Article

Cite This: Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX pubs.acs.org/IECR

Roles of Oxygen Functional Groups in Hydrogen Sulfide Adsorption

on Activated Carbon Surface: A Density Functional Study
Fenghua Shen, Jing Liu,* Chenkai Gu, and Dawei Wu
State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and
Technology, Wuhan 430074, China

ABSTRACT: The hydrogen sulfide (H2S) removal ability of activated

carbon is closely related to surface oxygen groups, yet the roles of oxygen
groups in the process of H2S adsorption on activated carbon have
heretofore been unclear. The interactions of H2S with various oxygen
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groups on activated carbon were detailed examined by density functional

theory. The results indicate that pyrone, carbonyl, ester, and carboxyl
groups are active sites for H2S adsorption, except for hydroxyl group.
H2S can react directly with carbonyl oxygen atom in these oxygen groups
leading to the formation of C−S, C−OH, and C−SH species. A pyrone
group can improve the activity of surface carbon sites for H2S adsorption. The presence of non-neighboring epoxy oxygen atom
increase evidently the activity of carbonyl oxygen atom for H2S adsorption. The relative position of the carbonyl oxygen atom
and epoxy oxygen atom plays a key role in the activity of oxygen groups.
Ind. Eng. Chem. Res.

1. INTRODUCTION Quantum chemistry methods based on density functional

Hydrogen sulfide (H2S) is generally regarded as an acidic air
pollutant produced in many industrial plants. H2S is harmful to
the central nervous system of human bodies. In addition, H2S
can destroy metallic catalysts and results in catalyst
deactivation.1 Recently, the removal of H2S by using sorbents
has attracted increasing attention. Among various materials,
activated carbon is considered as a useful H2S sorbent.2,3
Clarification of the detailed interactions of H2S with activated
carbon has great practical implication for achieving higher H2S
removal efficiency.
The surface chemistry property of activated carbon is one of
the key points in H2S removal. Heteroatom oxygen on
activated carbon surface is usually classified into different
oxygen groups. These oxygen groups have significant effects on
the surface chemistry of activated carbon,4−6 and thereby affect
H2S adsorption. Various experimental studies were performed
to investigate the influences of oxygen groups on H2S removal
capacity of activated carbon.7−10 However, there is no general
agreement on the role of different oxygen groups in H2S
adsorption. Cal et al.11 studied the effect of oxygen content on
H2S adsorption on activated carbon, and they found that H2S
uptake capacity of activated carbon increased with the raising
of oxygen content. They suggested that chemical reactions of
H2S with C−O complexes were involved in H2S adsorption.
Brazhnyk et al.12 investigated the oxidation of H2S by oxygen
groups on activated carbon. They found that the H2S removal
ability of activated carbon is mainly depending on the type of
oxygen groups rather than the oxygen content. Bouzaza et al.13
suggested that some oxygen groups are active for H2S
adsorption on activated carbon, whereas other oxygen groups
are inert for H2S adsorption. Thus far, the detailed roles of
different oxygen groups in H2S adsorption on activated carbon
surface are still not clear.
theory (DFT) have been increasingly used to clarify the
interactions in both homogeneous and heterogeneous
systems.14−17 Ashori et al.18 have studied the interactions of
H2S with carbon nanocone, nanotube, and graphene by using
DFT calculations. In our previous study,19 the adsorption
mechanism of H 2 S on activated carbon surface was
investigated. The results of DFT calculations indicated that
activated carbon improved H2S decomposition and provided
adsorption sites for H2S. However, to the best of the author’s
knowledge, no theoretical study has been conducted to
investigate the interactions of H2S with different oxygen
groups on activated carbon at the molecular level. Such a study
would help to give a better understanding of the effects of
oxygen groups on H2S adsorption on activated carbon.
The present study was conducted aiming to clarify the roles
of different oxygen groups in the adsorption of H2S on
activated carbon. The interactions of H2S with different oxygen
groups (pyrone, carbonyl, ester, carboxyl, and hydroxyl) on
carbon surface were studied by applying density functional
theory. The adsorption energy of H2S on each oxygen groups
is analyzed to determine their activity. This study provides an
understanding of the interaction mechanism of H2S with
oxygen groups, which is important for developing effective H2S
removal technologies.
Received: January 26, 2019
Revised: March 4, 2019
Accepted: March 25, 2019
Published: March 25, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.9b00507

Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Figure 1. Activated carbon surface with and without oxygen functional groups.

2. COMPUTATIONAL METHODS neighboring sp2 carbonyl oxygen atom and sp3 epoxy oxygen
All of the density functional theory calculations were atom and presents on activated carbon surfaces in a large
performed using the Gaussian09 package.20 Full geometry number. The pyrone group would be the most important
optimizations of all structures were conducted at B3PW91/6- oxygen groups account for the basicity of activated carbon.29 It
31G(d) level. has been proposed that the basicity of activated carbon is
The total adsorption energy can be calculated as following mainly due to pyrone-type structures.30 Therefore, it is
equation: reasonable to use carboxyl, ester, and hydroxyl to simulate
Eads = E(AB) − (E(A) + E(B)) the acidic oxygen groups and to employ pyrone and carbonyl
groups to simulate the basic oxygen groups on activated
where E(A) is the total energy of the adsorbate and E(B) is the carbon.
total energy of the substrate. E(AB) is the total energy of The optimized geometries of different oxygen groups are
adsorbate/substrate system in the equilibrium state. Adsorp- illustrated in Figure 1. Some pertinent bond lengths of C−O
tion of the adsorbate is exothermic if Eads is negative.21,22 A
are also given. Mulliken population analysis is employed to
more negative value of Eads corresponds to a stronger
adsorption. Normally, if the adsorption energy is less than evaluate the bond strength. A highly positive value of bond
−30 kJ/mol, then the interaction belongs to physisorption. If population means a strong interaction between the atoms,
the adsorption energy is higher than −50 kJ/mol, then the whereas no interaction exists if the bond population is close to
interaction belongs to chemisorption. zero.31,32 The bond populations of basic and acidic oxygen
Solid-state 13C NMR characterization experimental data groups on activated carbon surface are listed in Table 1. The
showed that carbon had chemical structures consisting of 3−7 values of C−O bond populations in these oxygen groups are
benzene rings.23 It was found that the reactivity of the active highly positive. This means a strong interaction of O atom with
sites strongly depended on its local shape rather than on the C atom, and the breaking of such C−O bond will be highly
size of the cluster models.24,25 Therefore, a seven-ring cluster
endothermic process.
model is used to represent the structure of activated carbon, as
shown in Figure 1. This cluster model is suitable to simulate
the activated carbon structure since its geometric parameters Table 1. Mulliken Populations for Oxygen Functional
are close to the experimental data.26,27 Groups on Activated Carbon Surface
It is important to establish reasonable models for oxygen-
pyrone carbonyl carboxyl ester hydroxyl
containing activated carbon surfaces in order to clarify the
detailed interactions of H2S with oxygen groups. Oxygen C(11)−C(8) 0.440 0.406 0.407 0.408 0.406
groups can be divided into two groups according to their acidic C(8)−C(9) 0.383 0.329 0.328 0.335 0.333
or basic character. The well-defined acidic oxygen groups on C(9)−C(10) 0.289 0.363 0.343 0.346 0.338
carbon surface are carboxyl, ester, and hydroxyl groups. The C(10)−C(20) 0.271 0.264 0.300 0.300 0.329
basic oxygen groups are commonly assumed to be pyrone and C(20)−C(23) 0.396 0.394 0.385 0.376 0.329
carbonyl groups.28 The pyrone group, formed by air exposure C(23)−C(26) 0.207 0.213 0.405 0.271 0.382
of heat-treated activated carbon, is the combination of non- C−O 0.581 0.576 0.546 0.622 0.316

B DOI: 10.1021/acs.iecr.9b00507
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Industrial & Engineering Chemistry Research
3. RESULTS AND DISCUSSION
3.1. Adsorption of H2S on Activated Carbon. The
adsorption of H2S on activated carbon surface was discussed.19
Two stable structures were obtained, including A and B, as
shown in Figure 2. A C−S species is formed by H2S adsorption
Figure 2. H2S adsorption on activated carbon surface.
in A with an adsorption energy of −664.9 kJ/mol. H2S
decomposes into SH and H atom in B, and then these two
fragments adsorb separately on surface C sites. C−SH is
formed by H2S adsorption in B. The adsorption energy of H2S
in B is −442.0 kJ/mol, which is lower than that in A. This
implies that C−S species is more likely to be formed by H2S
adsorption. The adsorption of H2S on carbon is highly
exothermic process, and belongs to chemisorption. Sun et al.33
performed H2S removal experiments by activated carbon, and
suggested that chemisorption was involved in the adsorption
process.
3.2. Effect of Pyrone Group on H2S Adsorption. The
effects of basic oxygen groups on H2S adsorption were studied
first. To exactly clarify the influence of pyrone group on H2S
adsorption, all the possible locations and orientations of H2S
approaching pyrone surface were considered. Four stable
surface complexes were obtained after optimization, namely,
1A, 1B, 1C, and 1D, as shown in Figure 3a. It can be inferred
from these surface complexes that H2S is likely to adsorb
Figure 3. Interactions of H2S with basic oxygen functional groups: (a) H2S on pyrone; (b) H2S on carbonyl.
C DOI: 10.1021/acs.iecr.9b00507
Article
dissociatively on pyrone. 1A and 1B represent the structures of
H2S adsorption on neighboring C sites of O atom. C−S species
is formed in 1A, and C−SH species is formed in 1B. C−S
bond length is 1.664 Å in 1A, which is 0.098 Å shorter than
that in 1B. The adsorption energy of H2S is −757.1 kJ/mol in
1A and −508.2 kJ/mol in 1B. The formations of C−S in 1A
and C−SH in 1B are more exothermic than that in A and B.
This indicates that pyrone group can improve the adsorption
of H2S on activated carbon surface. O−H bond is formed by
the reaction of H2S with O atom in 1C and 1D. The bond
lengths of C−O in 1C and 1D have been elongated by the
reaction of H2S with O atom, indicating that the interaction of
C atom with O atom has been weakened. The adsorption
energies of H2S in 1C and 1D are −557.7 and −259.1 kJ/mol,
respectively, suggesting that the reaction of H2S with pyrone is
highly exothermic. Therefore, although the adsorption energies
of H2S in 1C and 1D are lower than that in A and B, there are
still possibilities for their formation.
The bond populations of H2S on pyrone are listed in Table
2. The values of C−S and C−O bond populations in these
structures are highly positive. This implies the formations of
strong covalent bonds in these structures, and the C−S, C−
SH, and C−OH species formed by H2S adsorption on pyrone
are very stable. The bond population of C−S in 1A is 0.498,
which is higher than that in the other structures, suggesting the
interaction of C atom with S atom in 1A is stronger. The C−S
bond populations in 1B and 1D are lower than those in 1A and
1C. This means that the interaction of C atom with S atom in
C−S species is stronger than that in C−SH species.
Furthermore, the bond populations of C−O in 1C and 1D
are lower than those in pyrone, indicating that the C−O bond
has been weakened by the reaction of H2S with O atom.
3.3. Effect of Carbonyl Group on H2S Adsorption. The
interactions of H2S with carbonyl were investigated by allowing
H2S to approach carbonyl surface from different directions.
Four stable surface complexes were obtained after optimiza-
tion, as shown in Figure 3b. H2S adsorbs on neighboring C
sites of O atom in structures 2A and 2B by forming C−S
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Industrial & Engineering Chemistry Research Article

Table 2. Mulliken Populations for H2S on Basic Oxygen Functional Groups

pyrone carbonyl
bond 1A 1B 1C 1D 2A 2B 2C 2D
C(11)−C(8) 0.504 0.415 0.417 0.448 0.502 0.417 0.424 0.403
C(8)−C(9) 0.230 0.371 0.347 0.373 0.233 0.345 0.316 0.316
C(9)−C(10) 0.231 0.360 0.402 0.338 0.238 0.389 0.428 0.389
C(10)−C(20) 0.374 0.267 0.277 0.363 0.378 0.252 0.261 0.330
C(20)−C(23) 0.377 0.428 0.286 0.271 0.358 0.421 0.277 0.312
C(23)−C(26) 0.255 0.283 0.377 0.429 0.263 0.290 0.381 0.384
C−O 0.555 0.466 0.350 0.254 0.439 0.462 0.349 0.321
C−S 0.498 0.314 0.421 0.281 0.477 0.318 0.430 0.251

Figure 4. Interactions of H2S with acidic oxygen functional groups: (a) H2S on ester; (b) H2S on carboxyl; (c) H2S on hydroxyl.

species in 2A and C−SH species in 2B. The bond length of
C−S is 1.676 Å in 2A and 1.761 Å in 2B. The adsorption
energy of H2S in 2A is −674.7 kJ/mol, which is close to that in
A. Meanwhile, H2S adsorption energy is −443.5 kJ/mol in 2B,
which is only 1.5 kJ/mol higher than that in B. The above
results suggest that carbonyl group has no obvious effect on
H2S adsorption on neighboring C sites of O atom. Carbonyl
group can also react with H2S by forming C−OH species, as
indicated by 2C and 2D. The adsorption energy of H2S is
−499.4 kJ/mol in 2C and −228.6 kJ/mol in 2D. However, the
reaction of H2S with carbonyl is a less exothermic process than
D DOI: 10.1021/acs.iecr.9b00507
that with pyrone. This is owing to the presence of non-
neighboring epoxy O atom, which evidently increases the
activity of carbonyl O atom for H2S adsorption. More
information is derived from the bond population analyses, as
listed in Table 2. It is clear that the C−S, C−SH, and C−OH
species formed by H2S adsorption on carbonyl are very stable,
since the values of the bond populations of them are highly
positive. Shi et al.34 analyzed the adsorption of H2S on
activated carbon by using XPS and they found that C−S
groups can be formed by H2S adsorption.
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Table 3. Mulliken Populations for H2S on Acidic Oxygen Functional Groups

ester carboxyl hydroxyl
bond 3A 3B 3C 3D 4A 4B 4C 5A 5B
C(11)−C(8) 0.504 0.421 0.422 0.400 0.505 0.420 0.400 0.504 0.421
C(8)−C(9) 0.227 0.355 0.319 0.316 0.225 0.340 0.308 0.234 0.357
C(9)−C(10) 0.227 0.391 0.440 0.433 0.217 0.386 0.363 0.228 0.386
C(10)−C(20) 0.415 0.366 0.245 0.309 0.401 0.305 0.271 0.422 0.384
C(20)−C(23) 0.356 0.328 0.267 0.363 0.347 0.352 0.415 0.305 0.274
C(23)−C(26) 0.294 0.332 0.423 0.366 0.437 0.421 0.364 0.405 0.433
C−O 0.605 0.518 0.278 0.352 0.535 0.530 0.347 0.310 0.248
C−S 0.497 0.303 0.480 0.265 0.503 0.297 0.210 0.490 0.282

The calculation results are in agreement with the
experimental results that oxygen groups on carbon surface
can take part in H2S adsorption and even react with H2S
directly.35 Comparing the adsorption of H2S on pyrone, the
formations of C−S, C−SH, and O−H species of H2S on
carbonyl are less exothermic. It is thus sufficient to point out
that the presence of epoxy O atom improves significantly the
reactivity of carbonyl O atom in pyrone group for H2S
adsorption. This makes pyrone group more effective for H2S
adsorption than carbonyl group. The pyrone group plays a dual
role, not only facilitating the adsorption of H2S on neighboring
C sites but also offering an active site to react directly with
H2S. The basic oxygen groups are effective sites on the carbon
surface for H2S adsorption. H2S can react with carbonyl O
atom in pyrone and carbonyl leading to the formation of C−
OH species. Li et al.36 carried out an experiment to investigate
the removal of H2S by activated carbon and suggested that
pyrone groups can react with H2S. Feng et al.37 reported
experimentally that H2S removal ability of activated carbon was
correlated well with the amount of basic oxygen groups. They
suggested that H2S could be oxidized by oxygen groups during
the process of adsorption. Our calculation results are
consistent with the experimental results.
3.4. Effect of Ester Group on H2S Adsorption. The
roles of acidic oxygen groups in H2S adsorption on activated
carbon were investigated in the similar manner. Four stable
surface complexes, 3A, 3B, 3C, and 3D, were obtained by H2S
adsorption on different sites of ester, as shown in Figure 4a.
The adsorption energy of H2S is −674.2 kJ/mol in complex
3A, which is close to that in A. Meanwhile, the adsorption
energy of H2S in 3B is only 2.7 kJ/mol higher than that of B.
The results reveal that ester group has little effect on H2S
adsorption on neighboring C sites. Ester can also act as active
site to react with H2S, but the reaction of ester with H2S is less
exothermic than that with pyrone. O−H bond is formed in 3C
and 3D by the reactions of H2S with ester. The adsorption
energies of H2S in 3C and 3D are −327.9 and −116.6 kJ/mol,
respectively.
The bond populations of H2S on ester are listed in Table 3.
The values of C−S and C−O bond populations in these
complexes are highly positive. This implies that C−S, C−SH,
and C−OH species formed by H2S adsorption on ester are
very stable. The interaction of C atom with S atom in 3A is
stronger than that in the other structures, as indicated by the
higher C−S bond population.
The results of H2S on ester is different from those on
pyrone. The exothermicity of the adsorption of H2S on ester is
obviously lower than that on pyrone, indicating that pyrone is
more active for H2S adsorption. Upon careful examination of
the structures of pyrone and ester, it can be determined that
E DOI: 10.1021/acs.iecr.9b00507
the difference in H2S adsorption on pyrone and ester is closely
related to the relative position of the carbonyl O atom and
epoxy O atom, which plays a key role in the activity of oxygen
groups.
3.5. Effect of Carboxyl Group on H2S Adsorption. The
interactions of H2S with carboxyl via different approaches were
investigated. The stable surface complexes of H2S on carboxyl
are shown in Figure 4b, including 4A, 4B, and 4C. In 4A and
4B, the dissociated fragments of H2S adsorb on neighboring C
sites of carboxyl. A C−S species is formed in 4A with an
adsorption energy of −651.9 kJ/mol, which is close to the
adsorption of H2S in A. The bond length of C−S is 1.663 Å in
4A. C−SH species is formed in 4B with a binding energy of
−387.1 kJ/mol, which is lower than that in B, indicating that
carboxyl group can inhibit the formation of C−SH on activated
carbon. A carboxyl group can also react directly with H2S by
forming C−OH species. However, the reaction of H2S with
carboxyl is less exothermic than that of pyrone. This means
that the pyrone group is more active for H2S adsorption than is
the carboxyl group.
The bond populations of H2S on carboxyl are listed in Table
3. It appears that the interaction of C atom with S atom in 4A
is stronger than that in the other structures because of the
higher C−S bond population. Moreover, C−O bond
population decreases from 0.546 to 0.347 in 4C. This proves
that C−O bond has been weakened by the reaction of H2S
with carboxyl.
3.6. Effect of Hydroxyl Group on H2S Adsorption. The
following discusses the interactions of H2S with hydroxyl, and
two stable surface complexes are obtained, as shown in Figure
4c. It is clear that H2S tends to adsorb dissociatively on surface
C sites by forming C−S and C−SH species. The adsorption
energy of H2S is −672.5 kJ/mol in 5A and −409.1 kJ/mol in
5B. Hydroxyl group hinders the formation of C−SH species on
activated carbon. Unlike the results of carboxyl and ester, H2S
does not likely to react with hydroxyl. The hydroxyl like
oxygen functionalities are not surface-active centers for H2S
adsorption.
For the purposes of the present discussion, it suffices to
point out that H2S can react directly with carbonyl O atom in
oxygen functional groups leading to the forming of C−OH
species on activated carbon surface. The reactivity of oxygen
groups for H2S adsorption is related to their acid−base
properties. The pyrone group is more effective for H2S
adsorption than the other oxygen groups. The presence of a
pyrone group can improve H2S removal ability of activated
carbon via enhancing the activity of neighboring C sites.
Moreover, a pyrone group is an active center which can react
directly with H2S. In addition, carboxyl and hydroxyl groups
inhibit the formation of C−SH species on activated. This
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
indicates that the presence of carboxyl and hydroxyl groups has
negative effect on H2S adsorption on activated carbon. Guo et
al.38 investigated experimentally the removal of H2S by
activated carbons derived from oil palm shell. They suggested
that H atom in H2S can react with carbonyl (CO) oxygen
groups. Leuch et al.35 studied the H2S adsorption on activated
carbon surface. They found that the removal of H2S was
produced mainly by oxidation reactions. The basic oxygen
groups contribute particularly in H2S removal. Therefore, the
calculation result is in agreement with the available
experimental results.
4. CONCLUSION
Density functional theory was used to investigate the
interactions of H2S with different oxygen functional groups
on activated carbon surface. This provides an insight into the
roles of oxygen groups in the process of H2S adsorption. H2S
can react directly with carbonyl oxygen atom in pyrone,
carbonyl, ester, and carboxyl groups by forming C−S, C−SH,
and C−OH species. A pyrone group can not only improve the
adsorption of H2S by enhancing the activity of surface C sites
but also react directly with H2S by forming C−OH species.
Carbonyl and ester have no obvious effects on H2S adsorption
on surface C sites, and they are weak active sites to react with
H2S. Carboxyl and hydroxyl groups may inhibit the adsorption
of H2S on activated carbon surface. The presence of non-
neighboring epoxy oxygen atom can enhance the activity of
carbonyl oxygen atom for H2S adsorption. The relative
position of the carbonyl oxygen atom and epoxy oxygen
atom governs the activity of oxygen groups. These calculation
results serve to highlight the complexity of the interactions of
H2S with oxygen groups on the carbon surface.
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +86 27 87545526. Fax: +86 27 87545526. E-mail:
liujing27@mail.hust.edu.cn.
ORCID
Jing Liu: 0000-0001-6520-9612
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by National Key R&D Program of
China (2018YFC1901303), and National Natural Science
Foundation of China (51606078).
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G DOI: 10.1021/acs.iecr.9b00507
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX