higher than that of the second-order
acidic hydrolysis of Si(OCH3)4, so the precursor is in-
clined to hydrolyze further in acid solutions.
In the third-order acidic dimerization, adduct dH1-
3-P of C1-3-P and C1-H3-P hydrolyzes by hydrogen
transfer and demethanolization via dH1-3-TS1, with
an energy barrier of 111 kJ mol 1 and a total barrier
 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 0000, 00, 1 – 14
Silicon Alkoxide Hydrolysis–Oligomerization Reactions

of 93 kJ mol 1 (Figure S10 in the

Supporting Information).
The condensation of Si(OH)4
and Si(OH)3(OH2) + was also in-
vestigated in this study, as de-
picted in Figure S11 in the Sup-
porting Information. Si(OH)4 and
Si(OH)3(OH2) + dimerize to form
dH1-4-IM2 along with dehydra-
tion via dH1-4-TS with a total
barrier of 68 kJ mol 1.
From our computation it can
be seen that the dimerization
barriers are all higher than the
corresponding hydrolysis barri-
ers, so the precursor may be in-
clined to hydrolyze before con-
densation in acidic solutions.
Our calculation estimates that
the acidic dimerization processes
have lower total barriers than
the neutral ones and proton pre-
vent the cationic dimers from cy-
clizing, therefore, the precursor
Figure 8. Ring closing after the dimerization of the neutral first-order hydrolysis products. [a] In the gas phase and is inclined to form higher oligo-
SPE calculations at the B3LYP/6-31G(d,p) level, both estimated free energies are lower than transition-state d1-2- mers.[42, 43]
TS1.

Figure 9. The dimerization and subsequent cyclization reaction of the second-order neutral hydrolysis product (the ring mode).

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 Y. Liu et al.

Figure 10. The dimerization and subsequent cyclization reaction of the second-order neutral hydrolysis product (the open mode).

2.2.3. Dimerization in Alkaline

Solutions

There are two dimerization

mechanisms in alkaline solutions.
One involves the addition of two
hydrolysis products and subse-
quent demethanolization or de-
hydration on the same silicon
atom (SN1 mechanism). The
reason that the SN1 mechanism
can occur may result from the
dehydrogenized SiO oxygen
that can attack the other Si
atoms.[34–36, 39] Another is a con-
certed reaction and the two pro-
cesses occur synchronously (SN2
mechanism). The SN1 dimeriza-
tion mechanism of the first-order
anionic and neutral hydrolysis
products is shown in Figure 13.
In the SN1 mechanism, the addi-
tion of two products has a low
barrier of 46 kJ mol 1 via transi-
tion-state dOH1-1-TS1, the imag-
inary frequency of which is the
Si O stretching mode. This Si O
Figure 11. The dimerization of the first-order neutral and acidic hydrolysis products of Si(OCH3)4 (C1-1-P + C1-H1- bond is shorted to 2.394  in
P). dOH1-1-TS1. In intermediate

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Silicon Alkoxide Hydrolysis–Oligomerization Reactions

Figure 12. The SN1 dimerization mechanism for the third-order neutral and alkaline hydrolysis products of Si(OCH3)4 (C1-3-P + C1-OH3-P).

Figure 13. The SN1 dimerization mechanism for the first-order neutral and anionic hydrolysis products of Si(OCH3)4 (C1-1-P + C1-OH1-P).

dOH1-1-IM2, the tetra- and penta-coordinated Si atoms are
linked together by a bridging O atom. The departure of CH3OH
on the penta-coordinated silicon via dOH1-2-TS has a total bar-
rier of only 47 kJ mol 1. The SN2 mechanism is depicted in Fig-
ure S12 in the Supporting Information and the lowest frequen-
cies and Gibbs free energies involving the SN1 and SN2 mecha-
nisms are listed in Table S4 in the Supporting Information. Our
results indicate that the SN1 mechanism is energetically favora-
ble. The SN2 mechanism leading to the products of dOH1-1-
P + CH3OH via dOH1-1-TS2 has a high barrier of 191 kJ mol 1,
as shown in Figure S12 in the Supporting Information. In fact,
dOH1-1-P is an isomer of dOH1-2-P; they have distinct geo-
metrical structures, but nearly equal relative energies.
The SN1 dimerization mechanism of the second-order anion-
ic and neutral hydrolysis products is depicted in Figure S13 in
the Supporting Information and the SN2 mechanism is depict-
ed in Figure S14. In the SN1 mechanism, both the addition and
demethanolization transition states of dOH2-1-TS1 and dOH2-
2-TS also have low energy barriers and total barriers, in con-
trast to the high barrier for the SN2 mechanism. Subsequently,
we also investigated the cyclization mechanism through dehy-
dration and demethanolization, but the relative energies of all

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species and barriers were much higher than those of the dime-
rization processes (Figure S15 in the Supporting Information).
The SN1 mechanism of the third-order anionic and neutral
hydrolysis products is illustrated in Figure 12. The SN2 mecha-
nism and cyclization process are shown in Figure S16 in the
Supporting Information and they have very high energy barri-
ers. For the SN1 mechanism, the addition of C1-3-P and C1-
OH3-P via transition-state dOH3-1-TS1 has an energy barrier of
only 44 kJ mol 1 and a total barrier of 17 kJ mol 1, leading to
product dOH3-1-IM2. Subsequent dehydration via dOH3-2-TS1
and demethanolization via dOH3-2-TS2 on the penta-coordi-
nated Si atom also have relatively low barriers, but demetha-
nolization is energetically more favorable with a total barrier of
33 kJ mol 1, as depicted in Figure 12.
In the SN1 mechanism, if all the methyl groups are hydro-
lyzed, Si(OH)4 and [SiO(OH)3] are linked together through
three hydrogen bonds to form dOH4-1-IM1, decreasing the
free energy by 12 kJ mol 1 (Figure S17 in the Supporting Infor-
mation). Then, the oxygen atom with a negative charge attacks
the central Si atom via transition-state dOH4-1-TS1 to yield
dOH4-1-IM2. The energy barrier is only 26 kJ mol 1 and dOH4-
1-TS1 has a low relative energy of 14 kJ mol 1. Subsequently,
a water molecule leaves the penta-coordinated Si atom via
transition-state dOH4-2-TS with a barrier of 59 kJ mol 1. The
SN2 mechanism and cyclization process are shown in Fig-
ure S18 in the Supporting Information. Our calculations esti-
mate that the SN1 mechanism is much more favorable than
the SN2 mechanism.
In the SN1 mechanism, the imaginary frequencies of the di-
merizing transition states are assigned to the Si O stretching
modes, and those of the demethanolization or dehydration
transition states belong to the Si O H or O H O asymmetri-
cal stretching modes, involving the shifting hydrogen. In the
alkaline solutions, the precursor dimerizes very easily by the
SN1 mechanism and the reaction rates are much faster than
those of the classical sol–gel system,[44] favoring the formation
of denser colloidal silica particles and aerogels.[8] However, the
SN2 mechanism and the cyclization process have much higher
potential energy barriers.
3. Conclusions
The hydrolysis and oligomerization reactions in the initial stage
of Si(OCH3)4 sol–gel chemistry were studied extensively with
DFT. Above all, we investigated the hydrolysis of Si(OCH3)4 to
Si(OH)4 and compared it with the hydrolysis of Si(OC2H5)4. We
also carried out CPCM SPE calculations at the M06-2X/6-311 +
+ G(d,p) basis set level to compare the reactivity of Si(OCH3)4
and Si(OC2H5)4, but we found that the B3LYP results were
better for this reaction system. Our calculations showed that
the hydrolysis of silicon alkoxides was similar in character and
the hydrolysis barriers increased gradually.
In alkaline solutions, the first-order hydrolysis of Si(OCH3)4
was very easy with a free energy barrier of only 37 kJ mol 1
and the assistance of a water molecule did not aid hydrolysis,
but the second-order barrier increased remarkably to
157 kJ mol 1 and subsequent hydrolysis had much higher barri-
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Y. Liu et al.
ers. Our theoretical model showed that hydrolysis in acidic sol-
utions was energetically favorable. For the hydrolyses of
Si(OCH3)4 in acidic solutions, the total barriers were all under
53 kJ mol 1, which was much more favorable than the corre-
sponding neutral ones. A methoxy group was protonated first
and it was not H3O + that attacked the methoxy group to be
hydrolyzed; the precursor did not hydrolyze completely.
For condensation and cyclization in neutral solutions, the
condensation barriers were comparable to those of the hydrol-
ysis ones, but hydrolysis predominated. Cyclization had higher
free energy barriers. In acidic solutions, although the dimeriz-
ing processes was energetically favorable, the free energy bar-
riers of the condensation processes were higher than the cor-
responding hydrolysis ones, so the precursor Si(OCH3)4 was in-
clined to hydrolyze. Our theoretical model testified that the hy-
drolysis products oligomerized by a SN1 dimerization mecha-
nism in alkaline solution and the condensation rates were
rapid for the formation of denser colloidal silica particles and
aerogels. However, the SN2 dimerization and the subsequent
cyclization reactions were energetically unfavorable.
Acknowledgements
This work was supported financially by the Natural Science Foun-
dations of China (21173129 and 11174215).
Keywords: alkoxides · density functional calculations ·
hydrolysis · oligomerization · silicon
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Received: February 9, 2012
Revised: March 20, 2012
Published online on && &&, 2012
www.chemphyschem.org &13&
These are not the final page numbers! ÞÞ
ARTICLES
X. Cheng, D. Chen, Y. Liu*
&& – &&

Mechanisms of Silicon Alkoxide

Hydrolysis–Oligomerization Reactions:
A DFT Investigation
Overcoming barriers: The hydrolysis–
oligomerization mechanisms of silicon
alkoxides in neutral, acidic (see picture),
and alkaline solutions were revealed
with density functional theory calcula-
tions.

&14& www.chemphyschem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 0000, 00, 1 – 14
ÝÝ These are not the final page numbers!