Chemical Engineering Journal 427 (2022) 131561

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Chemical Engineering Journal

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CO2 capture (including direct air capture) and natural gas desulfurization of
amine-grafted hierarchical bimodal silica
John-Timothy Anyanwu, Yiren Wang, Ralph T. Yang *
Department of Chemical Engineering, University of Michigan, 3074 H.H. Dow, 2300 Hayward Street, Ann Arbor, MI 48109-2136, USA

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

Keywords: Amine grafting under hydrous conditions is emerging as a promising solution to developing amine grafted ad­
CO2 capture sorbents with high amine loading and superior capture performance. In this study, a hierarchical bimodal
Air capture mesoporous silica (HBS) that can be easily and cost-effectively synthesized was identified. Subsequently, HBS
Wet amine grafting
was amine grafted in anhydrous and hydrous conditions. The resulting material and its adsorptive performance
Pore structures
were investigated. Hierarchical bimodal silica supports allow aminosilanes to more easily access the deep
channels of the pores resulting in greater amine dispersion than SBA-15 type supports. The CO2 adsorption
capacity of amine grafted hierarchical bimodal silica adsorbents and SBA-15 type adsorbents were measured at
25, 75, 90, 100 ◦ C. The CO2 adsorption capacity and amine efficiency (reached 0.41 mol CO2/mol N) were
significantly higher than that of SBA-15 type adsorbents. This is because HBS possesses two series of mesopores
as opposed to one which promotes the diffusion of CO2 and allows for greater amine dispersion and consequently
greater amine utilization. Wet grafted HBS displayed excellent cyclic stability after approximately 10 adsorption-
desorption cycles. Under dry conditions and using ambient air containing 415 ppm of CO2 at 25 ◦ C, the fixed bed
breakthrough capacity of WG-HBS-0.6 was 1.04 mmol/g. To the best of our knowledge, the CO2 adsorption
capacity and the direct air capture capacity exceed reported literature values for amine-grafted silica adsorbents.
At similar amine loadings the H2S adsorption capacity of wet grafted hierarchical bimodal silica was similar to
SBA-15 type adsorbents suggesting thermodynamics as opposed to pore structure plays a greater role during the
H2S adsorption process. From the obtained results, hierarchical bimodal silicas are promising adsorbents for the
capture of CO2 from ambient air and industrial gas streams and are also suitable for the removal of H2S.

1. Introduction In particular, siliceous adsorbents such as silica gels, MCM-n, KIT-n

Energy generation for industrial processes is mainly achieved
through the combustion of fossil fuels. This has resulted in an unprec­
edented increase in global carbon dioxide (CO2) emissions [1]. CO2 is a
greenhouse gas that poses a considerable threat to the marine ecosystem
and consequently humans’ way of life [1,2]. Another acidic gas that is
generated during the energy generation process is Hydrogen Sulfide
(H2S). H2S is a highly toxic and corrosive that poses a threat to equip­
ment, personnel and the environment [3–7]. Considerable research ef­
forts have been undertaken to capture CO2 and H2S to combat their
detrimental impacts. In recent years, the most promising materials
employed for the removal of these harmful gases are activated carbons,
zeolites, metal organic frameworks, and mesoporous silicas [8–18]. This
is due to their beneficial porous properties which can be modified
[19–24].
and SBA-n functionalized with amines have attracted considerable
attention because they have been shown to be effective in capturing CO2
and H2S [25–30]. It is well established that accessible amines on the
silica surface improve adsorption performance. In particular, under dry
adsorption conditions amines react with CO2 molecules to form carba­
mates (zwitterion mechanism), whereas under wet conditions, hydrogen
bonded amines are released and more carbamate ion pairs can be formed
[31–37]. The reaction between H2S molecules and amines proceeds via a
rapid proton transfer mechanism [3,4]. Amine functionalization of silica
supports can be carried out through chemical grafting which is the co­
valent tethering of aminosilanes to the surface hydroxyl groups of
different types of silica supports (amine grafting) in anhydrous solution
[27,33,38–40]. Some of the initial uses of amine grafted adsorbents for
adsorption were reported by Leal et al. [41]. The group studied carbon
dioxide adsorption on amine grafted silica gel and observed a CO2

* Corresponding author.
E-mail address: yang@umich.edu (R.T. Yang).

https://doi.org/10.1016/j.cej.2021.131561
Received 25 May 2021; Received in revised form 26 July 2021; Accepted 28 July 2021
Available online 10 August 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
J.-T. Anyanwu et al.
capacity of 0.2 mmol/g at 1 bar. The low adsorption capacity can be
attributed to the small surface area of the silica gel support (200 m2/g).
Shortly after, Huang et al. displayed substantially higher carbon dioxide
adsorption capacity and high selectivity due to the much higher surface
area of amine-grafted MCM-48 (1400 m2/g) [42]. Many research groups
have followed up those earlier works on amine grafted silica adsorbents
given their favorable adsorption characteristics, however, due to the
limited amount of surface hydroxyls groups of silica supports their
adsorption performance was bounded [38–40,43].
To improve the amount of amines tethered on silica supports, water
is added during the chemical grafting process (wet grafting). Feng et al.
and Harlick et al. proposed that the surface of silica supports is hydrated
(increasing the silanol groups) and that the aminosilanes polymerize
through siloxane linkages of free aminosilanes to other grafted amino­
silanes upon water addition [44,45]. Kishor et al. reported a CO2
adsorption capacity of 1.56 mmol/g at 25 ◦ C and 1 bar for wet grafted
KIT-6 (3-aminopropyltriethoxysilane) [46]. Mittal et al. functionalized
SBA-15 in hydrous conditions with N1-(3-trimethoxysilylpropyl)dieth­
ylenetriamine (“DT”) and attained a CO2 adsorption capacity of 2.3
mmol/g at 75 ◦ C and 0.89 bar [47]. Loganathan et al. wet grafted ultra
large pore MCM-41 (30 nm) and reported a CO2 adsorption capacity of
1.80 mmol/g at 25 ◦ C and 0.2 bar [48]. Most of the work in literature on
wet grafting has focused on unimodal SBA-15, MCM-41 and KIT-6 type
supports and generally at high adsorption temperatures, low amine
loadings, and small water addition amounts. To the best of our knowl­
edge, systemic investigations analyzing amine grafted as well as wet
grafted hierarchical bimodal silica (HBS) supports are quite scarce. Hi­
erarchical bimodal silica supports have gained attention in recent years
due to the high surface area of the smaller series of mesopores and the
potential for enhanced availability of active sites within the structure
[49–53]. However, the synthesis of silica with hierarchical bimodal
structures is often demanding and complex [54,55]. HBS is generally
synthesized by utilizing the multi-template method in which one tem­
plate is employed to generate one mode of the mesostructure. Special
care has to be taken when choosing and combining the multi-templates.
This method can sometimes make the preparation costly, complicated
and challenging. In the last few years, a simple and cost-effective
method of synthesizing HBS was developed using a ternary nonionic
surfactant templating system (P123/HCl/TEOS) with well-defined hi­
erarchical bimodal structures [56,57]. To the best of our knowledge,
there has not been any work in the literature that has explicitly studied
the impact this hierarchical bimodal structure would have on CO2 and
H2S adsorption capacity.
The aim of this study is to investigate how hierarchical bimodal
structure affects the adsorptive performance. HBS was dry and wet
grafted and the resulting material was characterized using various
techniques and subsequently discussed. The amine loading, amine
density, adsorption of CO2 and H2S, and amine utilization were exam­
ined. Particularly, this study analyzed the performance of HBS under
conditions related to direct CO2 capture from ambient air as well as post
combustion gas. SBA-15 possesses a unimodal pore structure and com­
parable studies were carried out.
2. Materials
N1-(3-Trimethoxysilylpropyl)diethylenetriamine, Pluronic P123,
Hydrochloric Acid (HCl), Mesitylene and Tetraethylorthosilicate (TEOS)
were obtained from Sigma Aldrich. Anhydrous toluene was obtained
from Fisher Scientific.
2.1. Hierarchical bimodal silica
The synthesis of hierarchical bimodal mesoporous silica was per­
formed according to the procedure reported by Wang et al. [57] with
slight modifications. Eight grams of Pluronic P123 was dissolved in 152
mL deionized H2O and 20.7 mL of 37% HCl at room temperature. After
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Chemical Engineering Journal 427 (2022) 131561
the complete dissolution of Pluronic P123, the temperature was
increased to 40 ◦ C. 9.1 mL of TEOS was then added to the solution
dropwise (1st part) and left to pre-hydrolyze for 30 min while stirring.
After 30 min elapsed, 4.62 mL of Mesitylene (1,3,5-trimethylbenzene)
was added dropwise to the solution. After 4.5 h, 9.1 mL of TEOS was
then added to the solution dropwise (2nd part). The mixture was stirred
at 40 ◦ C for 24 h. It was then transferred to an autoclave and aged for 24
h at 100 ◦ C. The resulting white solid was collected by filtration, washed
with deionized water and dried overnight at 50 ◦ C. It was calcined for 6
h at 550 ◦ C under an air flow. It was designated as HBS.
2.2. SBA-15
The synthesis of SBA-15 was performed by adapting the synthesis
described by Wang et al. [58]. Eight grams of Pluronic P123 was dis­
solved in 2.0 M aqueous HCl (320 mL) at room temperature. After
Pluronic P123 completely dissolved, the temperature was increased to
35 ◦ C. 17.8 mL of TEOS was added dropwise to the solution and left to
pre-hydrolyze for 30 min while stirring. After 30 min elapsed, 4.62 mL of
Mesitylene (1,3,5-trimethylbenzene) was added dropwise to the solu­
tion. The mixture was stirred at 35 ◦ C for 20 h. The mixture was then
autoclaved and aged for 24 h at 90 ◦ C. The resulting white solid was
collected by filtration, washed with water and dried at 50 ◦ C overnight.
It was calcined for 6 h at 550 ◦ C under an air flow. It was designated as
SBA-15.
2.3. Dry grafting
The silica supports were dried at 100 ◦ C for at least 3 h prior to amine
grafting. In a typical synthesis, 100 mL anhydrous toluene was mixed
with 10 mL N1-(3-Trimethoxysilylpropyl)diethylenetriamine in an
erlenmeyer flask, and then 1 g of the silica support was added. The
mixture was stirred and refluxed at 85 ◦ C for 12 h. The grafted silica was
filtered and washed with copious amounts of toluene, then dried over­
night in a 50 ◦ C oven. Dry grafted supports were designated as AG-HBS
and AG-SBA-15.
2.4. Wet grafting
The silica supports were dried at 100 ◦ C for at least 3 h prior to amine
grafting. In a typical synthesis, a specific amount of H2O (0.2–0.8 mL)
was added dropwise to a solution containing 100 mL anhydrous toluene
and 1 g of the silica support. The mixture was stirred at room temper­
ature for 2 h. 10 mL N1-(3-Trimethoxysilylpropyl)diethylenetriamine
was subsequently added. The mixture was stirred and refluxed at 85 ◦ C
for 12 h. The grafted supports were filtered and washed with copious
amounts of toluene, then dried in a 50 ◦ C oven. Wet grafted adsorbents
were designated as WG-HBS-X and WG-SBA-15-X. X refers to the amount
of water (mL H2O/g SiO2) added during wet grafting.
3. Characterization
Carbon dioxide isotherms (0–1 bar) were measured at 25, 75, 90 and
100 ◦ C on a Micromeritics ASAP 2020 Sorptometer using a volumetric
technique. Nitrogen adsorption isotherms were measured at − 196 ◦ C on
a Micromeritics ASAP 2020 Sorptometer. All samples were degassed
overnight at 105 ◦ C prior to all measurements. Thermogravimetric
analysis was carried out on a Shimadzu TGA-50H. Amine loading
analysis was performed by pretreating the sample under a helium flow
for 2 h at 100 ◦ C, then heating to 850 ◦ C at a heating rate of 5 ◦ C/min
under a mixture of helium and air flow. Multi-cycle stability studies
were examined using a TGA under a dry 70% CO2 flow (in He) at 75 ◦ C.
The CO2 capacity after the first 60 s of adsorption during each cycle was
recorded. The sample was desorbed at 90 ◦ C in He after each adsorption
cycle.
Fixed-bed CO2 breakthrough adsorption measurement was carried
J.-T. Anyanwu et al.
Fig. 1. N2 adsorption-desorption isotherms at − 196 ◦ C for pristine, dry and wet grafted HBS (a) and SBA-15 (b).
Fig. 2. Amine loading of HBS (◆) and SBA-15 (●) using different amounts of
water during grafting.
out using a vertical, fixed-bed with an ambient air feed in a down-flow
manner. To constantly observe the CO2 concentration of the effluent gas
a Vaisala GMP343 CO2 probe was employed. The Vaisala GMP343 in­
corporates a silicon-based non-dispersive infrared sensor with a mea­
surement range of 0–1000 ppm of CO2. The fixed-bed column was 3.5
cm in height and 0.35 cm in diameter. An indent and a small piece of
quartz wool was employed to hold the fixed-bed. Prior to the adsorption,
the fixed-bed column was degassed at 105 ◦ C for 3 h under nitrogen
flow. Thereafter, the temperature was lowered to 25 ◦ C and the feed gas
(ambient air) was introduced.
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Chemical Engineering Journal 427 (2022) 131561
4. Results and discussion
4.1. Textural properties
Figs. 1 and S1 in the supporting information displays the N2 iso­
therms at − 196 ◦ C of SBA-15 and HBS. The supports both displayed a
type IV adsorption isotherm with H1 hysteresis loops which is indicative
of materials with mesopores and cylindrical pore channels [59,60]. The
nitrogen isotherm for HBS suggests the formation of two series of cy­
lindrical pore systems which is similar to hierarchical bimodal meso­
porous silica reported previously [56,57]. The first mode mesopores are
centered around 9.1 nm and the second mode mesopores are centered
around 33.8 nm. These results indicate HBS has hierarchical bimodal
mesopore structure. The pore size of SBA-15 is 10.4 nm. The BET surface
area and total pore volume are approximately 765 m2/g and 1.31 cm3/g
for SBA-15, and 611 m2/g and 1.59 cm3/g for HBS.
The grafting of all supports was carried out by using DT in anhydrous
(dry grafting) and hydrous (wet grafting) conditions. Thermal analysis
was conducted on all amine grafted adsorbents to confirm the presence
of amine moieties and determine the amine loadings. The weight loss
below 150 ◦ C was omitted because mainly atmospheric CO2 and
adsorbed water are removed [38,39,43,61]. Above 150 ◦ C, the loss of
grafted amines occurs and begins to level off around 600 ◦ C. The amine
loading of dry grafted SBA-15 and HBS were 26% and 28%, respectively
(Fig. 2). Compared to the dry grafted adsorbents, there is a substantial
increase in the amine loading after SBA-15 and HBS are grafted in the
presence of water. The amine loading increased from 26% to 49% for
SBA-15 and 28% to 50% for HBS. Under the synthesis conditions re­
ported in this study, the continuous addition of water from 0.2 to 0.8 mL
H2O/g SiO2, increased the amine loading of SBA-15 and HBS without
signs of plateauing (Fig. 2). For silica adsorbents, the elevated amine
loading is due to the hydrolysis and condensation of alkoxy groups in the
presence of water leading to aminosilane polymerization. The extent of
the polymerization of amines is influenced by the amount of water
added to the solution for alkoxy hydrolysis and condensation [62,63].
Overall, this confirms the presence of amine species and displays the
effectiveness of grafting in the hydrous conditions to increase amine
loading.
J.-T. Anyanwu et al. Chemical Engineering Journal 427 (2022) 131561

Table 1
Surface area and pore structure parameters.
Sample BET Surface Area Pore Diameter Total Pore Volume
(m2/g) (nm) (cm3/g)

SBA-15 766 10.5 1.32

AG-SBA-15 177 8.99 0.49
WG-SBA-15- 112 8.46 0.31
0.2
WG-SBA-15- 26 7.86 0.1
0.4
WG-SBA-15- 9.6 5.88 0.022
0.6
WG-SBA-15- 5 – 0.01
0.8
HBS 612 9.1, 33.8 1.59
AG-HBS 203 7.86, 26.4 0.96
WG-HBS-0.2 71 26.4 0.56
WG-HBS-0.4 62 26.4 0.4
WG-HBS-0.6 28 26.4 0.19
WG-HBS-0.8 7.1 – 0.02 Fig. 3. Amine density (mmol nitrogen per unit BET surface area) for HBS (□)
and SBA-15 (○).

The N2 isotherms at − 196 ◦ C of all amine grafted adsorbents are

depicted in Fig. 1 and the physical properties such as BET surface area,
pore size and pore volume are summarized in Table 1. For SBA-15, the
BET surface area, pore volume, and pore size of all amine grafted ad­
sorbents displayed a decreasing trend, confirming the presence of amine
moieties in the pores. This declining trend is a result of the clogging of
pores and major coverage of the supports’ surface by DT. Notably, the
BET surface area and pore volume of amine grafted HBS displayed a
decreasing trend while the pore size stayed the same beyond AG-HBS.
The surface area and pore volume decreased by 76.8% and 62.8% for
dry grafted AG-SBA-15, 85.3% and 76.5% for wet grafted WG-SBA-15-
0.2, 96.6% and 92.2% for wet grafted WG-SBA-15-0.4, 98.3% and
99% for wet grafted WG-SBA-15-0.6, and 99.3% and 99.2% for wet
grafted WG-SBA-15-0.8 compared to 66.8% and 39.6% for dry grafted
AG-HBS, 88.3% and 64.7% for wet grafted WG-HBS-0.2, 89.8% and
74.8% for wet grafted WG-HBS-0.4, 95.4% and 88% for wet grafted WG-
HBS-0.6, and 98.8% and 98.7% for wet grafted WG-HBS-0.8. This has
been observed in amine impregnated silica adsorbents using polymers
Fig. 4. CO2 adsorption isotherms at 25 ◦ C (closed symbols) and 75 ◦ C (open
like polyethyleneimine (PEI). The PEI polymers preferentially fill the symbols) for SBA-15 using 0 mL H2O (■), 0.2 mL H2O (), 0.4 mL H2O (◆), 0.6
smaller sized pores first leaving the larger pores intact. This results in a mL H2O (●) & 0.8 mL (▾) H2O.
decrease in total pore volume while the pore size diameter stays rela­
tively constant. As the PEI loading increases and eventually exceeds the
total pore volume of the pristine support, the pores become clogged and
the pore size drops dramatically [64]. This suggests that similar to amine
impregnated silica adsorbents, during wet grafting of HBS smaller size
pores are filled first, resulting in the observed plateau of the pore size.
This demonstrates that increasing the amine loading especially via wet
grafting correlates with a decrease in surface area, pore size, and pore
volume for conventional silica adsorbents and preferentially fills the
small sized pores of hierarchical bimodal silica supports.
The surface amine density (mmol N/m2) was calculated to better
understand the density of the amine moieties. Lashaki et al. synthesized
SBA-15 at different synthesis temperatures to achieve different pore
structures [65]. They proceeded to tether amines to the SBA-15 supports
and studied the surface amine density of the SBA-15 with different pore
sizes. They reported that large pore SBA-15 supports attained the highest
surface amine density due to increased number of triamines that can be
loaded on the surface. In this work, the surface amine density is provided
for SBA-15 and HBS as a function of water addition amount. Following
dry grafting, the surface amine density of SBA-15 and HBS were similar
due to the low amine loading. Wet grafted SBA-15, however, exhibited Fig. 5. CO2 adsorption isotherms at 25 ◦ C (closed symbols) and 75 ◦ C (open
increasingly higher surface amine densities with continuous addition of symbols) for HBS using 0 mL H2O (■), 0.2 mL H2O (▴), 0.4 mL H2O (◆), 0.6
water, whereas the amine density of HBS is stable till a slight increase mL H2O (●) & 0.8 mL (▾) H2O.
after the addition of 0.6 mL H2O/g SiO2 and a much larger increase after
0.8 mL H2O/g SiO2. This is attributed to significantly better amine supports. The large diameters of both series of mesopores allow the
dispersion for hierarchical bimodal supports compared to unimodal aminosilanes to more easily access deep channels without clogging the
pores whereas for unimodal supports like SBA-15, the singular pore

4
J.-T. Anyanwu et al.
system is more easily clogging by the grafted amines. This is evidenced
by the pronounced decrease in the pore volume of SBA-15 after wet
grafting. As the amine loading increases, the pore volume decreases to
near insignificant values, whereas the pore volume of HBS supports
decrease gradually. Additionally, despite marginally higher amine
loadings and lower BET surface area of HBS, the amine density of HBS
still remained lower than SBA-15 and pore volume still decreased
gradually. This indicates the grafted amines of HBS are more dispersed
and the CO2 implications are discussed below.
4.2. CO2 capture performance
4.2.1. Effect of amine loading and temperature on CO2 adsorption
The CO2 adsorption performance of dry grafted and wet grafted SBA-
15 and HBS at 25 and 75 ◦ C was measured and shown in Figs. 4 and 5. As
indicated in Fig. 4, the CO2 adsorption capacity at 25 ◦ C and 1 bar is
1.29 mmol/g for AG-SBA-15 and 1.72 mmol/g for AG-HBS. CO2
adsorption capacities at 25 ◦ C and 1 bar are 1.47 mmol/g (WG-SBA-15-
0.2), 1.13 mmol/g (WG-SBA-15-0.4), 0.57 mmol/g (WG-SBA-15-0.6),
and 0.38 mmol/g (WG-SBA-15-0.8) after wet grafting. For wet grafted
HBS (Fig. 5), the CO2 adsorption capacities are 1.96 mmol/g (WG-HBS-
0.2), 2.13 mmol/g (WG-HBS-0.4), 2.31 mmol/g (WG-HBS-0.6) and 1.58
mmol/g (WG-HBS-0.8) at 25 ◦ C. The adsorption capacity increased for
all supports grafted in the presence of 0.2 mL H2O/g SiO2 at 25 ◦ C.
However, the CO2 adsorption capacity for SBA-15 decreased upon
further increase in the amount of water added. Similarly, for HBS the
CO2 adsorption at 25 ◦ C, increased till the addition of 0.6 mL H2O/g SiO2
before decreasing substantially thereafter. There is an initial enhance­
ment of the CO2 capture capacity for wet grafted adsorbents at their
optimal water addition amounts at 25 ◦ C. In this instance, the optimal
amount is 0.2 mL H2O/g SiO2 for SBA-15 and 0.6 mL H2O/g SiO2 for
HBS. Further increase in the water addition amount during grafting
results in a decrease in the adsorption capacity at 25 ◦ C. This suggests
that the optimal water addition amount for high CO2 adsorption ca­
pacity at 25 ◦ C is dependent on the support’s pore structure and in­
dicates HBS is an excellent adsorbent for direct air capture.
Dry grafted SBA-15 and HBS attained their highest CO2 capacity at
25 ◦ C, nevertheless, the CO2 adsorption capacity reduced when the
adsorption temperature was increased to 75 ◦ C. This behavior demon­
strates the exothermic nature of CO2 adsorption for many adsorbents
grafted in anhydrous conditions. The CO2 adsorption capacity for all
supports grafted in the presence of water increased significantly as the
adsorption temperature was increased beyond 25 ◦ C. The adsorption
capacities at 75 ◦ C and 1 bar are 1.9 mmol/g (WG-SBA-15-0.2), 2.35
mmol/g (WG-SBA-15-0.4), 2.81 mmol/g (WG-SBA-15-0.6) and 2.78
mmol/g (WG-SBA-15-0.8). For wet grafted pore expanded SBA-15, the
adsorption capacities are 2.05 mmol/g (WG-HBS-0.2), 2.82 mmol/g
(WG-HBS-0.4), 3.26 mmol/g (WG-HBS-0.6), and 3.55 mmol/g (WG-
HBS-0.8). For all wet grafted supports at 75 ◦ C, it was observed that as
the amine loading increased, the adsorption capacity increased. Higher
adsorption temperatures reduce the viscosity of the polymer-like amines
resulting in easier access to inner amine sites [27,33,61,66,67]. How­
ever, as shown in Table S1, Figs. S1 and S2 in the supporting informa­
tion, the relationship between adsorption temperature and amine
loading beyond 75 ◦ C is more complex. The CO2 adsorption capacity of
SBA-15 grafted in 0.2 and 0.4 mL H2O/g SiO2 was highest at 75 ◦ C;
however, the adsorption capacity of SBA-15 grafted in higher than 0.4
mL H2O/g SBA-15 was highest at 90 ◦ C and started decreasing at 100 ◦ C.
The highest CO2 adsorption capacity achieved for wet grafted SBA-15 at
75, 90, and 100 ◦ C were 2.82 (WG-SBA-15-0.6), 3.27 (WG-SBA-15-0.8),
and 3.05 mmol/g (WG-SBA-15-0.8), respectively. For HBS, the CO2
adsorption capacity of supports grafted in 0.2, 0.4, and 0.6 mL H2O/g
SiO2 was highest at 75 ◦ C; however, the adsorption capacity of HBS
grafted in 0.8 mL H2O/g SBA-15 was highest at 90 ◦ C and eventually
started to decrease at 100 ◦ C. The highest CO2 adsorption capacity
achieved for wet grafted HBS at 75, 90, and 100 ◦ C were 3.26 (WG-HBS-
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Chemical Engineering Journal 427 (2022) 131561
0.6), 3.58 (WG-HBS-0.8), and 3.11 mmol/g (WG-HBS-0.8), respectively.
As mentioned earlier, one of the key barriers to adsorption for adsor­
bents with high concentrations of grafted amines is the diffusion of CO2
on the surface to the bulk of the grafted polymer-like amines. Depending
on the studied adsorbent and its pore structure, adsorption temperature
between 75 and 90 ◦ C (kinetically controlled regime) increases amine
mobility and aids the transfer of adsorbed CO2 from the surface into the
bulk of the grafted amines. The CO2 adsorption capacity is therefore
greatly enhanced because greater amounts of amine sites are revealed
for eventual CO2 adsorption. Although higher adsorption temperatures
expose CO2 to more capture sites, at 100 ◦ C CO2 desorption from capture
sites becomes more favored, resulting in the reduced CO2 adsorption
capacity (shift to thermodynamically controlled regime) [27,33,61,66].
This suggests that wet grafted unimodal silica adsorbents such as SBA-15
are greatly kinetically controlled. Unimodal adsorbents consist of one
pore system and when pore clogging occurs at high amine loadings, it
becomes difficult for CO2 to diffuse into and out of the pores and reduces
the accessibility of the amine moieties. However, the adsorption process
of wet grafted bimodal adsorbents with two series of pore systems is not
as strongly kinetically controlled as that of wet grafted unimodal ad­
sorbents. The mesopores are preserved even at high amine loading
resulting in enhanced diffusion of CO2 molecules and accessibility of the
grafted amines deep in the pore channels. This is further supported by
Fig. 3 which in effect shows that amines are better dispersed on HBS
structures as opposed to SBA-15 type structures. Amine density increases
somewhat proportionally to increasing amine loading, however, the
magnitude of increase in amine density of wet grafted HBS adsorbents is
lower than that of wet grafted SBA-15 adsorbents. This results in greatly
increased accessibility of amine groups and improved overall CO2
adsorption performance.
Capturing CO2 from flue gas generated after combustion of carbon-
based fuel is an important industrial practice and evaluating the per­
formance of these adsorbents under those conditions is essential. It is
noteworthy that hierarchical bimodal adsorbents displayed significantly
higher CO2 adsorption capacities than SBA-15 in the flue gas range. The
CO2 adsorption capacity increased from 2.07 mmol/g (25 ◦ C) to 3.05
mmol/g (75 ◦ C) in the flue gas range (~0.15 bar) as shown in Figs. 5 and
S2. When adsorption temperature was increased to 90 ◦ C and 100 ◦ C
(~0.15 bar), the CO2 adsorption capacity declined to ~2.5 mmol/g and
~1.7 mmol/g, respectively. Increasing the adsorption temperature
beyond 75 ◦ C resulted in a decrease in the adsorption capacity in the flue
gas range. It is likely that the aforementioned adsorption barriers also
manifest in the flue gas range. Moreover, flue gas is mostly composed of
carbon dioxide and nitrogen. Thus, for promising adsorbents it is
important to evaluate the selectivity of carbon dioxide over nitrogen.
The pure component selectivity was investigated and Fig. 3 shows the
nitrogen adsorption isotherms at 25 ◦ C and 1 bar of WG-SBA-15-0.6 and
WG-HBS-0.6. The CO2 adsorption capacity for WG-SBA-15-0.6 and WG-
HBS-0.6 were 0.57 and 2.31 mmol/g. While the N2 uptake for WG-SBA-
15-0.6 and WG-HBS-0.6 were 0.03 and 0.031 mmol/g, respectively. The
calculated CO2/N2 selectivity for WG-HBS-0.6 was 74.5, which is 4 times
greater than the value for WG-SBA-16-0.6 (19). In the flue gas range
(~0.15 bar CO2 and ~0.8 bar N2), the CO2/N2 selectivity for WG-HBS-
0.6 increases by ~2% to 77 while the CO2/N2 selectivity for WG-HBS-
0.6 decreases by ~17% to 15.7.
The amine efficiency (mol CO2/mol N) is an important component
used to assess amine-grafted adsorbents. Under anhydrous adsorption
conditions, the theoretical maximum amine efficiency is 0.5 mol CO2/
mol N and in hydrous conditions, values greater than 0.5 can be ach­
ieved [34,35,61]. Amine efficiency approximately conveys the portion
of wet grafted amine moieties that contribute during the adsorption of
CO2. Pore blockage and the location of the amines in the pore structure
affect overall amine efficiency. Table S1 in the supporting information
portrays the amine efficiencies of all grafted SBA-15 and HBS supports at
25, 75, 90 and 100 ◦ C. At 25 ◦ C, the amine efficiency of all amine grafted
SBA-15 adsorbents slowly decreases as water concentration and
J.-T. Anyanwu et al. Chemical Engineering Journal 427 (2022) 131561

Table 2
Summary of wet grafted silica adsorbents and their CO2 capture capacities.
Sample Amine used CO2 adsorption capacity Reference

CO2 partial pressure(bar) Temperature ( C)

◦
Adsorption Capacity (mmol/g, dry) Amine Efficiency(mol CO2/mol N)

MCM-41 DT 0.2 75 2.1 0.33 [48]

SBA-15 Diamine 0.15 60 1.36 0.29 [70]
SBA-15 DT 0.15 60 1.58 0.27 [70]
SBA-15 DT 0.89 75 2.36 0.31 [47]
WG-HBS-0.6 DT 1 25 2.31 0.29 Present work
WG-HBS-0.8 DT 1 75 3.55 0.41 Present work
WG-HBS-0.8 DT 1 90 3.58 0.41 Present work

Table 3
Summary of wet grafted silica adsorbents and their direct air capture capacities.
Sample Amine CO2 adsorption capacity Reference
used
CO2 Temperature Breakthrough
(ppm) (◦ C) CO2 Capacity
(mmol/g, dry)

Silica DT 415 25 0.77 [61]

Gel
MCM- DT 300 25 0.90 [45]
41
WG- DT 415 25 1.04 Present
HBS- work
0.6

subsequently amine loading increases. Relative to dry grafted SBA-15,

the amine efficiency of wet grafted SBA-15 adsorbents experienced a
maximum reduction of approximately 84% (0.29 mol CO2/mol N to
0.045 mol CO2/mol N) at 25 ◦ C. The amine efficiency trends for HBS are
somewhat similar except the reduction in efficiency is not as drastic. Fig. 6. CO2 (filled symbols) and N2 (open symbols) adsorption isotherms for
HBS adsorbents experienced a 50% decline (0.36 mol CO2/mol N to WG-HBS-0.6 (●), and WG-SBA-15-0.6 (■) at 25 ◦ C and 1 bar.
0.18 mol CO2/mol N) in amine efficiency at 25 ◦ C. For the best per­
forming adsorbent (WG-HBS-0.6), the amine efficiency was 0.29 mol
CO2/mol N, which is a modest 19% decline. These observed declines in
amine efficiency are attributable to increased blocking of the pores and
significant reduction in pore volume resulting in the diminished amine
efficiency at 25 ◦ C. This is further proven by Fig. 3, which shows
significantly higher amine density for SBA-15 as amine loading in­
creases. Amine efficiency trends at high adsorption temperatures (75, 90
and 100 ◦ C) for wet grafted SBA-15 and HBS are more ambiguous. Wet
grafted SBA-15 adsorbents achieved their highest amine efficiency at or
around 90 ◦ C with negligible decreases when the adsorption tempera­
ture is increased to 100 ◦ C. This is consistent with a kinetically limited
process and higher temperatures are needed to overcome the resistance
to diffusion of CO2 from the surface to the bulk of the grafted amines. In
the case of wet grafted HBS adsorbents, they achieved their highest
amine efficiency at 75 ◦ C, with significant drops when the adsorption
temperature is increased to 90 and 100 ◦ C. As mentioned earlier,
compared to unimodal adsorbents, the adsorption process of bimodal
adsorbents is less strongly kinetically limited. Past 75 ◦ C, desorption is Fig. 7. CO2 breakthrough curves for wet-grafted WG-HBS-0.6 under an
ambient air feed at 25 ◦ C, 0.96 bar and R.H. 0.0. Space velocity = 3,000 hr-1.
more preferential resulting in lower amine efficiencies. It is notable that
while the observed amine loading of dry and wet grafted HBS was mildly
higher than that of SBA-15, they generally achieved significantly higher 4.3. Fixed bed breakthrough curves
adsorption capacities and amine efficiencies at all studied adsorption
temperatures. This demonstrates that hierarchical bimodal supports Fixed-bed adsorption breakthrough experiments were carried out to
allow for better amine dispersion and promote the diffusion of CO2, investigate the adsorption performance of WG-HBS-0.6 under direct air
which leads to efficient utilization of amines to capture CO2 from all capture conditions. Breakthrough experiments were carried out using an
dilute and non-dilute sources. ambient air feed (with 415 ppm CO2) and an adsorption gas hourly space
To date, research on wet grafted adsorbents mainly utilize unimodal velocity of 3000 hr-1. The ambient air stream was dry (pre-dried with 3A
supports such as SBA-15 and MCM-41. Tables 2 and 3 outlined the re­ zeolite) and the results are shown in Fig. 7. The breakthrough time was
sults from this work and literature that employ amine grafted unimodal approximately 280 min and approaches saturation at approximately
adsorbents for the capture of CO2 from ambient air and non-dilute 1250 min. The calculated capture capacity was 1.04 mmol/g. To the best
sources. It is evident that wet grafted hierarchical bimodal adsorbents of our knowledge, 1.04 mmol/g is the highest recorded adsorption ca­
display significant potential for the capture of CO2. pacity for an amine-grafted silica adsorbent for direct air capture [2]. It

6
J.-T. Anyanwu et al.
Fig. 8. H2S adsorption isotherms for WG-HBS-0.6 (a) and AG-HBS (b) at 25 ◦ C
(closed symbols) and 50 ◦ C (open symbols) and 1 bar.
should be mentioned that wet impregnated adsorbents like TEPA/SiO2
achieve higher adsorption capacities in similar conditions (1.6 mmol/g)
[68]. Moreover, WG-HBS-0.6 outperforms zeolites under dry conditions.
Wilson et al. investigated the potential for zeolites to capture CO2 from
ambient air [9]. They found that APG-III displayed a high uptake of 0.42
mmol/g in dry conditions. Stuckert et al. carried out breakthrough ex­
periments on Li-LSX, K-LSX, and NaX zeolites [69]. They reported a
breakthrough capacity of 0.25 mmol/g for K-LSX, 0.32 mmol/g for NaX
and 0.82 mmol/g for Li-LSX, all of which are below the breakthrough
capacity of WG-HBS-0.6. They also found that the CO2 capture capacity
for Li-LSX, K-LSX, and NaX decreased by almost 100% in humid
adsorption conditions. The significant decline in overall CO2 adsorption
capacity of zeolites is because they are hydrophilic materials which re­
sults in competitive adsorption in the presence of water. Conversely,
moisture positively influences the CO2 adsorption capacity of amine
functionalized silica because hydrogen bonded amines are released and
additional carbamate ion pairs can be formed [35,61]. Therefore, WG-
HBS-0.6 should display improved performance under humidified
conditions.
4.4. H2S adsorption performance
Natural gas streams contain hydrogen sulfide (H2S), methane (CH4)
and several other components. However, harmful gases such as H2S need
to be removed to increase the calorific value of natural gas [3–5].
Therefore, measurements were conducted on the amine grafted HBS in
H2S gas mixtures to ascertain their H2S adsorption capacity. The low
concentration H2S adsorption isotherms at 25 and 50 ◦ C of AG-HBS and
WG-HBS-0.6 are presented in Fig. 8. From the isotherms, it is evident
that H2S adsorption is favorable for adsorbents with high amine load­
ings. Although, even at higher amine loadings, increasing the H2S
adsorption temperature resulted in a decrease in the H2S adsorption
capacity, which is in contrast with what was observed for CO2 adsorp­
tion. The maximum CO2 adsorption capacity of all wet grafted
7
Chemical Engineering Journal 427 (2022) 131561
Fig. 9. H2S adsorption isotherms for WG-HBS-0.6 (◆) and WG-SBA-15–0.6 (▴)
at 25 ◦ C (closed symbols) and 50 ◦ C (open symbols) and 1 bar.
adsorbents increased from 25 to 75 ◦ C, whereas the H2S adsorption
capacity decreased from 25 ◦ C to 50 ◦ C for all amine grafted adsorbents.
Further increase of the adsorption temperature beyond 50 ◦ C led to
negligible H2S adsorption. The work of Ma et al. explored H2S adsorp­
tion at high temperatures for amine impregnated MCM-41 and the study
attributed the capacity reduction to significantly lower diffusion limi­
tations for H2S. The estimated kinetic barrier for diffusion from surface
to bulk of aminopolymers was ~3 times higher for CO2 than H2S [70].
This reveals that H2S is predominantly thermodynamically controlled
since lower temperatures typically favors adsorption and the presence of
large amounts of amines does not significantly increase the diffusion
barriers. Building on their work, H2S isotherms of WG-HBS-0.6 and WG-
SBA-15-0.6 were compared in Fig. 9. Fig. 9 shows that the H2S
adsorption capacity of WG-HBS-0.6 at 25 ◦ C was marginally higher than
AG-SBA-15-0.6, most likely due to the higher amine loading. This sug­
gests that for H2S adsorption, adsorbents with hierarchical bimodal pore
structures-as compared to adsorbents with large pores-does not greatly
increase the adsorption performance. To examine this further for H2S
adsorption, the amine efficiency (mol H2S/mol N) was calculated. The
amine efficiency of WG-HBS-0.6 (0.013 mol H2S/mol N) and WG-SBA-
15-0.6 (0.013 mol H2S/mol N) were similar, indicating that H2S mole­
cules can adequately access the amine sites of hierarchical bimodal and
unimodal adsorbents.
Moreover, CO2 and H2S are both acidic gases and therefore as an
adsorbate their adsorptive behavior is quite comparable. From Figs. 6
and 9, it is observed that the shape of the H2S adsorption isotherm is
somewhat different than that of the CO2 adsorption isotherm. H2S has a
markedly lower initial isosteric heat of adsorption than CO2 [71]. This
translates into steeper isotherm shapes for CO2 compared to H2S at low
pressures/concentrations, where chemisorption likely predominantly
occurs. At higher pressures/concentrations, where physisorption likely
predominantly occurs, H2S uptake is more pronounced suggesting that
H2S adsorption is more strongly dependent on pressures/concentrations
than CO2 adsorption [71,72]. It is worth mentioned that in previous
works showed that amine grafted silica sorbents can be regenerated
without any loss of H2S adsorption capacity, indicating the H2S
adsorption is completely reversible on the amine grafted silicas adsor­
bents [42,71,72].
The pure component CH4 isotherm of AG-HBS and WG-HBS-0.6 at
25 ◦ C is presented in Fig. S4 in the supporting information. At 25 ◦ C, the
H2S adsorption capacity is 0.049 mmol/g for AG-HBS and 0.11 mmol/g
for WG-HBS-0.6. The CH4 adsorption capacity for AG-HBS and WG-HBS-
0.6 is similar at 25 ◦ C and 1 bar. Compared to the H2S adsorption ca­
pacity for AG-HBS and WG-HBS-0.6 at a much lower concentration (125
ppm), the methane adsorption capacity for both adsorbents is markedly
lower, demonstrating that the increased amine loading did not
J.-T. Anyanwu et al.
Fig. 10. Cyclic stability studies (70% CO2 (in He) flow) of WG-HBS-0.6 at 75 ◦ C
and 1 bar.
noticeable affect the CH4 adsorption capacity. However, the H2S
adsorption capacity doubled with the increase in amine loading. These
results show that WG-HBS-0.6 is an effective adsorbent for the removal
of H2S from natural gas.
4.5. Cyclic stability
For practical applications, it is essential that adsorbents be stable
after multiple adsorption-desorption cycles. The cyclic stability of WG-
HBS-0.6 (highest performing support) was investigated at 75 ◦ C. After
each adsorption measurement, WG-HBS-0.6 was regenerated in He at
90 ◦ C. As shown in Fig. 10, after 10 adsorption/desorption cycles at
75 ◦ C, there was no observable loss in the CO2 adsorption capacity.
These findings are congruous with previous studies for amine grafted
adsorbents and displays the cyclic stability of WG-HBS-0.6
[29,31,36,61]. However, the cyclic stability of the amine functional­
ized adsorbents eventually deteriorates in moisture-free conditions
[31,36,61]. Continued cycling of the adsorbent at elevated temperatures
results in the formation of stable urea groups, which serves to reduce
cyclic stability. The decomposition of carbamates may also play a role in
the worsening of the stability. Fortunately, under humid conditions, the
formation of stable urea groups is greatly hindered, resulting in fewer
amounts of deactivated amines [73]. Sayari et al. studied the stability of
amine grafted MCM-41 under humid conditions (7.5% R.H., 70 ◦ C) for
700 cycles. They demonstrated no significant loss in the adsorption ca­
pacity of amine grafted MCM-41 and attributed this to significant
reduction in the formation of urea groups under humid conditions [73].
Amine grafted HBS and SBA-15 are silica supports similar to MCM-41,
therefore the aforementioned effects should also be observed for those
adsorbents.
5. Conclusion
An easily synthesized hierarchical bimodal mesoporous silica (HBS)
was identified. It was grafted in the presence of water and the results
indicated that HBS achieved slightly higher amine loadings than SBA-
15, a unimodal support. It was found that wet grafted HBS exhibited
greater dispersion of the grafted amine compared to wet grafted SBA-15.
The large diameters of the series of mesopores allow the aminosilanes to
more easily access deep channels without blocking the pores. In addi­
tion, the impact of supports with one series as well as two series of
mesopores on the CO2 capture performance was examined. The CO2
adsorption capacity at various adsorption temperatures of wet grafted
HBS was found to be superior to other amine grafted adsorbents re­
ported in literature. HBS provided enhanced diffusion of CO2 molecules
8
Chemical Engineering Journal 427 (2022) 131561
and accessibility of the grafted amines in the pore channels resulting in
excellent amine efficiency. Even at higher amine loadings, it was also
found that the adsorption process of wet grafted HBS adsorbents is not as
strongly kinetically controlled as that of wet grafted unimodal adsor­
bents. Fixed-bed breakthrough experiments with a dry ambient air
stream containing 415 ppm CO2 were performed and the results
demonstrate that wet grafted HBS is a superior adsorbent for direct air
capture purposes. They also displayed exceptional stability after multi­
ple adsorption-desorption cycles. Lastly, while wet grafted HBS dis­
played high CO2 adsorption capacity and favorable pore properties, it
performed comparably to SBA-15 type adsorbents, demonstrating the
significantly lower kinetic barrier for the diffusion of H2S molecules
during the adsorption process.
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.
Acknowledgments
This work was supported by NSF Grant CBET-1826621, the Global
CO2 Initiative at the University of Michigan and the Blue Sky program of
the College of Engineering at the University of Michigan.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.131561.
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