Environmental Research 231 (2023) 116070

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Synthesis of ordered mesoporous silica from biomass ash and its application
in CO2 adsorption
Shihai Xu a, Chuncai Zhou a, *, Hongxia Fang a, Wenrui Zhu a, Jiaqian Shi a, Guijian Liu b
a
School of Resources and Environmental Engineering, Hefei University of Technology, No. 193, Road Tunxi, Hefei, 230009, China
b
School of Earth and Space Sciences, University of Science and Technology of China, No. 96, Road Jinzhai, Hefei, 230026, China

A R T I C L E I N F O A B S T R A C T

Keywords: It is possible to achieve high-value utilization of solid wastes and lower the cost of mesoporous silica synthesis by
Recycling synthesizing mesoporous silica from solid wastes. In this study, silica was extracted using the alkali fusion
Biomass ash method using biomass ash as the starting material. Biomass ash based mesoporous silica was successfully pre­
Mesoporous silica
pared by hydrothermal method with silicon extract solution as silicon source. The optimum conditions for
Hydrothermal synthesis
CO2 adsorption
preparation were determined as follows: addition of cetyltrimethylammonium bromide was 0.45g, hydrothermal
temperature was 120 ◦ C, hydrothermal time was 24h. The prepared mesoporous silicon was systematically
characterized, and the results showed that high surface area (495 m2/g) and ordered pore structure appeared in
the synthesized mesoporous silica materials. The synthesized mesoporous silica showed excellent CO2 adsorption
performance (0.749 mmol/g) at 25 ◦ C and 1 bar. According to the calculation of adsorption isotherm and
thermodynamics, non-linear Freundlich model can fit the adsorption isotherm better and the adsorption heat of
mesoporous silica is less than 20 kJ/mol, which belongs to physical adsorption. After five cycles of CO2
adsorption, the adsorption property was still above 90%, and the CO2/N2 adsorption selectivity reached 396.6,
showing good regeneration performance and adsorption selectivity. This research can provide a new possibility
for the high-value exploitation of biomass ash and reducing the cost of synthetic mesoporous silica.

Author contributions statement
Shihai Xu: Conceptualization, Writing-original draft, Writing-
review & editing, Chuncai Zhou: Resources, Writing - review & edit­
ing, Supervision, Hongxia Fang: Visualization, Formal analysis, Wen­
rui Zhu: Investigation, Formal analysis, Jiaqian Shi: Visualization,
Guijian Liu: Supervision, Writing-review & editing.
1. Introduction
With the constant consumption of fossil fuels worldwide and sus­
tained CO2 emissions from combustion, people are turning their atten­
tion to renewable and low-carbon energy fields (Ang et al., 2022).
Among them, biomass energy has been developed vigorously in the
world because of its renewability, low pollution, abundant reserves and
strong substitution ability (Munawar et al., 2021). However, due to the
large-scale development of biomass power generation, a large amount of
ash and slag are produced (Voshell et al., 2018), which need to be
treated to reduce the land occupation and environmental pollution. At
present, China now produces 3.494 billion tons of biomass annually,
with 460 million tons of conventional coal having the potential to be
developed as energy sources (Guo et al., 2022). In 2020, the biomass
power generation scale reached 29.52 million KW in China, ranking first
in the world. However, the rapid growth of biomass power plants has
resulted in a significant amount of ash production. Theoretically, China
will produce 829 million tons of straw resources annually by 2020, and
694 million tons of these resources will be collectible (Guo et al., 2022).
Calculated by the average ash production of dry biomass of 6.8%
(Vassilev et al., 2013), about 47 million tons of ash residue are produced
annually, which need to be treated urgently. The preparation of high
value-added materials such concrete-based materials, mesoporous mo­
lecular sieve (MCM and SBA series), photocatalyst offers, zeolite
(ZSM-5), and CO2 adsorbent a lot of potential for biomass ash due to its
high silicon content (Liou et al., 2022).
1992, M41S series of new mesoporous molecular sieves were suc­
cessfully synthesized by mixing surfactant, silicate and alkali in pro­
portion (Beck et al., 1992; Kresge et al., 1992). Because of its ordered
hexagonal pore structure, uniform pore size, controllable pore size,

* Corresponding author.
E-mail address: zhoucc@hfut.edu.cn (C. Zhou).

https://doi.org/10.1016/j.envres.2023.116070
Received 15 February 2023; Received in revised form 24 April 2023; Accepted 4 May 2023
Available online 5 May 2023
0013-9351/© 2023 Elsevier Inc. All rights reserved.
S. Xu et al.
modifiable surface, strong mechanical properties, and relatively inert
chemical composition, mesoporous silica is widely used as an adsorbent,
catalyst carrier, sensor material, polymer reinforced material, and other
advanced composite materials (Diagboya and Dikio, 2018; Nassar et al.,
2019; Shinde et al., 2021). The classic approach begins with the
extraction of silica from a source of silica, such as quartz sand. However,
this process requires temperatures as high as 1500 ◦ C and generates
significant amounts of CO2, Na2SO4, and wastewater, which is contrary
to the sustainable development goal (Mor et al., 2017; Zarei et al.,
2021). Recently, modern technologies such as physical/chemical vapor
deposition (PVD/CVD), inverted microemulsion, sol-gel method, etc.,
which use tetraethyl orthosilicate (TEOS) as silicon source to prepare
silica materials are more widely used (Karande et al., 2021). However,
due to the high temperature requirement, most chemical processes of
silica synthesis are also expensive (Anuar et al., 2018). In addition, Ni
(CO)4 and SiCl4 used in CVD method may explode and cause environ­
mental hazards (Yugandhar et al., 2015). Based on this, it is proposed to
use biomass ash with high silicon content as the precursor for preparing
silica. So far, different forms of silica materials have been prepared from
biomass ash, such as silica nanoparticles prepared from olive residue
(Rezaeian et al., 2021), silica aerogels and dry gel prepared from
biomass ash (Asim et al., 2019; Rajanna et al., 2015), and amorphous
porous silicon (Bakar et al., 2016; Dhaneswara et al., 2020) and meso­
porous silica (Andrade et al., 2022) prepared from rice husk ash. How­
ever, most researchers use the single biomass ash prepared in the
laboratory as the silicon source instead of using the ash generated by the
actual biomass power plant, which makes the feasibility of these
methods in the actual production still need to be studied.
Currently, the majority of CO2 capture is done using some traditional
techniques based on physical and chemical adsorption, low-temperature
distillation, absorption, microorganism and membrane separation
technology (Leung et al., 2014). Although chemical absorption using
liquid amines is the most advanced and economical technology for
direct large-scale capture of CO2 from flue gas, This approach still has
several significant drawbacks, including solvent breakdown, a low ca­
pacity for absorption and a high energy requirement for solvent regen­
eration (Policicchio et al., 2022). Finding novel materials for
high-capacity and renewable CO2 capture is still important to get
beyond these drawbacks. Mesoporous silica has attracted a lot of
attention in CO2 capture due to its good pore structure and great
chemical stability (Henao et al., 2020; Mao et al., 2022), but it is obvi­
ously uneconomical to use expensive materials such as silicon alkoxide
or silica aerosol as silicon source. Coal gangue was used as raw materials
to prepare mesoporous silica M-SiO2 with a CO2 adsorption capacity of
0.22 mmol/g and modified EDA-M-SiO2 with an adsorption capacity of
1.9 mmol/g (Du et al., 2018). Modified mesoporous silicon prepared
from rice husk ash greatly improved the adsorption performance and
selective adsorption capacity of CO2 (Henao et al., 2020). These studies
have shown that the use of solid waste with high silicon content as a
silicon source can not only reduce the preparation cost of mesoporous
silica materials, but also provide a feasible way for the resource utili­
zation of solid waste.
Silicon from biomass ash was extracted by alkali melting method,
and the effects of alkali-ash ratio, calcination time and calcination
temperature on the extraction rate of silicon were investigated. Hydro­
thermal method was used to synthesis mesoporous silica, and the
preparation conditions were optimized. Using the silicon extract of
biomass ash as silicon source, mesoporous silica with a specific surface
area of about 495 m2/g was successfully prepared, and the morphology
and structure of the synthetic mesoporous silica were characterized
systematically. In addition, the prepared mesoporous silica showed
excellent CO2 adsorption performance, and the adsorption process was
analyzed. This study established the viability of using biomass ash as a
source of silicon to synthesize mesoporous silica and use it for CO2
adsorption, serving as a benchmark for the efficient use of biomass ash
as a resource.
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Environmental Research 231 (2023) 116070
2. Materials and methods
2.1. Materials
Biomass ash was collected from a biomass power plant in Bozhou,
Anhui Province. The main fuel is a mixture of wheat straw, corn straw,
and forestry waste (5:2:3), with an annual fuel consumption of
approximately 303300 tons. X-ray fluorescence spectrometer (XRF) was
used to establish its major chemical composition (Table 1). The content
of SiO2 in biomass ash reaches 54.96%, and it also contains Fe, Al, Ca, K
and other major components. From the particle size distribution of
biomass ash, about 60% of particles are distributed below 5 mm. The
mineral phase composition of sample was examined using X-ray
diffraction (XRD), and the results are displayed in Fig. 1. It is evident
that quartz is the primary mineral phase of biomass ash. The reagents
mainly used in the experiment are hydrochloric acid, sodium hydroxide
and cetyltrimethylammonium bromide (CTAB), all of which are
analytically pure or higher. Pure water was also used throughout the
research.
2.2. Extraction of silicon from biomass ash
Alkali fusion method is used to extract silica from biomass ash
(Chandrasekar et al., 2008). Biomass ash (5g) ground to less than 200
mesh was mixed with a certain mass ratio of NaOH and placed in a nickel
crucible. The muffle furnace was used to calcinate the mixture at
450–500 ◦ C for 0.5–3h to obtain calcined clinker. Clinker and pure water
were mixed at a solid-to-liquid ratio of 1:10, and magnetic stirring was
used to mix the mixture for 2 h. After stirring, the extract was obtained
by filtration, which can be used as a silicon source for the synthesis of
mesoporous silicon materials.
In this process, the concentration of SiO2−
3 in the silicon extraction
solution is determined by acid-base titration (Yan et al., 2016). Excess
sodium fluoride is added to the solution to generate a quantitative so­
dium hydroxide. Excess hydrochloric acid solution is added to the so­
lution, and then the sodium hydroxide standard titration solution is used
for back titration (Gao et al., 2015). The principle of the method is
shown in equations (1) and (2):
SiO2−3 + 6F− + 2Na+ + 2H+ →Na2 SiF6 ↓ + 4OH− (1)
H+ + OH− →H2 O (2)
The calculation of SiO2−
3 leaching rate is shown in equation (3):
3
MSiO2 × CSiO2−3 × V × 10−
ηSiO2 = × 100% (3)
mBA × WSiO2
Where ηSiO2 : SiO2−
3 leaching yield, wt.%; MSiO2 : molar mass of SiO2, g/
mol; CSiO2− : concentration of SiO2−
3 , mol/L; V: volume of leachate, L;
3
mBA: the mass of biomass ash; WSiO2 : the SiO2 content in biomass ash.
2.3. Synthesis of mesoporous silica from biomass ash
Mesoporous silica was synthesized by hydrothermal synthesis using
the silicon extract prepared from biomass ash as the silicon source. CTAB
(C16H33(CH3)3NBr) was dissolved in 50 mL of silicon extract solution
and stirred fully at room temperature. Hydrochloric acid was used to
adjust the pH of the mixture to 10 ± 0.5. Magnetic stirring was used to
mix the mixture for 2 h. After that, the mixture was transferred to a
Teflon-lined Hydrothermal Reactor. After the hydrothermal reaction,
the white sediment was obtained by centrifugation, repeated washing,
and dried at 105 ◦ C. Finally, the surfactant template was removed from
the white powder by calcining it at 550 ◦ C for 6 h in a muffle furnace. In
this procedure, the effects of hydrothermal duration, hydrothermal
temperature, and CTAB addition on the final product’s adsorption per­
formance were investigated.
S. Xu et al.
Table 1
Chemical composition of the Biomass ash (BA) and Desilicified ash (DSA) (wt %).
Sample SiO2 Fe2O3 Al2O3 CaO
BA 54.96 11.56 10.88 8.04
DSA 38.74 17.75 12.56 13.11
L.O.I: loss on ignition.
Fig. 1. The XRD patterns of biomass ash and desilicified ash.
2.4. Characterization of mesoporous silica
The X-ray diffraction (Panalytical X-rert PRO MPD) was used to
obtain the small-angle and wide-angle patterns of prepared mesoporous
silica. The Nicolet™ 6700 spectrometer (Thermo Scientific, USA) was
employed to measure the Fourier transform infrared (FTIR) spectra of
the mesoporous silica, single beam reflectance spectra were recorded
over the wavenumber range 525–4000 cm− 1. Utilizing scanning elec­
tron microscopy (SEM; Regulus 8230, Hitachi, Japan), the microstruc­
ture and morphology of mesoporous silica were examined. A JEM-
1400flash microscope running at 120 kV accelerating voltage was
used for the transmission electron microscopy (TEM). The N2
adsorption-desorption isotherm at 77K recorded by the Autosorb iQ
instrument (Quantachrome, USA) and the BET model computation were
used to determine the BET specific surface area of the sample. All of the
samples were degassed under a vacuum for 8 h at 378K before to the test.
According to the N2 adsorption-desorption isotherm, the pore size dis­
tribution was calculated by the Density Function Theory (DFT) model.
And t-plot model was used to calculate the micropore volume of the
sample. Nano particle size and Zeta potentiometers (Nano ZS90, China)
were used to analyze the average particle size and particle size distri­
bution curve of mesoporous silica aggregates.
2.5. Adsorption test
The CO2 adsorption experiment is performed using the Micrometric
ASAP 2020 instrument (Micrometrics, USA). At 298K, the CO2 adsorp­
tion capacity of the samples was determined using an adsorption
analyzer. Before each adsorption test, all samples were degassed for 8 h
at 378K under vacuum to remove impurity gases. Then the CO2 gas is
introduced into the adsorption system, and the CO2 adsorption isotherm
at 298K under the pressure range of 0.01–1 bar is tested and the
adsorption capacity is calculated. The samples with better adsorption
effect were selected to determine the adsorption capacity at 298K, 318K
and 338K, and the cyclic adsorption experiments were carried out at
298K.
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Environmental Research 231 (2023) 116070
K2O TiO2 P2O5 MgO Na2O L.O.I
7.13 1.52 0.78 0.66 0.40 2.53
3.83 2.75 0.23 0.76 3.83 2.45
3. Results and discussion
3.1. Effect of operating conditions on silicon extraction
In the experiment, the influence of alkali-ash ratio, calcination time
and calcination temperature on the leaching concentration of silicon
element was considered through the single factor experiment, and the
results are presented in Fig. 2. Fig. 2a depicts the effect of alkali-ash ratio
on SiO2 extraction efficiency when the calcination period is 2 h and the
calcination temperature is 550 ◦ C. The extraction efficiency of silicon
improves with increasing alkali-ash ratio, and the extraction rate rea­
ches a maximum of 51.95% when the NaOH/ash ratio is 1.5. However,
with the further increase of the ratio, the extraction rate of silicon de­
creases slightly. Which could be interpreted as follows: First, with the
increase of NaOH/Ash, when pure water is added to stir after calcina­
tion, the increase of NaOH concentration can increase the collision
probability between molecules (Greenberg, 1957), thus promoting the
extraction of SiO2. Further, the reactivity of Al2O3 in the sample may
increase due to the continuous increase of NaOH, resulting in the reac­
tion with dissolved SiO2− 3 (Yan et al., 2016). Meanwhile, the high con­
tent of Na+ may promote zeolite formation (Hui et al., 2005), impeding
the synthesis of mesoporous silica. Therefore, the alkali-ash ratio of 1.5
was used for subsequent experiments.
Fig. 2b–c shows the silicon extraction efficiency at different calci­
nation times and temperatures respectively. It can be seen that when the
calcination time is 0.5h, the extraction rate of silicon element is 40.39%,
and when the time increases to 2h, the extraction rate of silicon element
reaches the maximum value, and then fluctuates around 50%. Similarly,
when the calcination temperature is less than 500 ◦ C, the extraction rate
of silicon is approximately 45%, but when the calcination temperature is
greater than 500 ◦ C, the extraction rate of silicon climbs to more than
50%. This may be because under alkaline conditions, increasing the
temperature is beneficial to the dissolution of glass phase (Chandrasekar
et al., 2008; Moghadam et al., 2019). When the temperature rises again,
the extraction rate of silicon does not increase significantly. Meanwhile,
increasing the temperature may improve the dissolution of Al2O3 in the
sample and the precipitation of sodalite, so 550 ◦ C is a suitable calci­
nation temperature (Yan et al., 2016). To sum up, in the following
experiment, mesoporous silica was synthesized by using the silicon
extract under the experimental conditions of NaOH/ash ratio of 1.5,
calcination time of 2h and calcination temperature of 550 ◦ C.
Fig. 1 illustrates the alteration of mineral crystal phase of desilicified
ash. The diffraction intensity of crystal phase of desilicified ash obtained
after extracting silicon element is greatly reduced compared with
biomass ash. In addition, Table 1 provides the proportion of elements in
desilicified ash, in which the content of SiO2 is obviously decreased, and
Fe, Al, Ca and other elements are slightly increased. All of these results
suggest that the silicon in biomass ash is successfully enhanced in the
extraction solution and can be used to produce mesoporous silica
materials.
3.2. Characterization of mesoporous silica
A variety of samples were synthesized under various experimental
conditions (Table 2) (CTAB addition, hydrothermal reaction time and
temperature) with silicon extract as silicon source. Through the char­
acterization of the sample and the test of CO2 adsorption performance,
the suitable preparation conditions of mesoporous silica from biomass
S. Xu et al. Environmental Research 231 (2023) 116070

Fig. 2. Extraction efficiency of silicon element under different conditions.

3.2.2. FTIR spectra

Table 2
The functional groups in the mesoporous silica are identified using
The corresponding experimental parameters of different mesoporous silica
the FTIR spectrum. Fig. 4a presents the infrared spectrograms of syn­
samples.
thetic mesoporous silica between 4000 and 525 cm− 1. It is easy to notice
Sample CTAB (g/50 mL) Time (h) Temperature (◦ C)
in the spectra that there are obvious absorption bands at ~806 cm− 1 and
CTAB-0.00 0 24 120 ~1100 cm− 1. These absorption bands are associated with the symmetric
CTAB-0.15 0.15 stretching vibration and the asymmetric stretching vibration of silicone
CTAB-0.30 0.30
(Si–O–Si), respectively (Li et al., 2014; Monash and Pugazhenthi, 2010).
CTAB-0.45 0.45
CTAB-0.60 0.60 Additionally, a tiny absorption peak at ~1626 cm− 1 can be seen, which
CTAB-0.75 0.75 is caused by the hydroxyl groups in the adsorbed water on the sample
Time-12h 0.45 12 120 surface vibrating in a bent manner. In addition, the FTIR spectra of the
Time-16h 16
samples prepared at various hydrothermal time and temperature shows
Time-20h 20
Time-24h 24
that the absorption peaks of all synthesized mesoporous silica samples
Time-28h 28 are basically consistent, and the absorption peaks are related to
Temp-75 ◦ C 0.45 24 75 silicon-oxygen bonds, suggested that the prepared sample is SiO2
Temp-90 ◦ C 90 adsorption material.
Temp-105 ◦ C 105
Temp-120 ◦ C 120
Temp-135 ◦ C 135 3.2.3. Thermogravimetric analysis
The related thermogravimetric curves of mesoporous silica adsor­
bents produced with various CTAB additions are presented in Fig. 4b.
ash source were determined. With the increase of temperature, the weight loss of the sample without
template CTAB is small, indicated that the silica-based adsorbent has
3.2.1. XRD analysis excellent thermal stability. However, when the adsorbent is exposed to
Fig. 3 depicts the XRD patterns of mesoporous silica synthesized the air, there will be physically adsorbed water and carbon dioxide in
under various conditions. As can be seen in Fig. 3a, there are no char­ the sample with template CTAB, which will be volatilized during the
acteristic peaks appear in the XRD patterns of CTAB-0.00, CTAB-0.15 heating process from 30 ◦ C to 105 ◦ C, and a slight weight loss process
and CTAB-0.30, while the diffraction peaks in the samples CTAB-0.45, occurs (Zhao et al., 2019, 2022). Another obvious weight loss occurs
CTAB-0.60 and CTAB-0.75 are between 2◦ and 2.5◦ , indicated an or­ near 800 ◦ C caused by the loss of isolated and terminal silanol of mes­
dered hexagonal phase mesoporous structure was synthesized (Boldrini oporous silica (Cerveny et al., 2012; Yan et al., 2017). Weight loss within
et al., 2019; Yan et al., 2016). Fig. 3b shows that the samples prepared the temperature range of 105–700 ◦ C may be caused by the degradation
under all hydrothermal time conditions have the similar diffraction of incompletely removed templates as well as the loss of geminal and
peak. By comparison, it is found that the diffraction intensity of the vicinal silanols of mesoporous silica particles (Yan et al., 2017). In
sample is higher when the hydrothermal time is more than 24h, sug­ addition, note that the obtained mesoporous silica can maintain good
gested that the prepared sample structure is more regular. And the hy­ thermal stability and can desorb the adsorbed sample at 105 ◦ C.
drothermal temperature of 120 ◦ C is more favorable for the preparation Meanwhile, the energy consumption of desorption is relatively small,
of mesoporous silica (Fig. 3c). The difference in XRD patterns caused by which makes it possible for the adsorbent to be recycled.
hydrothermal time and temperature indicates that temperature and time
affect the formation and growth rate of nanoparticles (Zhang et al., 3.2.4. Microscopic morphology analysis
2006). In addition, the wide-angle XRD patterns (Fig. 3d-f) reveal that SEM and TEM were used to examine the morphology of the meso­
all the synthesized samples have a wide peak between 20◦ and 25◦ , porous silica produced with various CTAB additions (Fig. 5). SEM im­
which confirms the presence of amorphous silica as skeleton particles, ages show that CTAB-0.00 (Fig. 5a) without template presents an
suggesting that the sample prepared is SiO2 adsorbent (Boldrini et al., aggregate of irregular particles, while mesoporous silica particles pre­
2019; Chandrasekar et al., 2008; Yan et al., 2016). Meanwhile, sharp pared with template present an aggregate of spherical particles with
peaks at 32◦ and 45◦ were observed in the XRD pattern, which can be smooth surface, the diameter of primary particles is about 100 nm, and
attributed to the characteristic peak of Al2O3 (Du et al., 2018), which the particles are evenly distributed, which indicates that the addition of
may be caused by the presence of aluminum in the sample. suitable mineralizers can promote the formation and growth of nano­
particles (Liu et al., 2008). TEM images show that there is no pore

4
S. Xu et al.
Fig. 3. The small-angle (a, b, c) and wide-angle (d, e, f) XRD patterns of mesoporous silica synthesized under different conditions.
structure in the silica particles without templates (Fig. 5a1). When 0.15g
CTAB is added, a disordered and irregular pore structure appear in the
particles of sample CTAB-0.15. With the further increase of templates,
hexagonal pores are orderly arranged in the particles of sample
CTAB-0.45, CTAB-0.50, and CTAB-0.75 (Fig. 5(d1-f1)). The average
particle size of mesoporous SiO2 aggregates was analyzed by
nano-particle size and Zeta potentiometers. The results show that when
the diameter of primary particles is about 100 nm, the average particle
size of mesoporous SiO2 aggregates is 500–800 nm. Meanwhile, the
average particle size increases when the surfactant CTAB is added to the
synthesis process, as the amount of CTAB increases. (Yan et al., 2016).
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Environmental Research 231 (2023) 116070
3.2.5. N2 adsorption isotherms
Fig. 6a presents the N2 adsorption isotherms at 77K of mesoporous
silica produced with various CTAB additions. Type II N2 adsorption
isotherms were exists in CTAB-0.00 and CTAB-0.15, however CTAB-0.15
exhibits an H3 type hysteresis loop at P⋅P-1
0 = 0.8–1.0 that is brought on
by capillary condensation of nitrogen in the pores between mesoporous
silicon particles (Yue et al., 2012). Meanwhile, The N2 adsorption iso­
therms of CTAB-0.30, CTAB-0.45, CTAB-0.60, and CTAB-0.75 transi­
tioned to a type IV model and demonstrated a rapid increase in capillary
condensation at a relative pressure of 0.25–0.40, which occurred when
the template CTAB was increased. Upon reaching 0.5 in the relative
pressure, a hysteresis loop appeared, which belongs to typical meso­
porous silica with narrow mesoporous distribution (Fu et al., 2015).
S. Xu et al. Environmental Research 231 (2023) 116070

Fig. 4. (a) Fourier transform infrared spectroscopy (FTIR) spectra and (b) thermalgravimetric analysis of mesoporous silica prepared with different CTAB additions.

Fig. 5. SEM (a–f) and TEM (a1-f1) images of mesoporous silica prepared with different CTAB additions (a, a1: CTAB-0.00; b, b1: CTAB-0.15; c, c1: CTAB-0.30; d, d1:
CTAB-0.45; e, e1: CTAB-0.60; f, f1: CTAB-0.75).

6
S. Xu et al. Environmental Research 231 (2023) 116070

Fig. 6. (a) N2 physisorption isotherms and (b) pore size distributions of different CTAB additions.

Fig. 6b shows the respective pore size distribution curves of the prepared are presented in Fig. 7a. CTAB-0.00 and CTAB-0.15 have lower CO2
mesoporous silica. Generally, in the absence of surfactant, the pore size adsorption capacities than 0.1 mmol/g. This is because when the tem­
distribution of nano-silica is 2–100 nm (Yan et al., 2014, 2016), just as plate agent of low concentration is added, the template agent of mixed
the pore size distribution of CTAB-0.00 and CTAB-0.15 in this study is species is lower than the critical micellar concentration (CMC), which is
scattered and not concentrated, which is caused by the low amount of not favorable to the creation of mesoporous structure of mesoporous
template. As anticipated, as the amount of template CTAB increases, silica (Awino and Zhao, 2013; Du et al., 2018). When the amount of
mesoporous silica tends to have a concentrated pore size distribution, CTAB increased to 0.45g, the CO2 adsorption capacity of the prepared
which is around 3.5 nm, indicating that the surfactant is involved in pore mesoporous silica improved. However, when the additions of CTAB
size regulation. continued to increase, the adsorption capacity of CO2 did not increase
Table 3 summarizes the physical characteristics of the synthesized significantly, even when the addition amount was 0.75g, the adsorption
mesoporous silica, including the specific surface area (SBET), total pore capacity was less than CTAB-0.45.
volume (Vpore), and average pore size (DDFT). The specific surface area The CO2 adsorption isotherms of mesoporous silica prepared at
and pore volume of CTAB-0.00 without template are 19.671 m2/g and various hydrothermal time and hydrothermal temperature are shown in
0.026 cm3/g, respectively. With an increase in CTAB content throughout Fig. 7b–c, respectively. When the hydrothermal time is less than 24h, the
the preparation process, the specific surface area of mesoporous silica adsorption capacity of the prepared samples is almost indistinguishable.
increased from 31.360 m2/g to 495.849 m2/g, and the pore volume It is worth noting that when the hydrothermal time is increased to more
increased from 0.076 cm3/g to 0.679 cm3/g. Both of these changes than 24h, the CO2 adsorption capacity is obviously improved. This
occurred simultaneously. When 0.75g was added, neither the specific might be as a result of the heterogeneous reaction mixture, which when
surface area nor the pore volume increased any further. According to the the hydrothermal duration is brief reduces the porosity of the meso­
DFT model, the average pore size of the prepared sample is about 3.5 porous silica. On the contrary, extending the hydrothermal period can
nm. Combined with the pore size distribution curve, the pore size dis­ increase the mesoporous silica’s entry diameters, enhancing its ability to
tribution is concentrated when the amount of template CTAB is 0.45g absorb CO2 (Kim et al., 2004). As shown in Fig. 7c, when the hydro­
and 0.60g, and the prepared mesoporous silica has excellent pore thermal temperature is 75 ◦ C and 90 ◦ C, the crystallinity of mesoporous
structure and is suitable to be used as adsorbent or catalyst carrier. silica may be poor due to the lower temperature, resulting in its weak
CO2 adsorption capacity. The high temperature can enhance the hy­
drolysis and cross-linking in the silica mixture when the temperature is
3.3. CO2 adsorption between 105 ◦ C and 120 ◦ C. As a result, mesoporous silica performs
better at CO2 adsorption as the temperature rises (Chen et al., 1997).
3.3.1. CO2 adsorption capacity of mesoporous silica However, when the temperature continues to rise, the electrostatic
The mesoporous silica obtained under different conditions was used interaction between CTAB and SiO2− 3 leads to a decrease in the number
for CO2 adsorption test. The samples were maintained at 105 ◦ C for 8 h of pores in mesoporous silica, which can explain the weakening of the
prior to the CO2 adsorption test to eliminate the water and contaminant adsorption capacity of mesoporous silica at 135 ◦ C (Sui et al., 2016).
gas adsorbed in the sample. Fig. 7 illustrates the corresponding CO2 Therefore, mesoporous silicon with excellent structural characteristics
adsorption isotherms of various samples. The CO2 adsorption isotherms and CO2 adsorption capacity can be successfully prepared under con­
of mesoporous silica prepared with different additions of template CTAB ditions of CTAB addition 0.45g, hydrothermal time 24h and hydro­
thermal temperature 120 ◦ C.
Table 3 Table 4 shows some of the materials used for CO2 adsorption.
Structural parameters of the samples synthesized at different CTAB additions. Compared with some adsorption materials reported in other literature,
Sample SBET (m2/g) Vpore (cm3/g) DDFT (nm) DDLS (nm) the CO2 adsorption capacity of mesoporous silica with MCM-41 struc­
CTAB-0.00 19.671 0.026 1.475 444.2 ture prepared in this paper is comparable to that of commercial MCM-41
CTAB-0.15 31.360 0.076 5.285 540.5 products. Meanwhile, compared with some modified materials based on
CTAB-0.30 162.149 0.272 3.775 576.7 MCM-41 matrix, although the mesoporous silica prepared in this paper
CTAB-0.45 467.096 0.555 3.537 682.5 has not been modified with amines, it still shows excellent CO2
CTAB-0.60 495.849 0.679 3.775 744.8
CTAB-0.75 424.974 0.494 3.179 794.5
adsorption performance. Due to the excellent pore size structure of the
mesoporous silica prepared in this paper, it is possible to use it as the
SBET: Specific surface area; Vpore: Total pore volume; DDFT: average pore size; substrate material to prepare solid amine material adsorbent to improve
DDLS: average size of silica particle aggregates.

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S. Xu et al. Environmental Research 231 (2023) 116070

Fig. 7. CO2 adsorption isotherms of different samples at 298K under the pressure range of 0.01~1 bar (a: CTAB additions; b: hydrothermal time; c: hydrothermal
temperature).

Langmuir equation parameter.

Table 4
Additionally, the Clausius-Clapeyron equation was employed to
Compared with several MCM-41 based materials and some other adsorbents.
comprehend how CO2 molecules interact with adsorbent surfaces, and
Material Adsorption Adsorption Ref. the calculation formula is as follows equation (6):
conditions capability (mmol/
[ ] ( )
g) (T2 × T1 ) P2
Qst = R ln (6)
EDA-SBA-15 sorbent 298.15K/1.0 0.45 Zheng et al. (2005) (T2 − T1 ) P1
bar
Large pore size 303.15K/1.0 0.60 Loganathan et al. Where Qst: isosteric heat of adsorption; T1, T2: the temperature of both
MCM-41 bar (2013) isotherms; P1, P2: the pressure where the isotherm of both temperatures
AF-MSM 333.15K/ 0.54 Araki et al. (2009)
20kpa
exhibits the same amount of adsorbate that has been adsorbed; R: uni­
M-SiO2 298.15K/8% 0.22 Du et al. (2018) versal gas constant.
CO2 Fig. 8 shows the adsorption isotherms of the synthesized mesoporous
Si-MCM-41-PEI-50 298.15K/1atm 0.75 Xu et al. (2003) silica at different temperatures, together with the matching curves fit by
Pristine Si-MCM-41 298.15K/1.0 0.63 Ahmed et al.
non-linear Freundlich and Langmuir models. The fact that the CO2
bar (2016)
MCM-41 298.15K/1.0 0.68 Mukherjee and adsorption capability of mesoporous silica steadily diminishes as
bar Samanta (2019) adsorption temperature rises indicates that the adsorption process of
MOF-177 313.15K/1.0 0.65 Mason et al. CO2 on the surface of mesoporous silica may be exothermic. Fig. 8b and
bar (2011) c show the curves fitted by Freundlich and Langmuir models respec­
unmodified X zeolite 398.15K/1.0 0.36 Chatti et al. (2009)
bar
tively, and Table 5 lists the specific values calculated. Freundlich model
Biomass ash-based 298.15K/1.0 0.75 This work fitting findings had an R2 greater than 0.999, outperforming Langmuir
mesoporous silica bar model fitting results. In addition, the n values obtained by fitting are all
greater than 1, indicating that there is a strong affinity between adsor­
bate and adsorbent (Tao et al., 2020; Yang et al., 2022). The physical
the adsorption performance of CO2.
adsorption is the main process of CO2 adsorption on the surface of
mesoporous silica, and the better fitting effect of Freundlich model in­
3.3.2. CO2 adsorption isotherm and thermodynamics
dicates that the adsorption sites on the prepared mesoporous silica are
Adsorption isotherm is an important curve in the study of gas
not uniformly distributed (Hu et al., 2022).
adsorption equilibrium, which refers to the state of gas molecules in
Determining the adsorption heat between adsorbent and gas is crit­
adsorption equilibrium at the solid-gas interface at a certain tempera­
ical for adsorbent application in gas adsorption because it helps explain
ture. The adsorption heat can be used to detect the scale of mutual re­
the interaction between CO2 and mesoporous silica. The CO2 adsorption
action between adsorbent and adsorbate molecules, that is, the
isotherms of selected samples were investigated at 298K, 318K, and
magnitude of strong interaction force between them (Kou and Sun,
338K using the Clausius-Clapeyron equation to calculate the adsorption
2016). Therefore, Therefore, we tested the adsorption isotherms of
equilibrium heat. The variation of equivalent adsorption heat of meso­
mesoporous silica at 298K, 318K and 338K using an adsorption instru­
porous silica with the adsorption amount of CO2 is shown in Fig. 8d.
ment. Meanwhile, in order to determine the adsorption mechanism of
Generally, the adsorption heat of physical adsorption does not exceed
CO2 on the mesoporous silica, the nonlinear Freundlich and Langmuir
40 kJ/mol. The Qst values of the prepared mesoporous silica at three
isotherm models were used to fit the adsorption isotherms at different
temperatures are all less than 20 kJ/mol, indicating that the physical
temperatures (Ahmed et al., 2021). The calculation formula is as follows
adsorption process is the main process of the interaction between CO2
equations (4) and (5):
and mesoporous silica (Yang et al., 2018). The equivalent adsorption
Non − linear Freundlich : q = KF Pn
1
(4) heat, however, falls as adsorption temperature rises, indicating that
adsorption of CO2 onto mesoporous silica is not facilitated by an in­
qm KL P crease in adsorption temperature. Adsorption heat steadily decreases as
Non − linear Langmuir : q = (5) temperature rises, indicating that the capacity for CO2 adsorption re­
1 + KL P
duces with time as CO2 is continuously adsorbing and building up on
Where q: CO2 equilibrium adsorption capacity (mmol/g); KF: Freundlich mesoporous silica. The heterogeneity of the sample and the effective
equation parameter (mmol/(g⋅atm1/n)); P: test pressure (bar); 1/n: mutual exclusion between the CO2 adsorbed on the sample surface and
Freundlich constant, qm: maximum monolayer adsorption (mmol/g); KL: the CO2 near the gas-solid contact may be to blame for this behavior of

8
S. Xu et al. Environmental Research 231 (2023) 116070

Fig. 8. CO2 adsorption isotherms (a) of mesoporous silica at different temperatures, and corresponding non-linear Freundlich (b) and Langmuir (c) model fitting
curves, (d) isosteric heat of adsorption of CO2 on mesoporous silica.

after five cycles, the adsorption capacity of mesoporous silica is essen­

Table 5
tially unaltered, indicating that the mesoporous silica adsorbent pre­
Fitting parameters of non-linear Freundlich and Langmuir adsorption isotherm.
pared in this paper has excellent recycling capacity.
T/K Freundlich Langmuir In addition, the selective adsorption capacity, as an important indi­
n KF R2 qm KL R2 cator of adsorbents, is of great significance for their practical applica­
298 1.314 0.524 0.99987 1.264 0.675 0.99784
tions (Fang et al., 2023). Since the adsorption experimental data of
318 1.211 0.440 0.99994 1.454 0.422 0.99895 mixed gases cannot be easily obtained, the ideal adsorption solution
338 1.173 0.415 0.99998 1.649 0.330 0.99889 theory (IAST) was used to predict the adsorption selectivity of mixed
KF: parameter of Freundlich equation; n: Freundlich constant; qm: maximum gases from the pure component isotherm (Wan et al., 2020). As shown in
monolayer adsorption; KL: Langmuir constant; R2: correlation coefficient. Fig. 10a, the adsorption capacity of the prepared mesoporous silica for
CO2 and N2 is 0.64 mmol/g and 0.038 mmol/g at 298K and 1 bar,
respectively. IAST theory was used to calculate the adsorption selec­
mesoporous silica (Ahmed et al., 2021; Zeng et al., 2017).
tivity of CO2 and N2 mixture on mesoporous silica, which is the typical
flue gas composition of power plant (at 25◦ C with CO2/N2 ratio is 15/85
3.3.3. Cycle and selective adsorption capacity
and 10/90), and the results were shown in Fig. 10b. The results pre­
Since the recycling of adsorbent is an effective way to reduce costs in
dicted by IAST show that the maximum adsorption selectivity of the
the process of CO2 capture, it is also important to evaluate their stability
prepared mesoporous silicon at the CO2/N2 ratio of 15:85 and 10:90 was
and adsorption capacity over multiple cycles. Meanwhile, in order to
396.6 and 162.1, respectively. The prepared mesoporous silica exhibits
reduce energy consumption, lower activation temperature can effec­
excellent selective adsorption performance in typical flue gas composi­
tively reduce energy consumption during desorption and regeneration of
tion, indicating its potential application in reducing CO2 emissions in
adsorbent. Combined with the thermogravimetric analysis (Fig. 4b) of
practical power plants.
the sample, the adsorbed water and impurity gas can be removed well at
105◦ C. Therefore, before each adsorption cycle, mesoporous silica was
4. Conclusion
kept in vacuum at 105◦ C for 8h. Mesoporous silica was used for five
consecutive CO2 adsorption cycles at 25◦ C and 1 bar. As illustrated in
In this work, a mesoporous silica material with ordered hexagonal
Fig. 9, the capability for CO2 adsorption of the produced mesoporous
mesopores structure can be successfully prepared from the ash produced
silica after five cycles is approximately 0.6 mmol/g, retaining more than
by biomass power plants, and is effectively applied to CO2 adsorption.
90% of the adsorption capacity, which may be due to inadequate
NaOH and biomass ash were mixed and roasted by alkali fusion method
desorption of CO2 deposited on the adsorbent. This result shows that

9
S. Xu et al. Environmental Research 231 (2023) 116070

Fig. 9. Cyclic CO2 adsorption isotherms of mesoporous silica at 298K and 1 bar.

Fig. 10. (a) CO2 and N2 adsorption isotherms for mesoporous silica (MS) at 298K and 1 bar and (b) IAST-predicted selectivity for CO2/N2 binary mixtures on
mesoporous silica at 25 ◦ C.

to extract silica, and the extraction rate of silica reached 51.95%. Mes­
oporous silica was successfully prepared by hydrothermal method using
silicon extract as raw material. The characterization of the prepared
samples shows that the specific surface area is 495.849 m2/g, and the
pore diameter is 3.775 nm. Meanwhile, it is determined that the syn­
thesized material is mesoporous silica with ordered structure and two-
dimensional hexagonal structure similar to MCM-41. The maximum
CO2 adsorption capacity of the synthesized mesoporous silica could
reach 0.749 mmol/g. The non-linear Freundlich isotherm model is
better than Langmuir model in fitting the adsorption isotherm of CO2 on
mesoporous silica, indicating that the distribution of the CO2 adsorption
sites on the mesoporous silica is not uniform. Combined with the
calculation of the equivalent adsorption heat Qst, the Qst is less than 20
kJ/mol, suggesting that the adsorption process is physical adsorption.
After five consecutive cycles of adsorption, the CO2 adsorption capacity
of mesoporous silica remains above 90%, and the CO2/N2 (15/85)
adsorption selectivity reached 396.6, indicating excellent cyclic and
selective adsorption capacity. This work explores the feasibility of
synthesizing mesoporous silica from biomass ash as a silicon source and
its application potential in CO2 adsorption. It also provides an idea for
the high-value utilization of biomass ash and the synthesis of meso­
porous silica.
Declaration of competing interest
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.
Data availability
Data will be made available on request.
Acknowledgments
This work is supported by the National Key Research and

10
S. Xu et al.
Development Project of China (2020YFC1908601), the National Natural
Science Foundation of China (42272196), the Key Research and
Development Program of Anhui Province (202004a06020030 and
202004b11020016), the Anhui Provincial Natural Science Foundation
(1908085MD113) and Project of Linhuan Coking Industry Company. We
acknowledge editors and reviewers for polishing the language of the
paper and for in-depth discussion.
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