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Porous structure of PEG-mediated silica controlled by solution pH

O.V. Gorbunova, O.N. Baklanova, T.I. Gulyaeva

PII: S1387-1811(20)30470-4
DOI: https://doi.org/10.1016/j.micromeso.2020.110468
Reference: MICMAT 110468

To appear in: Microporous and Mesoporous Materials

Received Date: 3 May 2020

Revised Date: 3 July 2020
Accepted Date: 5 July 2020

Please cite this article as: O.V. Gorbunova, O.N. Baklanova, T.I. Gulyaeva, Porous structure of PEG-
mediated silica controlled by solution pH, Microporous and Mesoporous Materials (2020), doi: https://
doi.org/10.1016/j.micromeso.2020.110468.

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Credit Author Statement

O.V. Gorbunova – Conceptualization, methodology, investigation, writing - original draft, writing -

review & editing, visualization.

O.N. Baklanova – Supervision, conceptualization.

T.I. Gulyaeva – Investigation.

Porous structure of PEG-mediated silica controlled by solution pH

O.V. Gorbunova, O.N. Baklanova, T.I. Gulyaeva

Center of New Chemical Technologies BIC, Boreskov Institute of Catalysis

644040, Omsk, Russian Federation

54 Neftezavodskaya Str.

e-mail: Oxana_Gorbunova@inbox.ru

Abstract

This paper continues our previous study of porous amorphous silica prepared by the sol-gel

method using polyethylene glycol (PEG) as structure-directing agent [O.V. Gorbunova, et al,

Microporous and Mesoporous Materials 190 (2014) 146-151]. Here we analyze the effect of

acidic pH on the porous structure of silica synthesized with PEG. The results of adsorption

studies and 29Si NMR spectroscopy data allow us to declare the possibility of tuning the porous

structure of the amorphous silica materials exploiting the PEG concentration and pH of the

growth solution. Our results reveal that a gradual increase of the solution pH in the presence of

PEG initiates the growth of specific surface area, specific mesopore volume and average pore

size. We found that PEG makes it possible to obtain microporous silica materials in the pH

region of stable sols (from 1 to 3). When pH is in the range from 4 to 5, micro-mesoporous

materials with pore size less than 4 nm are formed.

Key words: Sol-gel; Silica; PEG; pH; Structure-directing agent

1. Introduction

A great deal of unique properties of porous silica materials such as high chemical, thermal and

mechanical stability, low toxicity, adsorption properties and catalytic inertness, they are involved

in various industries [1-5]. Generally, the application of silica materials and its efficiency are
determined by the textural characteristics of the material: a specific surface area, pore volume

and pore size distribution.

As a rule, parameters of the silica porous structure are controlled by tuning the synthesis

conditions, such as silica precursor concentration, temperature, and pH [6]. The pH has the

strongest effect on the porous structure. It changes the reaction rate of the SiO2 condensation

which can result in the formation of gels or slightly soluble precipitate. At pH ~ 2 the produced

sols are resistant to the gelation. Increasing pH promotes the silica condensation reaction

resulting in the gel formation. However, at pH>8 the gelation time increases again since the

silica particles are charged and only particle growth occurs [6]. Changing the rates of sol

hydrolysis and condensation allows one to obtain various nanostructures, from weakly branched

to close packed ones [7, 8]. The latter has a direct effect on the porous structure of the

synthesized silica materials [9-11].

Utilization of structure-directing agents in sol-gel synthesis of porous silica materials is the most

effective and flexible method to control their porous structure [12-14]. As a rule, the structure-

directing agent are injected into a solution before the formation of silica sol and removed from

the obtained material during the calcination or extraction processes. The following types of

structure-directing agents are usually used in the synthesis of silica materials: amphiphilic

compounds (Pluronic, CTABr) [15, 16], proteins [17, 18], polysaccharides like chitosan [19, 20]

and water-soluble polymers such as polyethylene glycol (PEG) [21-27].

In our origin work, we studied the effect of the PEG molecular weight (from 400 to 200,000) and

its concentration in the growth solution on the porous structure of the amorphous silica. We has

demonstrated that using the simple water-soluble polymers such as PEG it is possible to tune the

porous structure of the amorphous silica from pure microporous to mesoporous one [28]. In this

paper, we investigate a cross-impact of the PEG directing effect and pH of the growth solution in

the formation of the SiO2 porous structure in the sol-gel process.

2. Experimental section

2.1. Sample preparation

Tetraethylortosilicate (TEOS) (C2H5O)4Si ("EKOS-1"), polyethylene glycol with a molecular

weight 6000 ("Loba-Chemie") and hydrochloric acid were used for sol-gel synthesis of the

porous silica materials.

The synthesis is carried out according to the following procedure. Firstly, we prepared HCl

solutions with pH = 1, 2, 3, 4 and 5. Based on the results of our early work [28], we used a PEG

with a molecular weight of 6000 as the structure-directing agents. It was shown that PEG with

molecular weight of 6000 can direct the formation both the microporous and mesoporous silica

depending on the concentration in the growth solution. The PEG was dissolved for 2 hours at a

temperature of 50 °C to obtain the PEG concentration of 5 mmol/L in the hydrochloric acid

solution of the given pH. TEOS was added with portions of 0.5-1 mL/min to the prepared

solution of polyethylene glycol at constant stirring. In all experiments, the molar ratio of the

components was fixed at PEG:TEOS = 1:70. The resulting suspension was stirred for 2 hours

and then left at room temperature for 24 hours. The product was separated from the growth

solution by filtration with the Buchner funnel and filter paper under vacuum. The precipitate was

washed with distilled water and dried in air to constant weight at 105 °C. The dried product was

calcined in the muffle furnace at 600 °C for 6 hours.

2.2. Characterization

The SiO2-PEG composites after drying was studied by thermogravimetric (DGA) and differential

thermal analysis (DTA) on a STA-449C ("Netzsch") in the temperature range 40-700 oC.

Heating flow is 20% O2–Ar, flow rate – 70 mL/min, gas purity – 99.999%.

The structure of dried SiO2-PEG samples was investigated by 29Si solid state NMR in standard

single-pulse experiment, when the samples were rotated at the magic angle with the frequency of
10 kHz. 29Si NMR spectra were recorded on a Avance-400 spectrometer (Bruker) using the SB-4

multi-core sensor at the Larmor frequency of 79.5 MHz.

The nitrogen adsorption-desorption isotherms at 77.4 K were obtained for the calcined samples

on an ASAP-2020M (Micromeritics) analyzer using standard continuous procedures. Prior to

the adsorption-desorption experiments the samples were treated under vacuum conditions at 300

ºС for 8-10 h. Relying on the adsorption-desorption data, the following texture characteristics

were calculated: BET specific surface area (ABET) in the 0.01-0.1 equilibrium relative pressure

range, specific pore volume (Vads at p/p0 = 0.99), specific volume of micropores (Vmicro) by αS-

method [29]. The pore size distribution was estimated from the N2 adsorption-desorption

isotherms by the non-local density functional theory (NLDFT) for silica cylindrical pores using

DFT Plus software for Windows (Micromeritics) [30].

When discussing the results, the obtained silica materials are marked as SiO2-PEG-X, where X

represents the pH value, SiO2-X corresponds to the samples prepared without PEG.

3. Results

Fig. 1 illustrates the TGA and DTA curves measured for non-calcined silica materials

synthesized at pH = 1, 3, 4 and 5. The weight loss below 180 °C is resulted from the evaporation

of the residual moisture and desorption of water molecules. The weight losses from 180 to 350

°C is associated with decomposition of the polyethylene glycol. This assumption is supported by

the exoeffect on the DTA curves and also confirmed by the thermal analysis of pure PEG. The

decomposition of pure PEG is known to begin at about 180 °C [31]. As it is seen, the increase of

pH from 1 to 5 leads to a monotonic decrease in the amount of PEG adsorbed on SiO2 primary

particles from 25 to 20 wt%.

The 29Si NMR spectra (Fig. 2) demonstrate the signals with chemical shifts corresponding to Q3

(XOSi*(OSi)3 (X=H or С) and Q4 (Si*(OSi)4). It can be seen that intensity of the Q3 signal

relative to the Q4 one depends on the pH of the growth solution.

The ether oxygen atoms of PEG (-δO-CH2-CH2-) have a high affinity for Si-OH silanol groups

and, therefore, play a role of proton acceptors in the hydrogen bonding between PEG

macromolecules and silica primary particles. The amount of silanol groups on the surface of

silica particles formed as a result of the polycondensation reaction increases, when pH of the

growth solution decreases, but still is in the region of acid values. Therefore, the pH of the

solution medium is correlated with the strength of the PEG-silica interaction – the lower pH the

stronger the interaction between PEG macromolecules and silica primary particles. On the other

side, the SiO2 hydrolysis reaction rate is higher than the polycondensation rate at low pH.

Therefore, the primary particles of silica are relatively small. Thus, at low pH the silica is formed

by small primary particles “linked” to each other by the PEG macromolecules adsorbed on their

surface. The higher the pH of the growth solution, the lower the hydrolysis rate and surface

density of Si-OH groups those determine the particle size and the strength of PEG-silica

interaction, correspondingly. It is supported by the results of the thermal analysis. The amount of

adsorbed PEG on the SiO2 particles decreases with increasing pH from 25 to 20% of the mass.

Nitrogen adsorption-desorption isotherms for calcined silica materials prepared at different pH of

the PEG solution are shown in Fig. 3. It is clearly seen that the pH does not significantly affect

the shape of the isotherms those can be classified as the type I related to microporous solids [32].

However, the adsorption isotherms for SiO2-PEG-4 and SiO2-PEG-5 samples demonstrated a

sharp increase of the nitrogen loading up to the relative pressure P/P0=0.4 (Fig. 3). It is not

typical for microporous materials and may indicate a certain fraction of small mesopores.

To emphasize the effect of PEG, we prepared the series of silica materials without addition of the

PEG at the solution pH from 1 to 5. Keeping the synthesis conditions at pH from 1 to 3, gelation

was not taken place. In the cases of pH equal to 4 and 5, the standard gel formation is occurred.

The nitrogen adsorption-desorption isotherms for the SiO2-4 and SiO2-5 samples are presented in

Fig. 3. The isotherms are of type IV, they are characterized by the presence of capillary-
condensation hysteresis loops of type H2(a) according to the IUPAC classification. It indicates a

mesoporous structure of all the silica materials prepared without PEG [32].

Analysis of the experimental adsorption-desorption isotherms of the considered samples allows

us to determine their main texture characteristics, the values of which are indicated in the Table

1. It is seen that the silica materials synthesized without PEG at pH 4 and 5 have similar texture

characteristics reflecting their evident mesoporous structure. As it can be seen from the Table 1,

the addition of PEG as the structure-directing agent at pH=1 leads to the formation of a

microporous silica material with Vmicro/Vads is 0.94. With a further increase of pH up to 3 both

the value of the specific pore volume and specific surface area grow, while saving the

microporous structure of the samples. Using the fundamentally different methods, namely the αS

and the NLDFT methods, we have found that the fraction of micropores in these materials is

0.87-0.95. The pore size distributions for the SiO2-PEG-1 and SiO2-PEG-2 samples calculated by

the NLDFT method using the adsorption branch of the isotherm demonstrate (Fig. 4) the

polymodal character with peaks in the ultra- and supermicropore (up to 2 nm) regions. It is worth

to note a small fraction of mesopores up to 3 nm size in the SiO2-PEG-3. Raising the pH to 4-5

keeps the tendency of increasing both the specific pore volume and specific surface area.

Unfortunately, the αS-method does not allow a reliable estimation of the micropore volume for

these samples. Although the N2 adsorption isotherms on the SiO2-PEG-4 and SiO2-PEG-5

samples can be attributed to the type I corresponding to microporous solids, the curves have a

sharp increase of the N2 adsorption in the region P/P0=0.1-0.4 (Fig. 3). It may indicate the

presence of an appreciable fraction of small mesopores. Besides, the BET constants for the SiO2-

PEG-5 and for SiO2-PEG-4 samples in the relative pressure range of 0.06-0.2 have values of 117

and 250, respectively. It is not typical for porous solids with a predominant contribution of

micropores. Usually, the linearity interval of the BET equation for microporous solids lies below

P/P0=0.1. Although the αS-method is often and reliably used to evaluate both ultramicropore and

total micropore volumes, the presence of very small mesopores with a size near to the upper
boundary of the micropore diameters (2 nm) can lead to an overestimation of the micropores

fraction [33-35]. Thus, the specific micropore volume for the SiO2-PEG-4 and SiO2-PEG-5

samples obtained by extrapolating the linear αS-graph to the region of αS≥0.9 that is higher than

αS≥0.6 for the silica materials prepared at pH up to 1-3 can be attributed to the small mesopores.

However, the contribution of a certain fraction of supermicropores cannot be excluded. The

micropore volume estimated by the NLDFT gives the possible limit of the micropore volume for

such materials (Table 1).

The NLDFT pore size distribution reveals the micro-mesoporous texture of the samples (Fig. 4).

Fig. 4 illustrates a redistribution of the pore volumes towards an increase of the contribution of

large micropores and small mesopores up to 4 nm in size, when pH increases from 1 to 5. The

SiO2-4 and SiO2-5 samples prepared without PEG are mesoporous materials with the wide pore

size distribution from 2 to 10 nm (Fig. 4). Thus, tuning the pH of the growth solution in the

range from 1 to 5 is the effective way to smooth control the porous structure of the silica

materials synthesized by the sol-gel method with PEG as structure-directing agent.

4. Discussion

The isoelectric point of SiO2 is in the pH range from 1 to 3 [6]. Near this point the rate of SiO2

condensation reaction is minimal and, therefore, the size of primary silica particles is relatively

small. All the textural characteristics of corpuscular materials are determined by the particle size

and their packing density, which primarily depend on the rate and duration of the condensation

process. Porous structure of such materials consists of the voids between the aggregated primary

particles of the silica. Near the isoelectric point either the microporous silica or the stable colloid

solution of fine silica particles are formed in the presence or absence of the PEG, respectively. In

this case, the PEG has a major role. The PEG macromolecules have a unique ability to form a

solution fluctuation network absorbing silica primary particles and, as a result, linking them

together. It leads to their precipitation from the growth solution and formation of the
microporous silica. Indeed, the average pore sizes of the SiO2-PEG-1 and SiO2-PEG-2 samples

are of the least values for this series (Fig. 4).

The self-assembly of the micro-mesoporous SiO2-PEG-4 and SiO2-PEG-5 at pH=4-5 occurs as a

result of the increasing rate of the condensation reaction and decrease of the surface density of

Si-OH groups. The PEG macromolecules interact with Si-OH groups, attracting silica particles

to each other, which leads to the formation of micropores. An increase in the particle size of the

silica results in the formation of mesopores and increase of the specific surface area. The general

principle of silica sol-gel synthesis with PEG as the structure-directing agent is the higher the pH

of the growth solution, the higher the specific surface area, specific mesopore volume and

average pore size.

4. Conclusion

In this work, we investigate a cross-impact of the PEG macromolecules and the growth solution

pH in the evolution of the porous structure of the silica materials synthesized by the sol-gel

method. The pH parameter determines the rate of SiO2 condensation reaction and the strength of

the interaction between silica primary particles and PEG macromolecules those are used as the

structure-directing agent. A gradual increase of the acidic solution pH initiates the smooth

changes in the porous structure of the silica from the microporous to micro-mesoporous one. It is

worth to note that PEG makes possible the self-assembly of the microporous silica under the

stable sol conditions, at the pH from 1 to 3. In the pH range from 4 to 5 the micro-mesoporous

materials with pore diameters not exceeding 4 nm are formed. Thus, we have proposed the

simple and effective way to control the porous structure of the amorphous silica obtained by the

sol-gel method.

Acknowledgments
We thank N.V. Antonicheva and Dr. V.P. Talsi from the Center of New Chemical Technologies

BIC, Boreskov Institute of Catalysis for their valuable contribution to this research. This work

was carried out within the state task of the Boreskov Institute of Catalysis (Project АААА-А19-

119061490024-3). The research was performed using equipment of the Shared-Use Center

"National Center for the Study of Catalysts" at the Boreskov Institute of Catalysis.

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Table

Table 1 Textural properties of the silica samples estimated from the adsorption-desorption

isotherms. Relative errors of the BET surface area and specific pore volume measurements are

2.5% and 4.3%, respectively.

-------------------------------------------------------------------------------------------------------------

Sample ABET, m2/g Vads, cm3/g Vmicro, cm3/g Vmicro (NLDFT), cm3/g

-------------------------------------------------------------------------------------------------------------

SiO2-4 671 0.41 0.03 0.07

SiO2-5 599 0.37 0.02 0.08

-------------------------------------------------------------------------------------------------------------

SiO2- PEG-1 410 0.16 0.15 0.19

SiO2- PEG-2 482 0.20 0.19 0.18

SiO2- PEG-3 704 0.31 0.27 0.23

SiO2- PEG-4 767 0.36 0.31 0.20

SiO2- PEG-5 1088 0.54 0.40 0.18

Figure captions

Fig. 1. TGA and DTA curves for the non-calcined silica prepared at different pH using PEG with

molecular weight 6000 as the structure-directing agent.

Fig. 2. 29 Si NMR spectra for non-calcined silica prepared at different pH using PEG with

molecular weight 6000 as the structure-directing agent.

Fig. 3. N2 adsorption–desorption isotherms of the calcined silica prepared at different pH using

PEG with molecular weight 6000 as the structure-directing agent.

Fig. 4. Pore size distribution curves calculated with NLDFT method for calcined silica prepared

at different pH using PEG with molecular weight 6000 as the structure-directing agent.
Figures

Fig.1.

Fig.2.
Fig.3.

Fig.4.
Highlights of the manuscript titled “Porous structure of PEG-mediated silica controlled by
solution pH” by O.V. Gorbunova, O.N. Baklanova, T. I. Gulyaeva.

1) Porous structure of PEG-mediated silica can be tuned by pH of the growth solution

2) The higher the pH, the higher the specific surface area, pore volume and pore size of silica
3) PEG makes possible the assembly of microporous silica in the pH region of stable sols
4) Micro-mesoporous materials with pore size less than 4 nm are formed at pH from 4 to 5
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: