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Kinetic analysis for cyclic CO2 capture using

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Cite this: Dalton Trans., 2018, 47,

lithium orthosilicate sorbents derived from
9038 different silicon precursors†
Ming Zhao, a,b Hanlu Fan,a Feng Yan, a Yinqiang Song,a Xu He,a
Muhammad Zaki Memon, a Suresh K. Bhatia c and Guozhao Ji *a

Received 23rd April 2018,
Accepted 10th June 2018
DOI: 10.1039/c8dt01617h
rsc.li/dalton
A series of Li4SiO4 was synthesized using LiNO3 and six different silicon precursors. The precipitated-
silica-derived Li4SiO4 presented the highest CO2 capacity in a 10 h sorption test, and ZSM-5-derived
Li4SiO4 demonstrated the most rapid CO2 sorption. The CO2 sorption kinetics predominantly followed
the nucleation mode and could be accurately described by the Avrami-Erofeev model. The Avrami-
Erofeev model provided an in-depth analysis of correlation between sorption performance and material
properties. Both the nucleation speed and nucleation dimensionality affected the overall sorption kinetics.
The kinetics and pore-size distribution suggest that the sorption kinetics was dependent on the quantity
of ∼4 nm-pores which favors nucleation dimensionality. For the cyclic tests, the precipitated-silica-
derived sample presented the poorest performance with the capacity decreasing from 31.33 wt% at the 1st
cycle to only 11.52 wt% at the 30th cycle. However, the sample made from fumed silica displayed an
opposite trend with the capacity increasing from 19.90 wt% at the 1st cycle to 34.23 wt% at the 30th cycle.
The radically distinct behaviour of samples during cycles was on account of the alternation of sorption
kinetics. The decrease in ∼4 nm-pores after cycles was responsible for the decrease of nucleation dimen-
sionality for the precipitated-silica-derived sample. The rearrangement during cycles could enrich the
pores of ∼4 nm for the fumed silica-derived sample, which improved the nucleation growth, thus enhan-
cing the kinetics with cycles.

1. Introduction elevate the H2 yield.2–4 This is a typical pre-combustion CO2

Flue gas from fossil fuel combustion has been known as one
of the significant contributors of anthropogenic CO2 leading
to climate change.1 Traditional fossil fuels such as oil, coal
and natural gas are still the major sources of energy for indus-
trial processes; hence, reducing fossil fuel usage and their
harmful impacts on the environment is critical to mitigate
climate change. This necessitates the development of an
alternative clean energy source with the advantages of low pol-
lutant emissions and more energy per mass. Hydrogen (H2)
production from sorption enhanced steam reforming (SESR)
seems a feasible solution to this issue, but SESR requires
in situ CO2 capture at high temperatures (400–700 °C) to
a
School of Environment, Tsinghua University, Beijing 100084, China.
E-mail: guozhao.ji@uqconnect.edu.au
b
Key Laboratory for Solid Waste Management and Environmental Safety,
Ministry of Education, Beijing 100084, China
c
School of Chemical Engineering, the University of Queensland, Brisbane, QLD4072,
Australia
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c8dt01617h
capture process. Traditional CO2 capture techniques such as
amine-scrubbing and cryogenic distillation are unable to be
applied in situ under the conditions for SESR.5–7 Developing
high temperature solid sorbents is thus of increasing impor-
tance for H2 production. In addition to such pre-combustion
capture applications, solid sorbents could also serve as accep-
tors of CO2 after combustion of fossil fuels.8,9 The post-com-
bustion goal can be fulfilled by using two parallel fluidized
beds serving as a carbonator and a regenerator, respectively, or
by setting up fixed-bed reactors with swinging carbonation/cal-
cination reactions.10,11 During regenerations, the carbonated
solid sorbents would release concentrated CO2 which is a valu-
able source for photosynthesis and production of useful
chemicals such as urea, methane and methanol.12
Furthermore, CO2 sorbents could also be employed to enhance
the efficiency of natural gas, coal bed gas, shale gas and land-
fill gas by removing the CO2 content and concentrating the
combustible components.1 In closed environments such as
spacecrafts, space stations, and submarines which are isolated
and lack gas exchange with the surroundings, restraining the
CO2 concentration by CO2 sorbents is an effective way to
ensure the life safety of human beings.

9038 | Dalton Trans., 2018, 47, 9038–9050 This journal is © The Royal Society of Chemistry 2018

Dalton Transactions
One such sorbent which has been widely used is a CaO-
based material due to its high theoretical sorption capacity
(78 wt% or 17.7 mmol g−1) and low cost. However, it has been
well known to suffer from rapid decays over multiple cycles of
sorption and desorption due to sintering-related
deactivation.13–16 In order to minimize the sintering effect and
improve the cycling stability, sacrifice of the sorption capacity
was accepted by incorporating high-melting-point inert
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materials such as Ca9Al6O18,17 Ca2Al2SiO7,18 CaZrO3,19
Ca2SiO4,19 MgO 20 and Al2O3 21,22 into CaO as a stabilizer (or
‘spacer’). To avoid the complexity and potential cost increment
by making such ‘hybrid’ type sorbents, it is motivated to
develop more efficient alternative sorbents that can be used
over repeated cycles. Recently, alkali metal oxide CO2 sorbents
such as Li4SiO4, Li2ZrO3 and Na2ZrO3 have attracted increasing
attention for their good CO2 chemisorption capacities and
excellent cycling stability.23,24 They could react with CO2 to
form carbonate as demonstrated in eqn (1)–(3)23,25,26
Li4 SiO4ðsÞ þ CO2ðgÞ Ð Li2 CO3ðsÞ þ Li2 SiO3ðsÞ ;
ð1Þ
ΔH298 ¼ 142 kJ mol1
Li2 ZrO3ðsÞ þ CO2ðgÞ Ð Li2 CO3ðsÞ þ ZrO2ðsÞ ;
ð2Þ
ΔH298 ¼ 160 kJ mol1
Na2 ZrO3ðsÞ þ CO2ðgÞ Ð Na2 CO3ðsÞ þ ZrO2ðsÞ ;
ð3Þ
ΔH298 ¼ 149 kJ mol1
The theoretical capacities of Li-based sorbents (36.7 wt% or
8.3 mmol g−1 for Li4SiO4 and 28.7 wt% or 6.5 mmol g−1 for
Li2ZrO3) are higher than that of the corresponding Na-based
one (23.8 wt% or 5.4 mmol g−1 for Na2ZrO3). This was likely
the reason why Li species were reasonably more attractive for
researchers. From an industrial perspective, Li4SiO4 is advan-
tageous over Li2ZrO3 because silicon (Si) is the second most
abundant element on the earth’s surface and silicon oxide
(silica) as a precursor is more widely available compared with
zirconium oxide (zirconia). In addition to the materials above,
a number of newly developed Li-based ceramics were also
investigated for CO2 capture, such as Li2CuO2,27–29 Li2TiO3,30
Li5AlO4,31,32 Li5FeO4,33–36 Li2O–Bi2O3 37 and LiNiO2.38 Current
research on these materials focuses on the improvement of
sorption capacity. Even though some of them showed higher
CO2 capacity than Li4SiO4, the material cost still remains as an
issue. Moreover, further investigations on the cycling stability
of these newly developed materials are still needed.
In view of the potential of Li4SiO4 as a CO2 sorbent, a
number of studies have been conducted to optimize the per-
formance of cyclic sorption. Li4SiO4 is commonly prepared by
solid state reactions between Li and Si precursors.39,40 It has
been found that a smaller particle size of the precursor results
in a more complete reaction during synthesis and thus higher
purity of Li4SiO4, which naturally leads to greater CO2 capture
capacity.41 Romero-Ibarra et al.42 deployed post-treatment of
Li4SiO4 by mechanical ball-milling and succeeded in reducing
the crystal size and increasing the surface area of the material.
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The consequent CO2 capacity was increased from 2.0 mmol g−1
(8.8 wt%) to 4.3 mmol g−1 (18.9 wt%). Venegas et al.43 employed
a precipitation method to achieve a small particle size of
Li4SiO4, being around 3 μm as opposed to 36 μm via the solid-
state reaction, and the smaller particles lowered the reaction
activation energy by half. Subha et al.44 found that Li4SiO4 pre-
pared via sol–gel routes showed improvements over the solid-
state samples in terms of both CO2 capacity (30 wt% or
6.8 mmol g−1 for sol–gel and 17 wt% or 3.8 mmol g−1 for the
solid state) and sorption kinetics (22.5 mg g−1 min−1 for sol–gel
and 13.2 mg g−1 min−1 for the solid state). It was believed that
doping hetero elements may create lattice vacancies which
accelerate O2− hopping, thus favouring CO2 sorption. Gauer
et al.45 incorporated Al and Fe into Li4SiO4 and promoted the
sorption rate from 0.01 to 0.12 and 0.15 wt% min−1. Seggiani
et al.46 developed K2CO3-doped Li4SiO4 and achieved a CO2
capacity of 27 wt% (or 6.1 mmol g−1). Chen and co-workers47
synthesized Ca-doped Li4SiO4 which reached a CO2 capacity of
35.1 wt% (or 8.0 mmol g−1). The Si precursor also plays a role in
affecting the performance of Li4SiO4 sorbents. Shan et al.48
compared the performance of Li4SiO4 derived from diatomite
and pure SiO2. The sorption capacity of diatomite-derived
Li4SiO4 reached 28.62 wt% (or 6.5 mmol g−1) which was
higher than that for pure SiO2-derived Li4SiO4 (22.08 wt% or
5.0 mmol g−1). Kim et al.40 prepared Li4SiO4 by fumed silica
with three different Li precursors: LiOH, LiNO3 and Li2CO3. The
sorbent made from LiOH was identified as the best in their
study, showing a CO2 capacity of 29.8 wt% (or 6.8 mmol g−1)
and a sorption rate of 56.1 mg g−1 min−1. Pan et al.49 developed
Li4SiO4 from very porous silicon precursor SBA-15 and reported
the highest CO2 capacity (36.3 wt% or 8.3 mmol g−1) in the
open literature so far. Another important concern of Li4SiO4 is
the decay of capacity during the cyclic sorption–desorption.
Almost all the reported cyclic capacities of Li4SiO4 declined
during cycles with different levels, and the mechanistic reason
for this decline is still yet to be disclosed.
However, Li-based sorbents have been criticized for their
slow CO2 sorption kinetics which limits their development and
application.50–53 Since kinetics is the limiting factor of the
application of Li-based sorbents, theoretical investigation of
sorption kinetics is of great importance for interpreting the
reaction mechanism and improving material design. The
double exponential model, being a popular data fitting tool,
has been frequently used to fit the kinetic sorption profile for
alkali metal ceramics.39,43,44,48,54 The shrinking core model, as
a common model for solid–fluid interaction, has also been
used in studying the CO2 sorption kinetics using alkali metal
based sorbents.55,56 Zhang et al.57 applied the shrinking core
model and the double exponential model as well as the
Avrami-Erofeev nucleation model to interpret the CO2 sorption
kinetics in Li4SiO4 and found that only the Avrami-Erofeev
model is able to explain the reaction mechanism and give
reasonable fitting.
As discussed above, Li4SiO4 sorbents developed from
diverse precursors resulted in different sorption performances.
This work aims to model and interpret the sorption kinetics of
Dalton Trans., 2018, 47, 9038–9050 | 9039
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Li4SiO4 samples made from six different Si precursors and
develop the correlation of sorption kinetics with the textual
property of the material. Since cyclic sorption–desorption gen-
erally alters the performance of CO2 capture, to the best of our
knowledge, there has not been any theoretical study to explain
the mechanism of this performance change during cycles.
This work applied the Avrami-Erofeev model, which has been
proved as a reasonable model of CO2 sorption in Li4SiO4, to
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of 30 °C min−1 to remove the pre-sorbed substances such
as H2O and CO2. Then the chamber temperature was con-
trolled to 650 °C under a stream of pure CO2 at 60 ml min−1
for 10 h.
Cyclic sorption/desorption tests were also carried out to
evaluate the long term stability of CO2 capture performance.
After pre-calcination in a 60 ml min−1 flow of pure N2 at
650 °C, the sample was kept at 650 °C under a stream at 60 ml

gain insight into the kinetic change caused by cycles. min−1 periodically switched between pure CO2 and pure N2 30
times. The duration of purging the CO2 stream in a cycle was
60 min and for the N2 purging it only lasted for 10 min.
2. Experimental and methodology The CO2 capacity of each cycle (Qi) is defined in eqn (4)
2.1 Material synthesis mmax;i  mmin;i
Qi ¼  100% ð4Þ
m0
The Li4SiO4-based sorbents were prepared by using the solid-
state reaction of LiNO3 with pure SiO2 with a molar ratio of where mmax,i and mmin,i are the maximum mass and initial
nLi : nSi = 4 : 1. Six types of pure SiO2, namely SBA-15 (JCNANO, mass at the ith cycle and m0 is the minimum mass of the
Nanjing, China), MCM-41 (JCNANO, Nanjing, China), ZSM-5 sample during the entire test. The total capacity (Qtotal ) over
(JCNANO, Nanjing, China), fumed silica (S5130; Sigma- the entire 30 cycles was also calculated in eqn (5)
Aldrich, USA), precipitated silica (Sipernat-306; Evonik, Essen,
X
30
Germany) and waste-derived silica, were selected as the Si pre- Qtotal ¼ Qi ð5Þ
cursors. The waste-derived SiO2 was synthesized through the i¼1
hydrolysis of SiCl4 (99 wt%; LDK Solar Ltd, Xinyu, China) at
Since the only difference among these Li4SiO4 samples is
150 °C and was collected and dried at 105 °C for 2 h. Initially,
the Si precursors, the Si precursor’s names are used to rep-
0.0666 mol LiNO3 (Fengshun Fine Chemicals Ltd, Shanghai,
resent the samples investigated in this study. For instance,
China) was dissolved in 40 ml of absolute ethanol (99.8%,
LS-SBA-15 means the Li4SiO4 made from the SBA-15 precursor.
Beijing Chemical works) and then sonicated for 20 min until it
completely dissolved. Then, 0.0166 mol pure SiO2 was added
to the solution and the mixture was stirred for 24 h at 300 rpm
at 60 °C until it evaporated completely. After drying in a 3. Results and discussion
vacuum oven at 60 °C for 8–12 h, the mixed powders were cal-
3.1 Characterization results
cined at 750 °C for 2 h with a ramping rate of 10 °C min−1.
After the calcination process, the products were ground to Fig. 1 shows the XRD patterns of the samples developed from
powder again in an agate mortar for later use. the six different Si precursors. The presence of Li4SiO4 was
confirmed in all the samples. No impurities were observed
2.2 Material characterization
Powder X-ray diffraction (XRD) was carried out on a Dmax/2500
X-ray diffractometer (Rigaku, Japan) with a 2θ range of 10–90°
(Cu Kα radiation, λ = 0.1542 nm). Morphological properties of
samples were detected using scanning electron microscopy
(SEM, Zeiss MERLIN VP Compact). All the sorbents for SEM
were sputter-coated with a layer of platinum (∼5 nm). N2 physi-
sorption was conducted on a Quantachrome autosorb iQ-C
instrument. Prior to analysis, the sorbent was degassed at
300 °C until the pressure increment rate in the sample
chamber was less than 20 μmHg min−1. The Brunauer–
Emmett–Teller (BET) surface area was estimated based on the
N2 adsorption isotherms with a P/P0 range of 0.05–0.3. The
total pore volume and pore size distribution were calculated
according to the Barrett–Joyner–Halenda (BJH) method.

2.3 CO2 sorption tests

CO2 sorption capacity of the sorbents was tested using a
thermogravimetric analyser (METTLER, TOLEDO, TGA/DSC 2).
In each test, ∼10 mg of the sample was first subject to purifi- Fig. 1 XRD patterns of Li4SiO4 samples derived from different Si
cation in a pure N2 flow of 60 ml min−1 with a ramping rate precursors.

9040 | Dalton Trans., 2018, 47, 9038–9050 This journal is © The Royal Society of Chemistry 2018
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from the samples of LS-SBA-15, LS-MCM-41, LS-Precipitated

and LS-Waste at least at the XRD detection level. As for the
samples made from ZSM-5 and fumed silica, some Li2SiO3
phase was shown as minor peaks which indicated the exist-
ence of a slight amount of Li2SiO3. The grain sizes of crystals
could not be provided by the Scherrer equation because the
sizes of all the samples were beyond 100 nm. As such, only the
full width at half maximum (FWHM) was reported here to indi-
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cate a qualitative comparison of grain sizes. The FWHM was

0.152 for LS-SBA15, 0.155 for LS-MCM41, 0.155 for LS-ZSM5,
0.160 for LS-Fumed, 0.147 for LS-Precipitated and 0.146 for
LS-Waste. These numbers of FWHM could possibly imply the
order of grain size as: dLS-Waste > dLS-Precipitated > dLS-SBA15 >
dLS-MCM41 = dLS-ZSM5 > dLS-Fumed.
The N2 physisorption isotherms of the six samples are
plotted in Fig. 2a. All of them exhibited type II isotherms.58
The information of the BET surface area, external area, average
pore size and pore volume is summarized in Table 1. The
highest surface area and pore volume were observed for
LS-ZSM-5, closely followed by LS-precipitated. Generally, all the
samples possessed a rather low surface area and small pore
volume. The calculated BET surface areas were equal to the
external areas for all the sorbents except LS-SBA-15, which
meant that most of these materials were barely porous. Every
material also presented hysteresis in the adsorption–desorp-
tion isotherms. The shape of the hysteresis (Type B, based on
D. Duong) suggested that the pores had a slit shape.59
Therefore, the scanty pores were most likely formed by the
gaps between particles or the cracks in the particles. The pore
size distributions (PSD) of the six samples in Fig. 2b all exhibi-
ted a narrow unimodal distribution with peaks at ∼4 nm.
Close to this pore size, LS-ZSM-5 contained the most pores, fol-
lowed by LS-precipitated, LS-MCM-41, LS-Waste, LS-Fumed
and LS-SBA-15.
The SEM images in Fig. 3 show the morphology of the six
samples. LS-SBA-15 presented some macro-pores (visible
holes) inside the solid. This was consistent with the measured
surface areas in Table 1. The BET surface area (1.09 m2 g−1) of
LS-SBA-15 was much more than the external area (0.45 m2 g−1)
suggesting that part of the surface area (0.64 m2 g−1) is attribu-
ted to internal macro-pores. For a dense material, the
Fig. 2 (a) N2 adsorption–desorption isotherms of Li4SiO4 samples
BET surface area should be equal to the external area because derived from different Si precursors; (b) pore size distributions of Li4SiO4
there is no internal pore to contribute the surface area. powders derived from different Si precursors.
Remaining materials were composed of dense agglomerate
particles with various sizes. The agglomeration was very
evident for the LS-MCM-41 material, and the size of the par-
ticle clusters was ∼60 μm. LS-Fumed and LS-Waste also of the Li4SiO4 particles to form a Li2CO3 and Li2SiO3 nucleus.
agglomerated but the cluster size was relatively smaller, This surface reaction is very rapid and almost requires no
ranging from 30 to 50 μm. Only LS-ZSM-5 and LS-Precipitated time. The further nucleation had to evolve from the existing
were shown as separated particles with an average size of nucleus on the surface. Hence, the CO2 capture rate in the
about 10 μm. second step partially relies on how much nuclei formed in the
first step. The second step lasts until the formation of an outer
3.2 Sorption kinetics shell consisting of Li2CO3 and Li2SiO3 grains. During the third
The mechanistic assumption of the CO2 sorption procedure in stage, diffusion resistance is significantly increased and thus
the Li4SiO4 sorbent has been proposed as three steps (Fig. 4). diffusion becomes the rate limiting factor.57 In the third stage,
The first step of CO2 capture started from the external surface several studies proposed that two separative product layers

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Table 1 Surface area, pore size and pore volume of the as-prepared also present on the external surface. Therefore as shown in
samples Fig. 4, Li2CO3 and Li2SiO3 were more likely to be mixed
together than to be separated.
Average Pore
BET surface External pore size volume The CO2 sorption kinetics of the freshly calcined samples
Samples area (m2 g−1) area (m2 g−1) (nm) (cm3 g−1) in 10 h at 650 °C was plotted as CO2 uptake versus time
(Fig. 5a) and the CO2 capture rate (Fig. 5b) which is defined as
LS-SBA-15 1.09 0.45 3.94 0.009
LS-MCM-41 0.99 0.99 4.18 0.008 the first order derivative of CO2 uptake with respect to time.
LS-ZSM-5 1.46 1.46 3.94 0.012 The sample derived from precipitated silica presented the
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LS-fumed 1.05 1.05 3.94 0.007

highest CO2 capacity over 10 h, namely, 0.35 g-CO2 per
LS-precipitated 1.43 1.43 3.95 0.009
LS-waste 1.06 1.06 3.94 0.006 g-sorbent. The capacities of LS-ZSM-5 and LS-Fumed almost
converged to the same value being ∼0.34 g-CO2 per g-sorbent,
which is slightly less than the capacity of LS-precipitated. This
was likely owing to the minor quantity of Li2SiO3 in LS-ZSM-5
and LS-Fumed (Fig. 1). The capacity order was then followed
by LS-Waste, LS-MCM-41 and LS-SBA-15. The uptakes of these
samples were still growing after 10 hours. The trend is
especially evident for LS-SBA-15. This indicated that the poor
capacity of the SBA-15-derived sample was mainly due to
the slow kinetics. Fig. 5b further confirmed this point as
the CO2 capture rate of LS-SBA-15 was the lowest through the
10 h test.
LS-ZSM-5 performed the most rapid CO2 sorption in the
initial stage with a maximum sorption rate of 21.14 wt%
min−1, followed by LS-precipitated, LS-MCM-41, LS-Waster,
LS-Fumed and LS-SBA-15. This order did not demonstrate any
correlation with the BET surface area, external area,
pore volume (Table 1) or FWHM, but it was in agreement
with the sequence of the pore surfaces around 4 nm (Fig. 2).
This strongly suggested that the sorption kinetics was
predominantly determined by the number of pores of ∼4 nm.
Fig. 5b shows that the sorption rates of all the samples
underwent a peak at around the 20th cycle after which the
sorption rate suddenly declined. The acceleration of CO2 sorp-
Fig. 3 SEM images of synthesized samples.
tion in the initial stage was a typical behaviour of nucleation
growth processes.61 The CO2 sorption process could be
regarded as a transformation from the Li4SiO4 phase to the
phase of Li2CO3 and Li2SiO3.
To interpret the kinetic behaviour further and deeply, the
Avrami-Erofeev model which has been used to express solid–
gas reactions was employed in this study. The nucleation
could be homogeneous or heterogeneous. Homogeneous
nucleation starts from a nucleus which is randomly and homo-
geneously generated over the untransformed portion of the
material.

dN ¼ V Ṅdτ ð6Þ

Fig. 4 CO2 uptake profile (a) and CO2 capture rates (b) of as-prepared
Li4SiO4 samples during a single cycle test (in pure CO2 at 650 °C for
10 h).
were formed with Li2SiO3 as the internal layer and Li2CO3 as
the external layer.40,41,47,60 However, the surface of the fully
chemisorbed sorbent presented the Si element in the EDX
mapping in this study (Fig. S1†) indicating that Li2SiO3 was
where dN is the number of nuclei in volume V generated
during time dτ and Ṅ is the nuclei generation rate.
The second assumption is that growth rate of the nuclei
size is independent of the transformation. So the radius of
nuclei is only a function of time.
r ¼ ṙðt  τÞ ð7Þ
where ṙ is the radius growth rate, τ is the time when nuclei are
generated and t is the time of growth (so t > τ).

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Fig. 5 Illustration of the CO2 sorption process in Li4SiO4.
The ideally converted volume of the solid is then expressed
as:
4π
ideal
dVconvert ¼ ½ṙðt  τÞ3 V Ṅdτ ð8Þ
3
However, with the evolution of transformation, there is a
possibility that some of the ideal converted volume lies on the
previously converted material, and this part should not be
counted repeatedly. The real nuclei increment dVconvert is only
based on the untransformed portion of the material as indi-
cated by eqn (9).
dVconvert dV ideal
¼ convert ð9Þ
V  Vconvert V 2
Upon integration and by defining α = Vconvert/V, eqn (9)
yields:
ideal
Vconvert π lnð1  αÞ ¼ kt 3
lnð1  αÞ ¼  ¼  ṙ 3 Ṅt4 ð10Þ
V 3
Therefore, eqn (10) can be simplified as:
lnð1  αÞ ¼ kt 4 ð11Þ
where πṙ3Ṅ/3 is lumped as k. Eqn (11) described the relation of
conversion and time for homogeneous nucleation. But some-
times nucleation is not absolute homogeneous. For hetero-
geneous nucleation, the nucleation growth starts from a
number of germ nuclei in the material. At the commencement
of the nucleation, there are a number of N0 germ nuclei. With
the progression of nucleation, the number of germ nuclei
available for nucleation declines due to two possible phenom-
ena: the first is that nucleation already occurred from some
germ nuclei and this part of nuclei is no longer available; the
second effect comes from the heterogeneity of the reaction as
some germ nuclei might be incorporated or ingested by the
actively growing growth nuclei. Hence, the rate of dis-
appearance of germ nuclei is given by
dN ¼ dN′ þ dN″ ð12Þ
The reduction of germ nuclei due to the transformation
from germ nuclei to growing nuclei is proportional
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to the number of available germ nuclei remaining in the
material
dN′ ¼ k′Ndτ ð13Þ
The second term dN′′ which refers to the inoperative germ
nuclei ingested by the growing product is given by62
N
dN′′ ¼  dα ð14Þ
1α
where α is the conversion. Eqn (12)–(14) lead to eqn (15) by
integrating from τ = 0 to τ = t,
 
1 2 1 3
 lnð1  αÞ ¼ 6k′′N0 expðk′τÞ  1 þ k′t  t þ t ð15Þ
6
By assuming k = k″N0 and omitting lower order terms pro-
vided that t is large, the final expression of eqn (15) is
ð16Þ
Eqn (11) for homogeneous nucleation and eqn (16) for
heterogeneous nucleation presented a similar format for
3-dimensional nucleation but heterogeneous nucleation
showed a lower order for time terms.
The above deductions were based on the assumption that
nuclei undergo three dimensional growth, which leads to the
power exponent of t as 4 and 3 for homogeneous and hetero-
geneous nucleation, respectively. For the situation where the
nuclei evolve in other numbers of dimensionalities (n), a
general format of the nuclei growth model for homogeneous
and heterogeneous nucleation should be:
lnð1  αÞ ¼ kt nþ1 ð17Þ
lnð1  αÞ ¼ kt n ð18Þ
Eqn (17) and (18) imply that the reaction kinetics depends
on the constant k and nucleation dimensionality n + 1 (or n).
k indicates the speed of nucleation, and the nucleation dimen-
sionality number indicates the available dimensions for nuclei
to grow. Taking logarithm for both sides, eqn (17) and (18)
provide,
ln½lnð1  αÞ ¼ ln k þ ðn þ 1Þln t ð19Þ
Dalton Trans., 2018, 47, 9038–9050 | 9043

Paper
ln½lnð1  αÞ ¼ ln k þ n ln t ð20Þ
Plotting ln[−ln(1 − α)] vs. ln(t ) yields a straight line with
slope = n + 1 or n. The magnitude of n implies the reaction
mechanism. When n > 1, the model is known as ‘nucleation
and nuclei growth model’ which means that the reaction rate
is determined by the rate of nuclei growth.57 For the situation
when n < 1, the reaction generally proceeds by diffusion
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control.63
Reaction (1) can be regarded as a transformation from
Li4SiO4 to Li2CO3 and Li2SiO3, so Li2CO3 and Li2SiO3 are the
nuclei. Fig. 6 displays the plot of ln[−ln(1 − α)] to ln(t ) in the
first cycle for the six as-prepared samples. Two distinct stages
were observed for all the samples as fast and slow periods,
respectively. By comparing with the data of pore size distri-
bution in Fig. 2, the slopes of the initial fast stages in Fig. 6
showed a consistent order with the order of ∼4 nm pores
(nLS-ZSM5 > nLS-Precipitated > nLS-MCM41 > nLS-Fumed ≈ nLS-Waste >
nLS-SBA15). This strongly implied that ∼4 nm pores have a posi-
tive effect on the sorption kinetics. A possible reason might be
that pores in this size allow rapid penetration of CO2 gases
into the interior of sorbent particles, and therefore some germ
nuclei grow from the core with all the dimensionalities avail-
able to propagate. In contrast, without these pores, germ
nuclei were only generated from the particle surface. The avail-
able direction for surface germ nuclei to grow is only towards
the particle centre. The nucleation dimensionality was then
significantly reduced. The existence of ∼4 nm pores tended to
proceed with the nucleation more homogeneously, leading to
a higher value of the kinetic slope (growth dimensionality).
With the evolution of the product shell, the nucleus was
more likely to grow into the converted volume, but growth in
this manner did not contribute to the total CO2 capture. When
Fig. 6 The kinetic correlation between ln[−ln(1 − α)] and ln(t ) for the six
samples in the first cycle.
9044 | Dalton Trans., 2018, 47, 9038–9050
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Dalton Transactions
the product shell became even thicker, some germ nuclei may
be fully surrounded by the converted volume, so they had no
available dimensionality to grow. Consequently, the kinetics
would eventually shift to a much slower stage (ln(t ) > 3) as
shown in Fig. 6. Since the kinetics in the second stage seem to
be different from the stage prior to the inflection point,
forcing it to fit the Avrami-Erofeev model to get a slope value
does not have any physical sense. It is more appropriate to
examine what the reaction mechanism of this stage is. The
first possible cause of the reduced reaction kinetics is that
nucleation can only proceed towards the centre of a particle
after the continuous product shell is formed. Hence, the
nucleation rate is limited by the geometry of the particle. This
type of process could be described by the reaction-controlled-
shrinking-core-model (or known as the contracting model);
the second possibility is that the product shell inhibits the
contact of reactants; therefore CO2 has to diffuse though the
product shell for further reaction. This type of process can be
generally described by the diffusion-controlled-shrinking-core-
model.
For the reaction controlled model (contracting model), if
the nucleation proceeds towards the centre at a constant
speed, the conversion with time is expressed as61
ð1  αÞ1=3 þ ð1  α0 Þ1=3 ¼ kðt  t0 Þ ð21Þ
where k is a constant and α0 is the conversion at time t0. So if
the plot of −(1 − α)1/3 against t follows a straight line, the
second stage after the inflection point corresponds to a reac-
tion controlled model.
However, in the second scenario where the reaction is
limited by CO2 diffusion across Li2SiO3 and the Li2CO3 shell,
the conversion is governed by eqn (22)
ð1  αÞ2=3 1  α ð1  α0 Þ2=3 1  α0
  þ ¼ kðt  t0 Þ ð22Þ
2 3 2 3
A straight line of [(1/2)(1 − α)2/3 − (1/3)(1 − α)] against t
should be expected if the reaction in the second stage is
limited by diffusion.
Fig. 7 shows that the diffusion controlled model gave a
better fitting to the experimental data than the reaction con-
trolled model, indicating that the slow kinetics in the second
stage is more likely to be diffusion limited.
3.3 Cyclic sorption–desorption performance
It seems that the sample from precipitated silica was the most
favourable sorbent for the 10 h sorption test (Fig. 5). However,
solid sorbents were not designed to be one-off in practical
applications. The cyclic sorption/desorption stability of sor-
bents is of greater importance for both pre- and post-combus-
tion applications. Therefore, all the samples were further
subject to a 30-cycle test in this study. Fig. 8 suggests that all
samples underwent self-activation in the initial few cycles.
Except the sample developed from fumed silica, all the other
sorbents experienced performance decay after reaching a peak
value of capture capacity. Not only the sorption uptake did not
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Dalton Transactions Paper

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Fig. 7 Comparison between the contracting model and diffusion con-

trolled model for the slow reaction stage.

reach the same value of the previous cycle, but also the desorp-
tion process failed to come back to the original base line. This
incomplete sorption and desorption resulted in poor reversi-
bility of Reaction (1). This kind of negative phenomenon was Fig. 8 Sorption and desorption performance in 30 cycles. Conditions:
sorption in pure CO2 for 60 min and desorption in pure N2 for 10 min at
especially evident for samples made from precipitated silica, 650 °C.
MCM-41 and waste silica. To inspect the effect of the desorp-
tion extent on the sorption capacity of the following cycle, the
30-cycled LS-Precipitated was further tested with five
additional sorption–desorption cycles. But the desorption time
in each additional cycle was extended to 30 min to achieve
more complete desorption. Remarkable improvement of sorp-
tion capacity was observed after more complete desorption
(Fig. S2†), but the capacity was still much lower than the
theoretical value. This indicated that incomplete desorption
did not solely result in the poor cyclic capacity. The uptake
slopes at the end of each cycle were still steep for these three
samples, suggesting that 60 min were insufficient to reach
their CO2 uptake ceiling. Surprisingly, the sorbent derived
from fumed silica captured more and more CO2 cycle by cycle Fig. 9 CO2 capture capacities for the 30 cycles. (a) Capacity of individ-
until the end of Cycle No. 30. At the last cycle, the CO2 uptake ual cycle; (b) total capacity over the 30 cycles.
was 34.23 wt%, corresponding to 93.27% conversion of
Li4SiO4. It seemed that the slope of CO2 uptake was nearly flat
at the end of each cycle, indicating that 60 min sorption was
sufficient for a full carbonation. the 1st cycle. The sample derived from precipitated silica,
The cyclic capacity in the 30 cycles is summarized in Fig. 9. which was identified as the best sorbent based on the single
The order of total uptake over the 30 cycles (Fig. 9b) was: LS- 10 h test (Fig. 5a), exhibited the most disappointing perform-
fumed > LS-ZSM-5 > LS-SBA-15 > LS-MCM-41 > LS-waste > LS- ance for the long term cyclic test. Its individual capacity for
precipitated, which is identical to the order of the individual Cycle No. 30 was 11.52 wt%, which was only 1/3 of that at
capacity at the 30th cycle (Fig. 9a). This means that the capacity Cycle No. 3 (the cycle it peaked in terms of individual cycle
at the last cycle was more important than the initial capacity at uptake). Its total CO2 captured all over 30 cycles was as low as

This journal is © The Royal Society of Chemistry 2018 Dalton Trans., 2018, 47, 9038–9050 | 9045
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Paper Dalton Transactions

5.46 g-CO2 per g-sorbent. Contrastingly, the sorbent made

from fumed silica presented an opposite trend. It showed the
second lowest CO2 capacity in the 1st cycle (19.90 wt%), but its
capacity grew with cycles until approaching the theoretical
maximum. During the following cycles, the capacity did not
present any observable decline, sustaining at a constant level
until the last cycle (34.23 wt%). Owing to such stable perform-
ance, it captured the most CO2 through the total 30 cycles,
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namely, 10.03 g-CO2 per g-sorbent.

The morphological transformations of the six samples
before and after the 30-cycle tests are displayed in Fig. S3.† For
all the samples, an evident change caused by the cycles was
the reduction of particle sizes. This phenomenon was consist-
ent with reports for other similar sorbents. It was likely due to
the structure rearrangements during sorption and desorption
processes.64 To further confirm the change of materials, the
30-cycled LS-Fumed and LS-Precipitated samples which exhibi-
ted the most contrasting behaviours were selected for the XRD
test. Both samples still preserved the Li4SiO4 phase after 30
cycles with observable minor peaks of the Li2SiO3 phase
(Fig. 10). The FWHM of cycled LS-Fumed and LS-Precipitated
was 0.178 and 0.179, respectively. According to the Scherrer
equation, these values implied that the grain sizes reduced
after cycles. But not all samples demonstrated better sorption
kinetics with the finer particle size at the 30th cycle than at the
1st cycle. Only the LS-SBA-15 and LS-Fumed ones did so.
As shown above, the LS-Precipitated sample and LS-Fumed Fig. 11 The kinetic correlation between ln[−ln(1 − α)] and ln(t ) at the
1st, 5th, 10th, 15th, 20th and 30th cycles.
sample displayed the most striking contrast in the cyclic test.
In order to interpret the contrasting behaviour, the kinetic
data for the 1st, 5th, 10th, 15th, 20th and 30th cycles were plotted as
The remaining Li2CO3 and Li2SiO3 from the previous cycle pro-
ln[−ln(1 − α)] vs. ln(t ) for the two samples. Since ln[−ln(1 − α)]
vided more seeds for the heterogeneous nucleation of the next
is a single increasing function of α, a higher value of ln[−ln
cycle, thus giving a higher k value. Another possible cause
(1 − α)] also indicates a higher value of α. k indicates how fast
could be the morphological change caused by cycles. The N2
the nucleation proceeds. The intercept value (ln k) for the
physisorption test of the 30-cycled LS-Precipitated sorbent was
LS-Precipitated sample in Fig. 11 increased with cycles,
conducted to evaluate the change of porous properties
suggesting that the nucleation proceeded at a faster rate at the
(Fig. S4†) and compared with that of the fresh sample. After 30
very beginning compared to that in previous cycles. This might
cycles, the enlarged surface area and pore volume (Table 3)
be due to the incomplete regeneration of the previous cycle.
indicated that the material became more porous. The derived
pore size distribution by the BJH method also confirmed that
there was an enrichment of pores for most pore sizes (Fig. 12).
The enriched pores stemmed from the reduced particle sizes.
Since the particle sizes were smaller after cycles, there must be
more particles. In turn, there were more gaps between them,

Table 2 Li4SiO4 conversion when the CO2 sorption mode switched

from the nucleation stage to the diffusion controlled stage

Conversion after nucleation – α (%)

Cycles
LS-fumed LS-precipitated

1 7 17
5 42 29
10 61 27
15 72 25
Fig. 10 XRD patterns of LS-fumed and LS-precipitated samples after 20 71 23
30 cycles. 30 71 20

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Dalton Transactions Paper

Table 3 Surface area, pore size and pore volume of LS-fumed and LS- tics was mainly dependent on the ∼4 nm pores, the enrich-
precipitated samples before and after 30 cycles ment of such pores was responsible for this improved cyclic
kinetics.
BET surface Average pore Pore volume
Samples areaa (m2 g−1) size (nm) (cm3 g−1) With higher cycle numbers (>10), the evident distinction
between LS-Precipitated and LS-Fumed was that
LS-fumed before 30 cycles 1.05 3.94 0.007
LS-Precipitated started from a higher conversion value but
LS-fumed after 30 cycles 3.65 3.94 0.034
LS-precipitated before 1.44 3.95 0.009 grew with a lower number of dimensionality afterwards. The
30 cycles higher starting conversion value of LS-Precipitated came from
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LS-precipitated after 3.17 3.94 0.036

the uncalcined Li2CO3 and Li2SiO3 in the previous cycle
30 cycles
(Fig. 8). Since heterogeneous nucleation is more favourable
a
BET surface area equals the external area. than homogeneous nucleation, the uncalcined Li2CO3 and
Li2SiO3 could act as seeds for heterogeneous nucleation and
formed larger clusters during the nucleation. The large clusters
were very likely to interfere with each other and reduce the
number of growing dimensionality. This is why the cycled
LS-Precipitated sample showed a higher k value and a lower
nucleation dimensionality value. As for LS-Fumed, since the cal-
cination in the previous cycle was more complete (Fig. 8), it had
to generate a new Li2CO3 and Li2SiO3 nucleus from zero in the
new cycle. So the commencement of the LS-Fumed sample to
nucleate is more homogeneous. This is why it showed a lower
Fig. 12 Comparison of pore size distribution for LS-fumed and LS-
starting point or intercept (Fig. 11). But the newly generated
precipitated samples before and after 30 cycles.
nuclei were more dispersed. So the chance of interfering with
each other is relatively lower and growth dimensionality was thus
relatively higher. Eqn (17) and (18) indicate that homogeneous
causing an enhancement of pores. Since the first step is the nucleation had one more order (n + 1) than heterogeneous
rapid surface reaction, the enlarged surface area might corre- nucleation (n) in the time term (t ), which also confirmed that the
late with the increased k value in the initial stage of CO2 sorp- nucleation of cycled LS-Fumed was more homogeneous and that
tion. This correlation needs to be further examined for the of cycled LS-Precipitated was more heterogeneous.
LS-Fumed material. The quantity of ∼4 nm pores seemed to have a reasonable
The slope for the LS-Precipitated sample during the nuclea- correlation with the dimensionality of nucleation. This could
tion stage continuously decreased from slope = 2.31 for the be further explained by Fig. 13. When gas was switched from
first cycle, to slope = 2.25, 1.52, 1.11, 0.99 and 0.82 for the 5th, N2 to CO2, the contact between CO2 and the surface of Li4SiO4
10th, 15th, 20th and 30th cycles, respectively (Fig. 11). Since the initiated the nucleation. In this regard, smaller pores were
slope value for the 20th and 30th cycles was less than 1, it was advantageous over larger pores as smaller pores provide more
even barely reasonable to refer to this stage as nucleation. An surface area to begin nucleation. However, the material
exceptional phenomenon of pore size distribution after 30
cycles in Fig. 12 was that a decrease of pores occurred for the
pore size of ∼4 nm. As discussed above (Fig. 2b and 6), the
nucleation dimensionality was sensitive to the number of
∼4 nm pores, its reduction might be the reason for the
decayed kinetics with cycles.
As for the LS-Fumed sample in Fig. 11, the value of ln[−ln
(1 − α)] at ln(t ) = 0 (or ln k) was almost constant in the 30th
cycles, which was on account of the complete regeneration in
each cycle (Fig. 8). The enlarged pore volume and surface area
after cycles (Fig. 12 and Table 3) did not show a higher starting
point (ln k) for LS-Fumed and hence proved that the starting
point was irrelevant to the material morphology. The slope
during the nucleation stage was promoted with cycles for the
LS-fumed sorbent. The slope value started from 2.05 for the
initial cycle and reached 2.88 for the last cycle. This strongly
suggested that the improved CO2 capacity with cycles was
ascribed to the increment of dimensionality for growing
during the nucleation growth stage. Fig. 12 reported an enrich-
ment of ∼4 nm pores after 30 cycles. Since the nucleation kine- Fig. 13 Schematic of nucleation of samples with different pore sizes.

This journal is © The Royal Society of Chemistry 2018 Dalton Trans., 2018, 47, 9038–9050 | 9047

Paper
will swell after being converted from Li4SiO4 to Li2SiO3 and
Li2CO3, because the molar volume of Li2SiO3 and Li2CO3
(35.542 cm3 mol−1 and 35.019 cm3 mol−1) is higher than the
molar volume of Li4SiO4 (50.146 cm3 mol−1). If the pores are
too small, the volumetric expansion would close the narrow
pore as depicted in Fig. 13, thus causing the blockage of CO2
transfer. In this small pore scenario, nucleation can only com-
mence from the external part of the sorbent. The experimental
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observation and theoretical analysis in this study indicated
that ∼4 nm was highly likely the optimum size for Li4SiO4
sorbents. Pores of this size were highly possible from the
minor cracks of particles, which allowed CO2 diffuse rapidly
into the interior of particle without being blocked when the
product was generated. In such a manner, the nucleation
could commence from anywhere of the particle. Hence, the
nuclei had many dimensionalities to grow. However, the
nucleation only started from the particle surface if the pores
are too small. Once the product shell was formed, the inner
part did not have a chance to be converted by the nucleation
mechanism, instead, the inner part could only be converted
via the diffusion limited mode. The favourable sorption kine-
tics by ∼4 nm pores was also evident in a number of other
Li4SiO4 studies.65–67
The Li4SiO4 conversion at the inflection point from the
nucleation stage to the diffusion-controlled stage denoted the
extent of sorption via nucleation growth. As shown in Table 2,
the conversion ratio at the inflection point increased with
cycle numbers for fumed silica derived sorbents. In the first
cycle, the sorbent conversion was only α ≈ 7% in the nuclea-
tion stage. After the inflection point, all the remaining Li4SiO4
had to be converted in the diffusion limited mode. With
increasing cycle numbers, the conversion after nucleation
stage increased to α ≈ 42% at the 5th cycle, 61% at the 10th
cycle, 72% at the 15th cycle, 71% at the 20th cycle and 71% at
the 30th cycle, respectively. Although the slow diffusion would
limit further CO2 capture, the diffusion limited stage only
accounted for a minor portion of the total CO2 sorption. This
implied that nucleation growth played a progressively impor-
tant role in a cyclic sorption test, especially with higher cycle
numbers. For the precipitated silica derived sample, the
nucleation stage converted 17% of the Li4SiO4 at the first cycle,
which is still rather a low conversion. But the diffusion con-
trolled stage demonstrated a decent rate of CO2 capture in the
first cycle, so this material performed great CO2 capacity
initially. With increasing cycle numbers, the conversion by
nucleation growth kept declining from the 5th cycle to the 30th
cycle for the LS-Precipitated sample. Likewise, the sorption
rate in the diffusion controlled stage also deteriorated with
cycles, thus leading to a declining trend of sorption capacity.
4. Conclusions
Six different Si precursors were used to synthesize Li4SiO4 sor-
bents. The sorbent derived from precipitated silica demon-
strated the highest CO2 capacity (0.35 g-CO2 per g-sorbent) in a
9048 | Dalton Trans., 2018, 47, 9038–9050
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Dalton Transactions
10 h sorption test in a pure CO2 stream at 650 °C. It was found
that the sorption kinetics had a positive correlation with the
quantity of ∼4 nm pores. As such, LS-ZSM-5 which had the
most number of ∼4 nm pores exhibited the most rapid sorp-
tion kinetics. The cyclic performance of these sorbents was
tested for 30 cycles of sorption/desorption. After 30 cycles, all
the materials presented a smaller particle size due to a self-
rearrangement effect with cycles. Only the sorbent made from
fumed silica presented outstanding cycling stability with its
capacity growing from 19.90 wt% for Cycle No. 1 to 34.23 wt%
for Cycle No. 30. Even though the cycles reduced the particle
size, all the other sorbents showed deteriorated sorption
capacity with cycles, especially for the sorbent made from pre-
cipitated silica. The diverse cyclic behaviour of different sor-
bents was attributed to the sorption kinetics after cycles. The
Avrami-Erofeev model was used to interpret the rates of nuclea-
tion for the cycled LS-Fumed sorbent. The kinetics was
boosted due to more homogeneous nucleation which might be
related to the enrichment of ∼4 nm pores after 30 cycles. The
cycled LS-Precipitated sample only showed an improved start-
ing point due to the remaining Li2CO3 and Li2SiO3 from the
incomplete regeneration in the previous cycle. But the
decrease of ∼4 nm pores in the cycled LS-Precipitated sample
reduced the dimensionality of nucleation and thus slowed
down the overall sorption kinetics.
Abbreviations
D Diffusion coefficient in the product shell, m2 s−1
k Constant
k′ Rate of germ nuclei disappearance
m0 Minimum mass of the sample during the entire test,
g
mmax,i Maximum mass at the ith cycle, g
mmin,i Minimum mass at the ith cycle, g
N Number of nuclei
Ṅ Generation rate of nucleus, s−1
N′ Reduction of germ nuclei due to transformation
N″ Reduction of germ nuclei due to ingestion
N Number of dimensions
Qi CO2 capture capacity at the ith cycle, wt%
Qtotal Total CO2 capture capacity, wt%
R Radius of nuclei, m
ṙ Growth rate of nuclei radius, m s−1
t Time for sorption, s
V Volume, m3
Videal
convert Ideally converted volume, m3
Vconvert Real converted volume, m3
α Sorbent carbonation conversion
τ Time when nuclei are generated, s
Conflicts of interest
There are no conflicts to declare.
This journal is © The Royal Society of Chemistry 2018

Dalton Transactions
Acknowledgements
The authors acknowledge the support by the National Natural
Science Foundation of China (grant no: 51506112). Dr. Ji is
grateful to the China Postdoctoral Science Foundation
(grant no: 2017M610910).
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