Diamond & Related Materials 98 (2019) 107480

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Diamond & Related Materials

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A simple method for synthesis of ordered mesoporous carbon T

a a,b,⁎ a
Xiuhua Ma , Hong Yuan , Meiqiu Hu
a
School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, China
b
State Key Laboratory of National Ethnic Affairs Commission Chemical Technology, North Minzu University, Yinchuan 750021, China

A R T I C LE I N FO A B S T R A C T

Keywords: A series of ordered mesoporous carbons (OMCs) was synthesized via a simple method using a nonionic surfactant
Ordered mesoporous carbon (block copolymer) P123 both as a structure–directing agent and as a carbon precursor at different carbonization
Simple method temperatures (500 °C, 600 °C, 700 °C, and 800 °C). Transmission electron microscopy (TEM) and small–angle
TEM X–ray diffraction (XRD) results indicated that OMC carbonized at 800 °C and 700 °C exhibited a highly ordered
Small–angle XRD
mesoporous structure, and the order of OMC decreased as the carbonization temperature decreased. N2–BET
N2–BET
analysis showed that the OMCs had BET surface areas of 427–713 m2/g and average pore diameters of
3.1–3.3 nm. Moreover, the BET surface area declined with decreasing carbonization temperature. Raman and
wide–angle XRD results indicated that OMCs synthesized under high carbonization temperature exhibited a
higher degree of graphitization than those synthesized under low carbonization temperature.

1. Introduction
Ordered mesoporous carbon (OMC) materials have become a hot
topic of research with regard to many fields (e.g., catalysis, adsorption,
and separation) due to their unique characteristics, such as regular
arrangement, single pore size distribution, adjustable size, high specific
surface area, and hydrothermal stability [1–4].
At present, mesoporous carbon materials with different structures
have been synthesized, such as rod–like, fiber–like, plate–like, do-
nut–like, and ball–like morphologies. The factors affecting their
morphologies include the morphology of the template, concentration of
synthetic media, additives (e.g., organic bulking agents), and interac-
tion between carbon precursor and surfactant [5–8].
Yu et al. [5] used triblock copolymer EO20PO70EO20 as a struc-
ture–directing agent and tetramethyl orthosilicate as a silica source to
synthesize highly ordered mesoporous silica (SBA–15) with different
morphologies (e.g., fiber–like, rod–like, plate–like, and donut–like
morphologies). These ordered mesoporous silica materials with dif-
ferent morphologies were used as templates and sucrose was used as a
carbon precursor to synthesize OMCs with different morphologies.
Their surface areas were in the range of 1558–1899 m2/g, and pore size
was in the range of 6.98–8.03 nm. Liu et al. [6] used triblock copolymer
(P123) and glycerol both as structure–directing agent and carbon pre-
cursor and tetraethoxysilane (TEOS) as a silicon source to synthesize a
series of OMCs. When the hydrochloric acid concentrations were 3 and
1 mol/L, OMC material with rod–like morphology was synthesized.
When the hydrochloric acid concentrations were 2.5, 2, and 1.5 mol/L,
gyroid–shaped, plate–like, and flower–type OMC materials were syn-
thesized, respectively. These mesoporous carbon materials have specific
surface areas, pore volume, and pore diameter in the ranges of
970–1312 m2/g, 1.09–2.20 cm3/g, and 4.7–6.5 nm, respectively. Zhang
et al. [7] used P123 as a structure–directing agent and hexadecane or
decane as organic–swelling agent to synthesize OMC (FDU–15) with a
2D hexagonal structure (p6m). By increasing the ratio of P123 to
phenol, a mesoporous carbon material (FDU–14) with a bicontinuous
cubic (Ia3hd) structure was synthesized. Wang et al. [8] synthesized a
mesoporous carbon material MC–S using soluble starch as a carbon
precursor and triblock copolymer (F127 and P123) as soft template by a
facile hydrothermal method. In hydrothermal synthesis, soluble starch
was hydrolyzed to form glucose, and glucose was assembled with a
pluronic copolymer through hydrogen bond interactions. The obtained
MC–S demonstrated a specific surface area of 439 m2/g and uniform
pore size of 4.5 nm.
The hard–template method [9] (two–step method) is the most
common technique for synthesizing OMC materials. In general, the
pre–existing ordered mesoporous material (ordered mesoporous silica)
is used as template, and carbon precursor is filled in the pores; after
polymerization–carbonization and template removal, OMC can be ob-
tained [10].
In 1999, Ryoo et al. [11] first reported the preparation of meso-
porous carbon materials by the hard–template method. The mesoporous
silica molecular sieve MCM–48 was employed as a template. An

⁎
Corresponding author at: School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, China.
E-mail address: yuanhong@nun.edu.cn (H. Yuan).

https://doi.org/10.1016/j.diamond.2019.107480
Received 9 April 2019; Received in revised form 27 June 2019; Accepted 18 July 2019
Available online 19 July 2019
0925-9635/ © 2019 Elsevier B.V. All rights reserved.
X. Ma, et al.
aqueous solution containing sucrose and sulfuric acid was filled twice
into the mesoporous channel of MCM–48. Sucrose was carbonized by
calcination at 800 °C–1100 °C in an inert atmosphere. Finally, the silica
skeleton was removed by NaOH/ethanol solution to obtain a highly
ordered carbon molecular sieve (CMK–1) with a specific surface area of
1380 m2/g and a pore diameter of 3.0 nm. In 2000, Jun et al. [12]
replaced MCM–48 with mesoporous molecular sieve SBA–15 to syn-
thesize OMC materials with a BET area of 1520 m2/g and pore diameter
of 4.5 nm. Thereafter, reports of the synthesis of OMC materials using
different hard templates or carbon precursors were published. Fuertes
et al. [10] used SBA–15 as a template to synthesize OMC materials with
paratoluene sulfonic acid and furfuryl alcohol. The BET surface area
was in the range of 1500–1800 m2/g, and the pore diameter was in the
range of 3.0–5.2 nm. Lin et al. [13] used mesoporous silica molecular
sieve MCM–41 as a template and sucrose as a carbon precursor to
synthesize an OMC with surface area of 1200 m2/g and pore volume of
1.0 cm3/g by a nanocasting process. Gokulakrishnan et al. [14] used
SBA–15 as a template and 2, 3–dihydroxynaphthalene as a fused aro-
matic carbon precursor to synthesize an OMC with a specific surface
area of 724 m2/g and pore diameter of 3.4 nm via nanocasting.
Boschnavarro et al. [15] utilized MCM–41 as a template and anthracene
molecule as a carbon precursor to form a mesoporous carbon material
with a BET surface area of 98 m2/g, pore volume of 0.08 cm3/g, and
pore size of 1.74 nm.
The hard–template method is used to synthesize OMC materials,
which has the disadvantages of a cumbersome synthesis process and
long cycle. In this process, a mesoporous silica molecular sieve is first
synthesized, filled into silicon oxide mesopores with a suitable carbon
precursor, and carbonized to finally synthesize a mesoporous carbon
material. Whether the carbon precursor is uniformly and efficiently
filled in the silicon oxide pores directly affects the order and structural
integrity of the final mesoporous carbon.
Researchers are also keen to find a preparation method of OMCs via
a simple preparation process and easily controllable orderability. The
soft–template method mainly uses a surfactant to guide the self–-
assembly of the carbon precursor to synthesize mesoporous carbon [9].
In 1999, Moriguchi et al. [16] pretreated phenol and formaldehyde to
form a phenol–formaldehyde polymer as a carbon precursor and a ca-
tionic surfactant cetyltrimethylammonium bromide as a structure–-
directing agent. A complex ion is formed under the action of static
electricity, but the removal of the surfactant results in a disordered
mesoporous carbon material. An increasing number of researchers have
used nonionic surfactants (block copolymers) as structure–directing
agents to prepare OMCs. Zhuang et al. [17] first prepolymerized phenol
and formaldehyde to form water and ethanol–soluble phenolic resins.
They then used phenolic resin as a carbon sources and triblock copo-
lymer F127 as a structure–directing agent to synthesize an ordered 2D
hexagonal mesostructure mesoporous carbon, which showed a surface
area of 398–2580 m2/g and uniform pore size of 4.5–6.4 nm. Wang
et al. [18] used phenol, resorcinol, and phloroglucinol as carbon pre-
cursor and F127 as a structure–directing agent to synthesize OMC with
2D hexagonal structure via self–assembly. The OMC had a BET surface
area of 1100 m2/g and adjustable pore size of 3.6–6.2 nm. Cheng et al.
[19] utilized amphiphilic carbonaceous material as a precursor and
P123 as a soft template to synthesize carbon tarballs with partially
ordered mesopores and hollow carbon nanofibers. Xiao et al. [20]
employed P123 as a soft template; glucose, D–fructose, D–maltose,
sucrose, and b–cyclodextrin as carbon precursors; and TEOS as a silicon
source to synthesize P123/silica/glucose composite via hydrothermal
method. The OMC was obtained by removing the templating agent and
silica and showed a specific surface area in the range of 330–620 m2/g.
The OMC material obtained by the soft–template method is sub-
jected to co–assembly in which a nonionic structure–directing agent
(block copolymer) and carbon precursor are co–assembled. When a
carbon precursor is added, the hydroxyl group on the surface can be
guided to the OMC material by hydrogen bonding with the hydrophilic
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Diamond & Related Materials 98 (2019) 107480
end PEO of the nonionic structure–directing agent (block copolymer).
For the soft–template method, the nonionic structure–directing agent
used mainly contains carbon, hydrogen, and oxygen. To this end, re-
searchers used the nonionic structure–directing agent directly as a
carbon precursor without adding a carbon source to synthesize OMC.
Kim et al. [21] synthesized SBA-15/P123 nanocomposite from tetra-
ethyl orthosilicate and P123 triblock copolymer. Tetraethyl orthosili-
cate was used as the silicon source, and P123 served both as a carbon
precursor and a structure-directing agent. After pretreatment with
sulfuric acid, pre‑carbonization was carried out at 100 °C and 150 °C,
followed by carbonization at 900 °C. After carbonization, silicon oxide
was removed to obtain the ordered mesoporous carbon (OMC) material.
Liu et al. [22] used P123 and mesoporous silica SBA-15 as a template to
fabricate a nanoporous carbon material with a bimodal pore system.
P123 acted both as a surfactant and carbon precursor in the mesopores
during synthesis at 550 °C. Li et al. [23] synthesized a silica/P123/su-
crose composite, in which P123 and sucrose served as structure-di-
recting agents and as carbon precursors. Following pretreatment with a
small amount of sulfuric acid and a short pre‑carbonization step, car-
bonization was performed at 850 °C. The silicon oxide was removed to
obtain the OMC material. The experimental procedure of Li et al. was
simpler and faster and required relatively little sulfuric acid. In the
work described herein, a simple OMC synthetic procedure was devel-
oped without sucrose. P123 was used as both a structure-directing
agent and carbon precursor along with tetraethyl orthosilicate as a
source of silicon. Pretreatment was first carried out with a small amount
of sulfuric acid. Following a short pre‑carbonization step, carbonization
was performed at 500 °C, 600 °C, 700 °C, and 800 °C. The silicon oxide
was removed, and the P123/silica composite was converted to an OMC.
The effects of carbonization temperature on the order, mesoporosity,
pore size, and graphitization of the OMC were investigated.
2. Experimental
2.1. Materials
P123 (PEO–PPO–PEO triblock copolymers), average Mn~5800, was
supplied from Sigma–Aldrich; TEOS (Tetraethyl orthosilicate, 98%,
reagent grade) was purchased from Aladdin; H2SO4 (98%) and hydro-
chloric acid (36%) was purchased from Sinopharm Chemical Reagent
Co., Ltd. (China).
2.2. Synthesis of OMC
The synthesis of the OMC is depicted as follows [23]: about 4 g of
P123, 120 g of HCl (2 mol/L), and 30 g of deionized water were mixed
and stirred well. Approximately 8.5 g of TEOS was slowly added to the
mixture, which was stirred at 40 °C for 24 h. Thereafter, the mixture
was aged at 100 °C for 48 h, filtered, and dried at 100 °C for 6 h to
obtain white powder (P123/silica composite), named P123/silica.
About 1 g of P123/silica composite was weighed and added to 10 g of
deionized water in which 0.1 g (98%) of sulfuric acid was dissolved,
stirred, and mixed uniformly. The mixture was ultrasonicated for 5 min
and pre–carbonized at 160 °C for 1 h. Subsequently, the mixture was
carbonized at 500 °C (heating rate of 1 °C/min) for 5 h under a nitrogen
atmosphere to obtain a carbon/silica composite, named C/silica–n,
where n is the carbonization temperature (600 °C, 700 °C, and 800 °C).
Finally, the silica/carbon composite was soaked in 10% HF solution for
24 h to remove the silica, and the obtained carbon material was named
OMC–500. Using different carbonization temperatures (600 °C, 700 °C,
and 800 °C), the carbon materials were named OMC–600, OMC–700,
and OMC–800, respectively.
2.3. Characterization methods
Transmission electron microscopy (TEM) of the samples was
X. Ma, et al.
Fig. 1. TEM, HRTEM, SAED and SEM images of OMC, C/silica and P123/silica.
conducted by using a Tecnai G2 F20 (FEI). The morphology and mi-
crostructure of the samples were measured by scanning electron mi-
croscopy (SEM) on a ZEISS EVO18 (Germany). The N2 adsorption ex-
periments were carried out with a Micromeritics ASAP 2020 Surface
Area and Porosity Analyzer. X–ray diffraction (XRD) patterns were
gathered on a SmartLab (Rigaku) X–ray diffractometer with Cu Kα ra-
diation at 40 kV and 30 mA. Raman measurement was performed on a
Horiba Evolution Raman spectrometer (France) with a laser wavelength
of 633 nm. Thermogravimetric analysis (TGA) was conducted using a
STA449F5 synchronous thermal analyzer apparatus (Netzsch,
Germany) at a heating rate of 10 °C/min under air atmosphere. X–ray
photoelectron spectroscopy (XPS) was carried out on a Thermo
Scientific/Escalab spectrometer equipped with Al Kα radiation.
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Diamond & Related Materials 98 (2019) 107480
3. Results and discussion
3.1. TEM and SEM
Fig. 1 shows the TEM images of the sample at different carboniza-
tion temperatures. Fig. 1a is the TEM image of the OMC carbonized at
800 °C. From the perpendicular channel direction (Fig. 1a left), regular
strip–shaped channels were noted. By contrast, hexagonally arranged
pore structures were observed along the channel direction (Fig. 1a
middle). These images showed that the OMC synthesized at 800 °C was
a typical 2D hexagonally ordered nanorod array mesoporous material.
A TEM image of the OMC synthesized by Li et al. [23] from P123 and
sucrose showed ordered channel arrays in parallel. However, their
X. Ma, et al. Diamond & Related Materials 98 (2019) 107480

Fig. 1. (continued)

4
X. Ma, et al.
Fig. 1. (continued)
Fig. 2. N2 adsorption–desorption isotherms and pore diameter distribution of OMC (a–d), C/silica (e–h) and P123/silica (i).
mesoporous carbon synthesized using only P123 as the structure-di-
recting agent and carbon precursor did not have the same morphology.
TEM images of the OMCs carbonized at 700 °C and 600 °C in this work
are shown in Fig. 1b, c. Both channel-like pores and a hexagonally ar-
ranged pore structure were observed. In comparison, the channel
structure of Fig. 1b was clearer than that of Fig. 1c, indicating that
700 °C was more favorable for the synthesis of OMC materials than
600 °C. Figs. 1d is the TEM image of the OMC carbonized at 500 °C. The
pores of the OMC were not clear but still exhibited an ordered structure.
Kim et al. [21] directly prepared mesoporous carbon by using as–-
synthesized SBA–15/P123 nanocomposite at 900 °C. The TEM image of
mesoporous carbon showed a clearly ordered pore structure. Li et al.
[24] used soluble, low–molecular–weight phenolic resin as carbon
precursor and F127 as template through the soft–template method to
synthesize OMC at 800 °C. The TEM image of mesoporous carbon also
showed a clearly ordered pore structure. Liu et al. [22] synthesized
mesoporous carbon CS15NS using as–synthesized SBA–15 as the tem-
plate and the surfactant P123 as the carbon precursor at 550 °C. The
TEM image of CS15NS showed a fuzzy visible pore structure. Therefore,
the carbonization temperature was an important factor affecting the
order of pore structure of OMC.
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Diamond & Related Materials 98 (2019) 107480
HRTEM images and SAED patterns of OMCs carbonized at different
temperatures are shown in Fig. 1a–d. In the HRTEM images of OMCs
carbonized at 600 °C, 700 °C, and 800 °C, a highly ordered, strip–shaped
pore structure was observed. The sample carbonized at 500 °C exhibited
only partial order. Highly ordered channels were clearly visible, and the
cell wall thickness was ~6.4 nm. Two distinct diffraction rings were
visible in the SAED patterns of OMCs carbonized at 700 °C and 800 °C.
The SAED patterns of OMCs carbonized at 600 °C and 500 °C did not
contain such a distinct diffraction ring. This indicated that graphitiza-
tion was more advanced in the OMCs obtained following high-tem-
perature carbonization than it was in samples carbonized at lower
temperatures [25,26].
TEM images of C/silica carbonized at different temperatures and
P123/silica composites are shown in Fig. 1e–i. Regular stripe-like
channels and a hexagonally arranged pore structure were clearly
visible. These composites exhibited a more highly ordered mesoporous
structure than the OMCs due to the presence of silica. SEM images of
the OMC, C/silica and P123/silica composite carbonized at 800 °C are
shown in Fig. 1j. Each material exhibited a rod-like morphology com-
prised of carbon rods, P123/silica rods, or carbon/silicon composite
rods with diameters of ~0.5 μm.
X. Ma, et al.
Fig. 2. (continued)
3.2. N2–BET
Fig. 2 shows the N2 adsorption–desorption isotherms and pore
diameter distribution of OMC, C/silica and P123/silica. As shown in
Fig. 2a–d, the curve shapes of nitrogen adsorption and desorption iso-
therms of all OMCs show typical type IV adsorption isotherm [27]. At
low relative pressure, the thickness of the adsorbed layer increased with
the increase in relative pressure. As the relative pressure increased,
condensation occurred at P/P0 = 0.2–0.9, and the hysteresis loops ap-
peared, indicating that all OMCs presented a good mesoporous struc-
ture [28,29]. The appearance of these hysteresis loops was due to the
capillary condensation phenomenon caused by the presence of meso-
pores. Although the hysteresis loops were narrow, they were typical
characteristics of mesoporous carbon materials. As the carbonization
temperature was increased from 500 °C to 800 °C, the width of the
hysteresis loop did not change significantly. The pore diameters of
OMCs were calculated from the adsorption branch using density func-
tional theory. When the carbonization temperature was in the range of
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Diamond & Related Materials 98 (2019) 107480
500 °C–800 °C, the pore diameter was 3.1–3.2 nm, which was similar to
the diameter of 3.2 nm (carbonized at 900 °C) reported by Kim et al.
[21] and to 3.6 nm (carbonized at 850 °C) reported by Li et al. [23].
However, our observed pore diameter was smaller than the diameter of
4.3 nm (550 °C) reported by Liu et al. [22]. The nitrogen adsorption/
desorption curves of C/silica and P123/silica shown in Fig. 2e–i were
typical type IV isotherms [30,31]. Hysteresis loops were observed at
relative pressures (P/P0) from 0.2 to 0.9. The hysteresis loops were
wider, which was indicative of a mesoporous structure. As shown in the
insets of Fig. 2e–i, the pore diameters had unimodal distributions. The
largest average pore diameter (7.9 nm) was observed in P123/silica,
whereas the pore diameters of the C/silica samples carbonized at dif-
ferent temperatures ranged from 5.5 to 5.9 nm. The larger pore dia-
meter of the P123/silica sample could be attributed to less extensive
micropore formation after carbonization [32]. The surface areas of the
OMCs, C/silica, and P123/silica were determined using the Bru-
nauer–Emmett–Teller (BET) method (Table 1). The BET surface area of
OMC carbonized at 800 °C reached 713 m2/g. The BET surface area of
X. Ma, et al. Diamond & Related Materials 98 (2019) 107480

Table 1 the BET surface area of 1150 m2/g (900 °C) was reported by Kim et al.
BET surface areas and average pore diameters of OMC, C/silica and P123/silica. [21]. Therefore, a high temperature was favorable for the increase in
Sample S/BET (m2/g) DDFT (nm) Pore volume(cm3/g) the surface area of OMCs. The BET surface areas of C/silica samples
carbonized at different temperatures were 412, 453, 575, and 657 m2/
OMC–500 427 3.3 0.33 g. These were lower than the surface areas of the OMCs but higher than
OMC–600 643 3.1 0.50
those of P123/silica, which was in agreement with results reported in
OMC–700 676 3.2 0.53
OMC–800 713 3.2 0.57
the literature [22]. The relative size of the BET surface area of OMCs
P123/silica 220 7.9 0.43 and C/silica was opposite to their adsorbed nitrogen amounts (Fig. 2 y
C/silica–500 412 5.9 0.58 axis). The BET surface area of the C/silica samples increased with the
C/silica–600 453 5.5 0.65 carbonization temperature, which was also observed with the OMCs.
C/silica–700 575 5.5 0.80
The pore volumes of OMCs carbonized at different temperatures were
C/silica–800 657 5.4 0.88
550 °C [22] 782 4.3a 0.77 smaller than those of the C/silica samples, which were consistent with
850 °C [23] 610 3.0b 0.66 their adsorbed nitrogen amounts (Fig. 2 y axis). The pore volume of the
850 °C [23] 720 3.6b 0.86 C/silica complex was reduced with the removal of silica, and the sur-
900 °C [21] 1150 3.2c 1.34
face area of the obtained OMC was larger due to the reduction in pore
diameter.
SBET: BET surface area; DDFT: pore diameter calculated from DFT method.
a
The calculation method is not specified.
b
The pore size distribution curve was calculated by the BJH
3.3. XRD
(Barrett–Joyner–Halenda) method from the desorption branch.
c
The pore size distribution was calculated from the analysis of the adsorp-
Fig. 3 shows the small–angle and wide–angle XRD spectra of OMC,
tion branch of the nitrogen isotherm using the BJH (Barrett–Joyner–Halenda)
method. C/silica and P123/silica. In Fig. 3a, the small–angle XRD spectra of
OMCs carbonized at 800 °C and 700 °C revealed a strong diffraction
the OMC synthesized by Li et al. [23] with P123 and sucrose following peak and two weak diffraction peaks in the range of 2θ = 1.0°–2.2°,
carbonization at 850 °C was 610 m2/g. The BET surface area of their which corresponded to the (100), (110) and (200) crystal plane of the
mesoporous carbon synthesized with P123 as the exclusive carbon hexagonal unit cell, which were attributed to the hexagonal structure
precursor was 720 m2/g following carbonization at 850 °C. The BET [33]. These diffraction peaks were similar to the small–angle XRD
surface area of the OMC increased with the carbonization temperature. spectra of mesoporous carbon materials prepared by Li et al. [23] at the
The literature reported that the carbonization temperature is an im- carbonization temperature of 850 °C. When the carbonization tem-
portant factor affecting the surface area (Table 1). For example, the BET peratures were 600 °C and 500 °C, only the (100) diffraction peak ap-
surface area of 782 m2/g (550 °C) was reported by Liu et al. [22], and peared. Besides, the diffraction peak significantly weakened when the
carbonization temperature was 500 °C. The small–angle XRD spectra of

Fig. 3. XRD spectra of OMC, C/silica and P123/silica: (a, b) small–angle spectra and; (c, d) wide–angle spectra.

7
X. Ma, et al.
Fig. 4. Raman spectra of OMC, C/silica and P123/silica.
mesoporous carbon prepared by Liu et al. [22] at a carbonization
temperature of 550 °C only showed a (100) diffraction peak. Therefore,
the small–angle XRD results demonstrated that the carbonization tem-
perature was an important factor affecting the order of OMC mesos-
tructure, which was consistent with the TEM results. For mesoporous
carbon with carbonization temperatures of 700 °C and 800 °C, the cal-
culated mesoporous carbon wall thickness was 6.0 nm [23,28], which
was similar to the TEM results. The small-angle XRD patterns of C/silica
carbonized at different temperatures are shown in Fig. 3b. A strong
diffraction peak and two weak diffraction peaks were observed in the
range of (2θ) 0.8°–1.7°. These corresponded to the (100), (110), and
(200) crystal planes of the hexagonal unit cell, which was similar to that
of the ordered mesoporous molecular sieve SBA-15 [28]. One strong
and two weak diffraction peaks were also observed from (2θ) 0.7° to
1.6° in the small-angle XRD patterns of P123/silica. These corresponded
to the (100), (110), and (200) crystal planes of the hexagonal unit cell
[31]. The carbonization process induced slight shrinkage of the meso-
porous structure, which shifted the position of the C/silica diffraction
peaks relative to those of P123/silica [32]. After removal of the silica
skeleton from C/silica, shrinkage of the OMC mesoporous structure
resulted in a shift of the strong diffraction peak (100) from (2θ) 0.8° to
between 1.0° and 1.1°. However, the OMC order was not affected,
which was consistent with the TEM observations.
Fig. 3c illustrates the wide–angle XRD spectrum of mesoporous
carbon. Each sample showed a strong diffraction peak at
2θ = 23.7°− 25.2°, and a weak peak appeared at 2θ = 42.3°− 43.4°,
which corresponded to the diffraction of the (002) and (100) planes of
the graphite structure [34,35]. As the carbonization temperature in-
creased, the diffraction peak also increased, indicating that the graphite
properties of the carbon material were enhanced. All of the C/silica and
P123/silica patterns contained a strong diffraction peak in the range
from (2θ) 21.9° to 22.5° (Fig. 3d), which was the broad characteristic
diffraction peak of amorphous SiO2 [36].
3.4. Raman spectra
Fig. 4a shows the Raman spectra of mesoporous carbon carbonized
at 500 °C, 600 °C, 700 °C and 800 °C. Two distinct peaks were found at
1320 and 1589 cm−1, which corresponded to the vibrations of amor-
phous carbon (D peak) and crystalline graphite (G peak), respectively
[37]. It can be seen that the D peak was wider than the G peak, in-
dicating that the prepared carbon material contained more amorphous
carbon [29]. At 800 °C, the G peak was slightly higher than the D peak,
indicating that the carbon material contains more crystalline graphite
carbon than amorphous carbon. In addition, the intensity ratios (ID/IG)
of the D and G peaks at 500 °C, 600 °C, 700 °C and 800 °C were 1.18,
1.12, 1.06 and 0.98, respectively. Thus, the mesoporous carbon syn-
thesized under high carbonization temperature had a higher degree of
8
Diamond & Related Materials 98 (2019) 107480
graphitization than that under low carbonization temperature. These
findings were consistent with the wide–angle XRD results.
The Raman spectra of C/silica carbonized at different temperatures
and P123/silica are shown in Fig. 4b. The two weak peaks at 1334 and
1570 cm−1 in the spectra of samples carbonized at 700 °C and 800 °C
corresponded to the vibrations of amorphous carbon (D band) and CeC
stretching in the graphite lattice (G band), respectively. The D and G
peaks gradually disappeared in the spectra of samples carbonized at
temperatures below 600 °C, possibly because the presence of silica af-
fected the appearance of the peaks. Similarly, the D and G bands in the
Raman spectra of P123/silica were barely visible.
3.5. XPS
Fig. 5a shows the C1s spectra of mesoporous carbon carbonized at
500 °C, 600 °C, 700 °C and 800 °C, which were divided into three single
peaks at binding energies of 284.8, 286.2, and 289.3 eV. The peak
center at 284.8 eV was attributed to the C]C bond in pure carbon. The
peak at 286.2 eV was due to C]O, and the peak at 289.3 eV could be
attributed to the carboxylic group. After heat treatment, oxygen was
present in the carbon grid in different forms of carboxyl groups, ester
groups, and hydroxyl groups. Oxygen was further measured by XPS, as
shown in Fig. 5b. The mesoporous carbon carbonized at 500 °C, 600 °C
and 700 °C showed a peak at 533 eV, which was attributed to the
characteristic peak of ester. The mesoporous carbon carbonized at
800 °C was divided into a peak at 532.6 eV, which was assigned to the
C]O characteristic peak [38,39]. The XPS result showed that the me-
soporous carbon only contained C and O elements and hardly contained
silicon.
The C 1 s, O 1 s, and Si 2p XPS spectra of C/silica and P123/silica
are shown in Fig. 5c–f. The C 1 s spectra were deconvoluted into four
individual peaks at binding energies of 283.7, 284.8, 286.2, and
287.8 eV. An additional C 1 s peak was observed in the spectra of C/
silica and P123/silica at 283.7 eV, which could be ascribed to carbon in
CeS bonds. The peak centered at 284.8 eV was attributed to C]C
bonds in pure carbon. The peaks at 286.2 and 287.8 eV were ascribed to
carbon in C]O bonds [38,39]. The XPS patterns of C/silica carbonized
at different temperatures showed an O 1 s peak at 532.3 eV, which was
attributed to oxygen in C]O bonds [33,34], whereas the corresponding
peak in the O 1 s spectrum of P123/silica appeared at 531.6 eV [40].
With increasing carbonization temperature, the peak intensity (C]O)
at 286.2 eV in the C/silica spectra gradually decreased due to the re-
duction in oxygen content. The Si 2p spectra of C/silica and P123/silica
all contained a peak at 103.0 eV, which was assigned to silicon in
eSieOeSie bonds [41,42].
X. Ma, et al. Diamond & Related Materials 98 (2019) 107480

Fig. 5. XPS spectra of OMC, C/silica and P123/silica.

3.6. TGA
The thermal stability of OMC, C/silica and P123/silica were in-
vestigated by TG under air atmosphere (Fig. 6). OMCs at different
carbonization temperatures showed similar TG curves. They demon-
strated significant mass loss of 95.78% (500 °C), 94.46% (600 °C),
90.32% (700 °C), and 85.93% (800 °C) in the range of 450 °C–600 °C,
which due to the oxidation of carbon. Given that the graphitization
degree of mesoporous carbon at carbonization temperatures of 700 °C
and 800 °C was high, the thermal stability of mesoporous carbon at
these two carbonization temperatures was relatively good. C/silica
carbonized in the 500 °C–600 °C range underwent 4.19%–8.28%

9
X. Ma, et al.
Fig. 6. TG spectra of OMC, C/silica and P123/silica.
reductions in mass (Fig. 6) due to carbon oxidation. The mass of P123/
silica was reduced by 40.03% in the carbonization temperature range of
180 °C–600 °C, which was mainly due to the oxidation of carbon and
hydrogen in the P123 block copolymer. Due to the presence of silica,
the mass reduction of P123/silica and C/silica was much smaller than
that of mesoporous carbon at the same carbonization temperatures.
4. Conclusion
We prepared a series of OMCs from the carbonization of as–-
synthesized silica/P123 composites at different carbonization tem-
peratures (500 °C, 600 °C, 700 °C, and 800 °C). The synthetic proce-
dures, especially the carbonization temperature, offer important
information for the carbon–free precursor–added one–step synthesis of
OMC. Results indicated that a high carbonization temperature
(> 600 °C) was advantageous to yield carbon with highly ordered
mesoporous structure, large BET surface area, and high thermal stabi-
lity. The graphitization degree of carbon material increased with the
carbonization temperature.
Funding
Financial support for this work from the National Natural Science
Foundation of China (21266001), Natural Science Foundation of
Ningxia (NZ17094), Ningxia Scientific and Technological Innovation
Leading Personnel Training (KJT2017006), Ningxia low–grade resource
high value utilization and environmental chemical integration tech-
nology innovation team project, New Catalytic Process in Clean Energy
Production (ZDZX201803) are gratefully acknowledged.
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