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org/JACS Communication

Ordered Mesoporous Silica Pyrolyzed from Single-Source Self-

Assembled Organic−Inorganic Giant Surfactants
Qing-Yun Guo,# Xiao-Yun Yan,# Wei Zhang,* Xing-Han Li, Yongsheng Xu, Shuqi Dai, Yuchu Liu,
Bo-xing Zhang, Xueyan Feng, Jiafu Yin, Di Han, Jiahao Huang, Zebin Su, Tong Liu, Mingjun Huang,
Chih-Hao Hsu,* and Stephen Z. D. Cheng*
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ABSTRACT: We report the preparation of hexagonal mesoporous silica from single-source giant surfactants constructed via
dihydroxyl-functionlized polyhedral oligomeric silsesquioxane (DPOSS) heads and a polystyrene (PS) tail. After thermal annealing,
the obtained well-ordered hexagonal hybrid was pyrolyzed to afford well-ordered mesoporous silica. A high porosity (e.g., 581 m2/g)
and a uniform and narrow pore size distribution (e.g., 3.3 nm) were achieved. Mesoporous silica in diverse shapes and morphologies
were achieved by processing the precursor. When the PS tail length was increased, the pore size expanded accordingly. Moreover,
such pyrolyzed, ordered mesoporous silica can help to increase both efficiency and stability of nanocatalysts.

M esoporous materials, with ordered structures and high

porosity, have demonstrated striking properties in
diverse application scenarios, such as separation,1 catalysis,2−5
a silicon-containing phase at high temperature while keeping
an eye on sufficient chain mobility as well as the high
percentage of nonvolatile elements. Therefore, despite these
superconducting materials,6 sensors,7−9 and drug delivery.10,11 striking merits of the single-source method, applying this
Among all strategies,12−19 the soft-templating method is strategy to prepare silica-based materials still remains a
extensively utilized for its convenience and low-cost. This formidable task.
strategy involves multiple components: the self-assembled Herein, we demonstrate a facile strategy to fabricate ordered
molecules (e.g., surfactants20−23 or block copolymers24−27) mesoporous silica with high porosities by pyrolyzing single-
involved to organize precursor species into ordered meso- source giant surfactants (Figure 1a).40−44 Polyhedral oligo-
structures. Though soft-templating method13,28 has received meric silsesquioxane (POSS), a type of “molecular nano-
significant success, the direct control over self-assembled particle”45−47 with precisely defined chemical structure and
structures and the alleviation of stringent amphiphilicity diverse functionalization capabilities,46,48,49 was chosen as the
requirements between templating molecules and precursors preceramic species38,50,51 and was covalently linked with a
still remain as big challenges. polystyrene (PS) chain to generate POSS−PS conju-
On resolving these issues, a single-source strategy was gates.40,41,43,52,53 The surface of the POSS cages was
proposed as an alternate. This method involves pyrolyzation of functionalized with highly hydrophilic dihydroxyl groups
single-source self-assembled macromolecules (e.g., block (DPOSS) providing the driving force of self-assembly due to
copolymer) containing nonvolatile elements.29−32 Such an the high immiscibility between DPOSS and PS (Figure
approach demonstrates excellent controllability over self- 1b).41,42,54−57 PS was adopted for its high hydrophobicity to
assembled structures and minimizes the usage of toxic and provide strong phase segregation strength as well as the
flammable organic solvents. It also showed the advantage of convenient synthesis via atom transfer radical polymerization
achieving desired shapes and morphologies by well-developed (ATRP) (a detailed discussion is resented in Supporting
polymer processing techniques.15,29 Subtle molecular engineer- Information Text 3.1). High-temperature pyrolysis can convert
ing in elemental composition of starting macromolecules has the POSS cages to silica and remove the PS tails to create
succeed to fabricate well-ordered mesoporous BN,30 SiC,32 pores with uniform size. 58,59 The pyrolyzed, ordered
mesoporous silica can also be utilized as catalyst support.
SiCN-type ceramics,31 and carbon33 by pyrolyzing single-
Giant surfactant 3DPOSS-PS22, which contains three
source block copolymers.
DPOSS heads and a PS tail with 22 repeating units (Figure
Interestingly, though studies on mesoporous silica occupy an
unambiguously dominant position,20−22,25,34 single-source
silica preparation still remains a missing puzzle. Commercially Received: May 24, 2021
available silicon-containing polymers, like polydimethylsiloxane Published: August 13, 2021
(PDMS), may serve as a promising candidate to prepare silica-
based materials.35−37 Unfortunately, PDMS derivatives suffer
depolymerization at high temperature.38,39 Substitution for
PDMS derivatives is another dilemma: people need to stabilize

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12935 J. Am. Chem. Soc. 2021, 143, 12935−12942
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Figure 1. (a) Schematic illustration of preparing ordered mesoporous silica by pyrolyzing single-source giant surfactant; (b) molecular structure of
giant surfactant 3DPOSS-PS22 as an example.

1b), was first synthesized. In the synthesis procedure, three mesostructure was obtained by thermal annealing, rather
vinyl-substituted POSS (VPOSS) were first connected with a than by a time-consuming evaporation-induced self-assembly
PS chain by the highly efficient copper-catalyzed azide−alkyne process which is commonly used in soft-templating synthesis
cycloaddition (CuAAC) reaction. Upon photoinitiated thiol− (a detailed discussion is presented in Supporting Information
ene radical addition with 1-thiolglycerol, the giant surfactant Text 3.2). The self-assembly of giant surfactants 3DPOSS-PS30
3DPOSS-PS22 was obtained (Scheme S2). As a well-defined and 4DPOSS-PS50 also results in the formation of highly
giant surfactant, 3DPOSS-PS22 can be readily dissolved into ordered hexagonal mesostructures (a detailed discussion is
THF, a common solvent for both blocks, affording a clear and presented in Supporting Information Text 3.4). For all three
transparent solution (Figure S7). Giant surfactant 3DPOSS- giant molecules, the structural characterization and key
PS30 was also synthesized following the same synthesis route, parameters of the self-assembled hybrids are demonstrated in
while giant surfactant 4DPOSS-PS50 was synthesized following Table 1.
our previously reported method.43 The detailed synthesis and Thermogravimetric analysis (TGA) of DPOSS, PS, and
chemical characterizations are shown in the Supporting 3DPOSS-PS22 were performed to help design the temperature-
Information. elevating program for pyrolyzing (Figure 2a). Comparing the
Self-assembly of giant surfactant 3DPOSS-PS22 was studied TGA thermodiagrams of DPOSS and 3DPOSS-PS22, the first
by small-angle X-ray scattering (SAXS) and transmission weight-loss stage (190−260 °C) can be attributed to the
electron microscopy (TEM). After thermal annealing at 130 thermal decomposition of DPOSS. According to the
°C for 2 h, 3DPOSS-PS22 showed a SAXS pattern with a set of thermogravimetric analysis-mass spectroscopy (TG-MS) re-
scattering vector (q) value ratios of 1: 3 : 2: 7 : 12 : 13 sults, H2O (m/z = 18) was observed as the main decomposed
, which is characteristic for a highly ordered hexagonal gaseous product (Figure S9) at this stage. The first weight-loss
structure (Figure 2b). The TEM image (Figure 2c) exhibited stage can be assigned as the dehydration between hydroxyl
a clear hexagonal pattern. The gray PS domains were groups on the DPOSS surfaces. It is accompanied by the cross-
embedded in the darker matrix composed of DPOSS cages. linking of the DPOSS phase since there are 14 hydroxyl groups
As a single-source giant molecule, a highly ordered on a single POSS cage surface. The second weight-loss stage
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Figure 2. (a) TGA curves (heating rate: 1 °C/min) of DPOSS, PS and 3DPOSS-PS22. (b) SAXS results of self-assembled 3DPOSS-PS22 and
corresponding pyrolyzed mesoporous silica C1. TEM images of (c) self-assembled 3DPOSS-PS22 and (d) C1. (e) XPS survey spectrum and (f)
solid-state 29Si NMR spectrum of C1.

Table 1. Summary of Self-Assembled Structures of Giant Surfactants in Bulka

sample mesostructure d100 (nm) a (nm) Vf, PS dPS (nm) Vf, DPOSS dDPOSS (nm)
3DPOSS-PS22 HEX 9.8 11.3 0.410 7.6 0.590 3.7
3DPOSS-PS30 HEX 10.8 12.5 0.486 9.1 0.514 3.4
4DPOSS-PS50 HEX 11.8 13.7 0.525 10.4 0.475 3.3
a
Detailed calculations are presented in Supporting Information Text 3.3.

Table 2. Summary of Ordered Mesoporous Silica Pyrolyzed from Self-Assembled Giant Surfactantsa
d100 pore size wall thickness BET surface area micropore surface pore volume micropore volume
sample precursor mesostructure (nm) (nm)b (nm) (m2/g) area (m2/g) (cm3/g) (cm3/g)
C1 3DPOSS-PS22 HEX 5.6 3.3 3.4 581 540 0.51 0.45
C2 3DPOSS-PS30 HEX 6.3 4.1 3.2 531 420 0.55 0.43
C3 4DPOSS-PS50 HEX 6.8 4.7 3.2 499 447 0.53 0.45
a
Detailed calculations are presented in Supporting Information Text 3.5. bObtained from N2 adsorption experiments.

(300−400 °C, ca. 60% weight loss) was assigned as the further heating rate under nitrogen atmosphere, followed by
decomposition of both DPOSS periphery groups and PS calcination in air at 500 °C for 24 h to remove the carbon
according to the TG-MS result, which showed H2O (m/z = formed by PS carbonization. The pyrolyzed ceramic product
18), H2 (m/z = 2) and ethylene (m/z = 28) as the main was characterized by SAXS and TEM. SAXS pattern of the
decomposed gaseous products (Figure S9). Other byproducts ceramic sample pyrolyzed from 3DPOSS-PS22 (denoted as C1)
including acetylene (m/z = 26), styrene (m/z = 104), and exhibited clear scattering peaks (Figure 2b) with q value ratios
benzene (m/z = 78) were also observed at this stage (Figure of 1: 3 : 2 , which indicated the preservation of hexagonal
S10), which were attributed to the depolymerization of PS and structure. The stability would be partially explained by the
high temperature gaseous reaction of the decomposed strong phase segregation strength43,60 between highly hydro-
products. philic DPOSS and hydrophobic PS as well as the cross-linking
On the basis of the TGA results, we pyrolyzed the self- of DPOSS cages by dehydration between hydroxyl groups. In
assembled 3DPOSS-PS22 at 800 °C for 2 h with a 1 °C/min the TEM image, C1 clearly show a hexagonal structure (Figure
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Figure 3. (a) N2 adsorption−desorption isotherms of C1. (b) Pore size distributions of C1 and C2. (c) Pictures of 3DPOSS-PS22, silica−carbon
composite, and C1 plate.

2d). The darker ceramic matrix was formed by POSS component pyrolyzed from 3DPOSS-PS22 can be concluded as
decomposition, while the pores were created by the removal amorphous silica.25
of PS. The d-spacing of the primary (100) scattering decreased The pyrolyzed mesoporous silica showed large surface areas
from 9.8 to 5.6 nm after pyrolysis, indicating large volume that useful in adsorption and separation.64−68 The Brunauer−
shrinkage due to the removal of organic components.31,32 Emmett−Teller (BET) surface area of C1 was measured as
TEM image (Figure 2d) indicated the distance between two 581 m2/g by N2 adsorption−desorption isotherms. A uniform
neighboring pore centers is 6.8 nm. This number is close to the and narrow pore size distribution with an average pore
value obtained from SAXS (6.5 nm). Pyrolysis of self- diameter of 3.3 nm was obtained (Figure 3a,b). On increasing
assembled 3DPOSS-PS30 and 4DPOSS-PS50 hexagonal hybrids the PS tail length to 30 repeating units, mesoporous silica C2
also yields hexagonal mesoporous silica (denoted as C2 and pyrolyzed from 3DPOSS-PS30 showed an average pore
C3, respectively, detailed discussion presented in Supporting diameter of 4.1 nm (Figure 3b). For mesoporous silica C3
Information Text 3.6). Key parameters of pyrolyzed meso- pyrolyzed from 4DPOSS-PS50, the average pore diameter was
porous silica are presented in Table 2. measured as 4.7 nm (Figure S15). These results indicate that
In order to identify the composition of the pyrolyzed high porosity with uniform and adjustable pore size was
product, X-ray photoelectron spectroscopy (XPS), solid-state achieved by manipulating the PS tail length and molecular
29
Si NMR, and wide-angle X-ray diffraction (WAXD) were geometry (Table 2).
conducted. XPS result demonstrated that the pyrolyzed A significant advantage of producing ordered mesoporous
ceramic product C1 is mainly consisted of silicon and oxygen materials from a single-source giant surfactant is the versatile
(Figure 2e). The atomic fractions of silicon and oxygen are processability of the precursors, which can help to control the
31.0 and 65.6%. (Table S1). The molar ratio of oxygen to morphology and monolithic shape of pyrolyzed product.15,29
silicon is close to 2, while a small amount of carbon was also For example, a solution of 3DPOSS-PS22 in THF was added
detected. Solid-state 29Si NMR spectrum of C1 showed signal into a mold, followed by evaporating the solvent and annealing
ranging from −100 to −125 ppm (Figure 2f). The major the discotic sample. Pyrolysis of the annealed sample resulted
chemical shift at −114 ppm can be assigned as Q4 ((SiO)4Si) in the formation of a mesoporous silica plate, while size
silicon atoms, and the minor shift at −104 ppm can be shrinkage was observed (Figure 3c).29,31,32,69 The excellent
assigned to Q3 ((SiO)3Si−O−C).61 No T3 ((SiO)3Si−C, Si of processability also allowed 3DPOSS-PS22 to be extruded into
POSS species) signal at around −67 ppm was observed, fibers or spin-coated into thin films. Silica fibers and thin films
indicating that the POSS cage has decomposed during with hexagonal structures were obtained after pyrolysis
pyrolysis.62 For the WAXD profile (Figure S12), only a (Figures S16 and S17).
broad peak was observed, indicating that the pyrolyzed ceramic For a simple demonstration, the mesoporous silica prepared
product is amorphous.63 Combining these results, the main by single-source strategy was fabricated into a support material
12938 https://doi.org/10.1021/jacs.1c05356
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pubs.acs.org/JACS Communication

for metal nanoparticle catalyst.3,70−75 We synthesized platinum AUTHOR INFORMATION

nanoparticles by reducing H2PtCl4 in the nanosized pores of Corresponding Authors
C1 and characterized the supported catalyst Pt@C1 by WAXD
Stephen Z. D. Cheng − South China Advanced Institute for
(Figure 4b) and TEM (Figure S18). Highly dispersed Pt(0)
Soft Matter Science and Technology, School of Molecular
Science and Engineering, South China University of
Technology, Guangzhou 510640, China; Department of
Polymer Science, School of Polymer Science and Polymer
Engineering, University of Akron, Akron, Ohio 44325-3909,
United States; orcid.org/0000-0003-1448-0546;
Email: scheng@uakron.edu
Wei Zhang − Department of Polymer Science, School of
Polymer Science and Polymer Engineering, University of
Akron, Akron, Ohio 44325-3909, United States;
orcid.org/0000-0002-9321-6411; Email: wz25@
zips.uakron.edu
Chih-Hao Hsu − Department of Polymer Science, School of
Polymer Science and Polymer Engineering, University of
Akron, Akron, Ohio 44325-3909, United States;
Email: ch45@zips.uakron.edu
Authors
Figure 4. (a) Reduction of 4-nitrophenol by H2 catalyzed by Pt@C1. Qing-Yun Guo − South China Advanced Institute for Soft
(b) WAXD profile of catalyst Pt@C1; (c) 400 nm absorbance on
Matter Science and Technology, School of Molecular Science
UV−vis spectroscopy and fitted line of ln(c0/c) to reaction time. (d)
Recyclability of Pt@C1 catalyst. and Engineering, South China University of Technology,
Guangzhou 510640, China; Department of Polymer Science,
School of Polymer Science and Polymer Engineering,
University of Akron, Akron, Ohio 44325-3909, United States
nanoparticles were identified. The catalytic activity of Pt@C1 Xiao-Yun Yan − South China Advanced Institute for Soft
was evaluated by the reduction of 4-nitrophenol (Figure 4a) Matter Science and Technology, School of Molecular Science
with UV−vis monitoring.75 In 90 min, 99.20% of starting and Engineering, South China University of Technology,
material was consumed (Figure 4c). The reaction was found to Guangzhou 510640, China; Department of Polymer Science,
be first-ordered, and the kinetic constant was calculated as School of Polymer Science and Polymer Engineering,
0.0515 min−1, which is significantly higher than that using University of Akron, Akron, Ohio 44325-3909, United States
same loading of unsupported Pt nanoparticles (0.0169 min−1) Xing-Han Li − South China Advanced Institute for Soft
(Figure S19). It can be concluded that the support by C1 can Matter Science and Technology, School of Molecular Science
significantly increase the reaction rate by inhibiting the and Engineering, South China University of Technology,
aggregation of platinum nanoparticles.72−75 Even in the third Guangzhou 510640, China
cycle, 99.48% of starting material was consumed in 90 min Yongsheng Xu − School of Chemical Engineering and
(Figure 4d and Table S4). This result indicates that Pt@C1 Technology, Tianjin University, Tianjin 300350, China;
catalyst exhibited excellent stability and reusability, which are orcid.org/0000-0002-4959-9013
important for practical applications. Shuqi Dai − South China Advanced Institute for Soft Matter
In summary, we demonstrate a new method to prepare well- Science and Technology, School of Molecular Science and
ordered mesoporous silica by pyrolyzing single-source giant Engineering, South China University of Technology,
surfactants. Ordered mesostructures were preserved after Guangzhou 510640, China
pyrolysis. Diverse morphologies, including monolith, fiber, Yuchu Liu − Department of Polymer Science, School of
and coating, were achieved by processing the precursor. High Polymer Science and Polymer Engineering, University of
porosity and uniform and tunable pore sizes were identified. Akron, Akron, Ohio 44325-3909, United States
When platinum nanoparticles were loaded, excellent catalyst Bo-xing Zhang − South China Advanced Institute for Soft
efficiency and stability were achieved. Through further Matter Science and Technology, School of Molecular Science
chemical structural diversification of precursor molecules, and Engineering, South China University of Technology,
well-ordered mesoporous materials with more diversity of Guangzhou 510640, China; orcid.org/0000-0002-3399-
composition, structure, and functionality are expected in the 5548
future. New opportunities for achieving functional mesoporous Xueyan Feng − Department of Polymer Science, School of
materials are opened up. Polymer Science and Polymer Engineering, University of

■
Akron, Akron, Ohio 44325-3909, United States
ASSOCIATED CONTENT Jiafu Yin − South China Advanced Institute for Soft Matter
Science and Technology, School of Molecular Science and
* Supporting Information
sı
Engineering, South China University of Technology,
The Supporting Information is available free of charge at Guangzhou 510640, China
https://pubs.acs.org/doi/10.1021/jacs.1c05356. Di Han − College of Polymer Science and Engineering, State
Synthesis and characterization data of giant surfactants, Key Laboratory of Polymer Materials Engineering, Sichuan
methods, experimental details, additional results and University, Chengdu 610065, China; orcid.org/0000-
discussions (PDF) 0001-5794-6145
12939 https://doi.org/10.1021/jacs.1c05356
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