Chemical Engineering Journal 431 (2022) 134097

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Chemical Engineering Journal

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CuFe2O4/activated carbon adsorbents enhance H2S adsorption and

catalytic oxidation from humidified air at room temperature
Shanshan Chen a, Yiyue Guo a, Jianan Zhang a, Yingchun Guo a, Xiaoyi Liang a, b, *
a
State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
b
Key Laboratory of Specially Functional Polymeric Materials and Related Technology (Ministry of Education), School of Chemical Engineering, East China University of
Science and Technology, Shanghai 200237, China

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

Keywords: A variety of CuFe2O4-based adsorbents with different active phase loadings were synthesized to remove H2S from
CuFe2O4 humidified air at room temperature. The materials were characterized by adsorption of nitrogen, SEM-EDX, XPS,
Activated carbon XRD, and TGA. According to the results, the activated carbon with 20 wt% CuFe2O4 exhibited the best H2S
H2S removal
adsorption performance, reaching 292 mg/mL (667 mg/g). Furthermore, the H2S adsorption capacity reduced by
Catalytic oxidation
Reactive adsorption
7% after two cycles of thermal regeneration. During the desulfurization process, FeOOH formed as an inter­
mediate played a catalytic role. The products comprised sulfide, elemental sulfur, and sulfates. Elemental sulfur
was the predominant product. The H2S removal involved both reactive adsorption and catalytic oxidation. In
addition to the chemical properties of the active phase, structural characteristics like pore volume also deter­
mined the adsorption capacity. Pore volume of less than 6 nm pores could enhance catalyst dispersion, provide
adsorption centers and store the oxidation products. This study will offer novel insights for the efficient synthesis
of metal oxide-based adsorbents and the extensive application of their reactive adsorption capacity at the
nanoscale level.

1. Introduction to its developed pore structure, large surface area, and unique surface
chemical properties. In addition, the use of metal oxides as desulfurizers
Hydrogen sulfide (H2S) is a colorless, corrosive, flammable, and is gaining tremendous interest among researchers due to their strong
highly toxic gas with the characteristic foul odor of rotten eggs [1]. The chemical affinity for H2S. Thus, researchers have recently examined the
olfactory threshold of H2S is 0.41 ppb in the air. It can irritate the eyes, reaction of H2S with oxides of Cu [8], Fe [9], Zn [10], Mg [11], and other
nose, and throat even at a low concentration of 5 ppm [2]. Exposure to metal oxides. Nonetheless, bare metal oxides have poor H2S removal
H2S causes olfactory nerve paralysis at high levels (100–150 ppm), capacity. The adsorbents formed by loading metal oxides on the porous
resulting in the loss of the ability to smell the gas even though it still carbon materials have both an active phase and a developed porosity,
exists [2]. Generally, H2S is produced by industrial processes such as thereby improving the desulfurization performance notably. The
coal pyrolysis, natural gas purification, crude oil refining, and waste­ removal of H2S from humidified air at room temperature is performed
water treatment [3]. H2S corrodes metal pipes and equipment and using ZnFe2O4 loaded on activated carbon by Yang et al. [12]. The
pollutes the environment, severely risks human health. Thus, removing adsorption capacity of H2S is negligible for the pure ZnFe2O4 sample or
H2S from industrial gases is crucial, and strict control of H2S emission activated carbon. However, the removal capacity of H2S increases
standards is followed globally. Recently, the research on novel effective considerably with activated carbon loaded with 10% ZnFe2O4.
H2S adsorbents has been reinforced continuously. It has been shown that ZnFe2O4-based adsorbents exhibit appealing
Catalytic oxidation of H2S into solid sulfur is considered a promising desulfurization performance at room temperature [12-14]. The synthe­
strategy to remove H2S. In recent studies, carbon-based supports, such as sized nano ferrites show distinguished behavior for optical, electro­
activated carbons [4], carbon aerogels [5], graphene [6], and carbon chemical, and photocatalytic performance. They are widely used in
nanotubes [7], have been reported for the desulfurization process. water remediation. The better photosensitivity of CuFe2O4 than that of
Among various supports, activated carbon is frequently utilized owing ZnFe2O4 is due to its smaller charge transfer resistance [15]. ZnFe2O4 is

* Corresponding author at: East China University of Science and Technology, Shanghai, China Meilong Road 130, 200237.
E-mail address: [email protected] (X. Liang).

https://doi.org/10.1016/j.cej.2021.134097
Received 26 October 2021; Received in revised form 6 December 2021; Accepted 8 December 2021
Available online 13 December 2021
1385-8947/© 2021 Published by Elsevier B.V.
S. Chen et al. Chemical Engineering Journal 431 (2022) 134097

Fig. 1. SEM image of CFOW-20 (a); the corresponding (to b) element mapping of C, O, Cu, and Fe (c, d, e, f).

not as efficient as CuFe2O4 in removing organic matter from aqueous conical flask filled with the activated carbon. The resultant mixture was
solutions [16]. From this, we presumed that their performance in the gas placed in a shaker at 28 ◦ C for 24 h. Subsequently, the activated carbon
phase might be better than that of ZnFe2O4-based adsorbents. Therefore, was placed in an oven at 40 ◦ C overnight. Eventually, the dried mixture
desulfurization experiments are carried out with CuFe2O4-based adsor­ was calcined in a tube furnace at 400 ◦ C in N2 atmosphere for 3 h while
bents at room temperature. Unfortunately, as far as we know, there are maintaining the heating rate at 2 ◦ C/min. The experimental procedure is
almost no studies on the removal of H2S by CuFe2O4-based desulfurizers. shown in Fig. S1 (in Supplementary Material). The synthesized adsor­
Thus, a series of CuFe2O4-based adsorbents are prepared to obtain high- bents were called CFOW-x, where CFO and W represented CuFe2O4 and
efficiency desulfurizers at room temperature. The activated carbon is WAC, respectively, and × expressed the content of CuFe2O4. After
selected as the support because of its highly developed pore structure desulfurization, the spent samples are denoted by adding the letter “E”
and unique surface chemical properties, which are essential for the to their names (CFOW-x-E).
highly dispersed active phase [17].
For the above reasons, it is thought worthwhile to prepare a series of 2.3. Characterization
CuFe2O4-based adsorbents to remove H2S from moist air at room tem­
perature. Wood-based activated carbon is chosen as the support due to The surface morphology of the material was characterized by scan­
its micro/mesoporous structure and tunable surface chemistry. Both ning electron microscopy (SEM) using Zeiss Sigma HD with an accel­
these properties are significant for high dispersion active phase depo­ eration voltage of 5 kV. An electron dispersive X-ray spectroscopy (EDX)
sition. The structure–activity relationship of the adsorbents is deter­ analysis was conducted at a magnification of 5 KX with an accelerating
mined on the basis of the adsorption performance and comprehensive voltage of 15 kV to estimate the elemental content of the surface. The
characterization. By analyzing the collected data, we presented a specific surface area and pore structure distributions of the materials
detailed report introducing the cost-effective and regenerable adsor­ were analyzed using Quadrasorb SI Chemisorption Analyzer (Quan­
bents for the removal of H2S. The adsorbents have great feasibility and tachrome, USA). Before the experiments, the samples were degassed in a
capability to remove H2S from humidified air at room temperature. vacuum at 120 ◦ C for 12 h, followed by N2 adsorption and desorption
experiments at 77 K. The specific surface area of the materials was
2. Experimental calculated by the Brunauer-Emmett-Teller (BET) method. The total pore
volume (Vt), the micropore volume (Vmic), the mesopore volume (Vmes),
2.1. Materials and pore size distributions (PSDs) were evaluated by density functional
theory (DFT model) [18]. X-ray diffraction (XRD) analysis was con­
Cupric nitrate (Cu(NO3)2) and ferric nitrate hydrate (Fe ducted on a Bruker AXS D8 Advance X-ray powder diffractometer with
(NO3)3⋅9H2O) were purchased from Shanghai Macklin Biochemical Co., Cu Kα radiation (λ = 0.15406 nm) to determine the phase and crystal
Ltd. Commercial wood-based activated carbon was obtained from Fujian structure of materials. The step length was 0.02◦ , the scanning speed was
Xinsen Carbon Co. Ltd., chemically activated with phosphoric acid, 5◦ /min, and the scanning range was 10◦ ~ 80◦ . X-ray photoelectron
referred to as WAC. Its particle size is between 20 and 40 mesh. All the spectroscopy (XPS) was performed on a Thermo Scientific Escalab 250XI
chemicals were used in reagent grade without additional purification. to estimate the surface chemical compositions of materials. The excita­
tion source was monochromatic Al Kα. Peak processing was performed
2.2. Preparation of the adsorbents using XPSPEAK software, a nonlinear least-square curve fitting program.
Temperature Programmed Desorption (TPD) was carried out on a
Adsorbents with different loadings of CuFe2O4 (5 wt%, 10 wt%, 20 Micromeritics Autochem II 2920 unit equipped with a thermal con­
wt%, and 25 wt%) were prepared using a wet impregnation method ductivity detector (TCD), and the temperature was increased from 80 to
followed by a calcination process. The molar ratio of CuO to Fe2O3 was 600 ◦ C. The thermogravimetric analysis (TGA) was performed using the
1:1. The weighed Fe(NO3)3⋅9H2O and Cu(NO3)2 were dissolved in an SDT Q600 (TA Company, USA), primarily to measure the difference in
appropriate amount of water, and the solution was transferred to a the thermogravimetric weight loss of modified activated carbons before

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S. Chen et al. Chemical Engineering Journal 431 (2022) 134097

Fig. 2. The PSDs of the samples by using the DFT method (a); dependence of surface area and pore volume of less than 6 nm pores (S0.6–6 nm and V0.6–6 nm) on the
CuFe2O4 loadings (b).

and after the adsorption of H2S. The TGA was performed under a ni­ EDX analysis of the original activated carbon is shown in Fig. S3 (in
trogen atmosphere, the heating rate was maintained at 10 ◦ C/min, the Supplementary Material). It can be seen that the unmodified activated
flow rate was 100 mL/min, and the temperature was increased from carbon contains C, O, Na, P, and Cl elements and the contents of them
room temperature to 850 ◦ C. The pH of the activated carbons suspension are 87.97 at.%, 10.16 at.%, 1.28 at.%, 0.47 at.%, and 0.12 at.%,
provided information about the average acidity/alkalinity of the ad­ respectively. In the yellow area, C, O, Na, P, and Cl elements have
sorbents. A weighed mass (0.4 g) of dried activated carbon powder was increasing response intensity in order, which is related to the atomic
added to 20 mL deionized water. The suspension was placed in an number of the elements [20-22]. The content of P element is higher than
oscillating shaking water bath maintained at constant temperature for that of Cl element, but the distribution of P element in the yellow region
24 h. The pH of the filtrate was measured using a pH meter (PHS-3E). is quite different from that of Cl element, which is not related to the
content of elements. The same phenomenon occurs in modified acti­
vated carbon in Fig. 1 (in the yellow areas). The atomic number of O
2.4. Breakthrough tests
element is smaller than that of Cu and Fe elements, and the corre­
sponding signal will not be as good as that of Cu and Fe. Our sample is a
The H2S breakthrough capacity measurements were performed at
three-dimensional structure, and Mapping is done by scanning a specific
room temperature using a fixed-bed column. The home-made test was
surface area of the samples. The surface of activated carbon is uneven
designed based on the standard test ASTM D6646–03 according to the
and has holes, which may also cause the signal of O element to be
fixed space velocity and modified to a small-scale laboratory sample
inferior to that of Fe and Cu. Atomic concentrations of C, O, Cu, and Fe
[19]. Breakthrough capacity was determined by continuously passing a
are 84.46 at.%, 13.72 at.%, 0.60 at.%, and 1.21 at.%, respectively. The
stream of moist air (relative humidity 80% at room temperature, 922
atomic ratio of copper to iron was 1:2, which is in agreement with the
mL/min flow rate) containing 1% hydrogen sulfide (10000 ppm, 240.6
molecular formula of CuFe2O4.
mL/min) through a glass column of activated carbon (diameter 5.08 cm;
The N2 adsorption and desorption isotherms of the prepared samples
bed height 4.6 cm) until H2S appears in the effluent gas. The testing
are shown in Fig. S4 (in Supplementary Material). All samples had
equipment scheme is described in Fig. S2 (in Supplementary Material).
similar isotherm types with the original carbon support, but the amount
The hydrogen sulfide breakthrough capacity of the test samples was
of N2 adsorbed slowly decreased as the content of CuFe2O4 grew. This
calculated using the following equation:
indicated that the structure of activated carbon changed, but it was not
C
×F×T×
1L 1mol 34.1gH2 S significantly affected by CuFe2O4 deposition and the heat treatment.
g − H2 S × × (1) According to the IUPAC classification [23], all samples exhibit the Type I
= 100 1000mL 22.4L mol
mL − AC V N2 adsorption isotherm with H4 hysteresis loop, representing their hi­
erarchical pore structure. The isotherms experience a sharp rise at lower
where C is the concentration of hydrogen sulfide in the air stream (%); F
P/P0, implying the presence of micropores in the sample structure. The
is total H2S/air flow rate (1162.6 mL/min); T is time to breakthrough
hysteresis loop for the filling and emptying of mesopores at the higher P/
(min); V is the actual volume of the carbon bed in the absorption tube
P0 range is related to the presence of mesopores. The PSDs by using the
(mL).
DFT method (Fig. 2a) demonstrate that pore volume of pores below 6 nm
The H2S breakthrough capacity (mg-H2S/g-AC) was determined
decreased with an increasing content of CuFe2O4. The cumulative pore
using the following equation:
volume distributions of the samples are given in Fig. S5 (in Supple­
mg-H2 S mg H2 S/mL AC mentary Material). The volume of pores above 6 nm for WAC and
= (2)
g-AC apparent density CFOW-20 is 0.059 and 0.057 cm3/g, respectively. The pore volume of
the modified activated carbon is only 0.002 cm3/g smaller than that of
3. Results and discussion the original activated carbon. It can be observed that the surface area
and pore volume of pores less than 6 nm pores decline almost linearly
3.1. Characterization of the fresh adsorbents with growing CuFe2O4 loading in Fig. 2b, and their regression values
(R2) are 0.9976 and 0.9907, respectively, which are higher than those of
Fig. 1 illustrates a representative SEM image of the CFOW-20 surface area and pore volume corresponding to different range of pore
adsorbent and distribution maps of C, O, Cu, and Fe obtained through size displayed in Fig. S6 (in Supplementary Material). The results
EDX analysis. The SEM image of the CFOW-20 adsorbent showed the demonstrated the deposition of the active phase primarily occurred in
rich pores channel and the rough and irregular surface (Fig. 1a). The pores smaller than 6 nm.

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S. Chen et al. Chemical Engineering Journal 431 (2022) 134097

(2 2 0), and (2 2 4) planes of CuFe2O4. However, these characteristic

peaks are not visible in the diffraction patterns of CFOW-5, CFOW-10,
and CFOW-20, which can be attributed to the fact that the copper ferrite
was uniformly dispersed on the surface of the supports.
Fig. 4(a, b, c, d) depict XPS results on the CFOW-20 sample. Fig. 4a
exhibits the high-resolution C1s core energy level spectrum. It is
deconvoluted into four peaks at 284.8 eV, 286.1 eV, 287.2 eV, and
288.5 eV, corresponding to C = C/C–C in aromatic substances, C-O
(epoxy and hydroxyl), C = O (carbonyl), and O-C = O (carboxyl) groups,
respectively [12,25]. Fig. 4b displays the O1s spectrum, which is
assigned to C = O (oxygen in carbonyl and ketones) and C-O (oxygen in
epoxy and hydroxyl) at 531.1 eV and 533.3 eV, correspondingly, ac­
counting for 41.83 at.% and 26.06 at.% [26]. Oxygen ascribed to
adsorbed H2O/chemically adsorbed O2 (32.11 at.%) is detected at 534.3
eV [12]. For the Cu2p spectrum in Fig. 4c, there is a peak at 933.5 eV,
corresponding to Cu2p3/2 [27]. This peak has a satellite intensity near
941.3 eV, indicating the existence of Cu2+ species. The intensity ratio of
Fig. 3. XRD pattern of the samples.
the satellite peak to the main peak (IS/IM) is 0.54, which is similar to the
IS/IM of CuO (0.5–0.6) [28]. There is also a peak of Cu2p1/2 at 953.3 eV,
which exhibits the Cu(II) oxidation state [29]. The XPS Fe2p spectrum is
The detailed textural parameters are listed in Table 2. The original
fitted to obtain the detailed distribution of deconvolution peaks, as
activated carbon has a large surface area of 1365 m2/g and a pore vol­
shown in Fig. 4d. Two peaks at 711.4 eV and 724.8 eV are considered to
ume of 0.865 cm3/g. With the growth of CuFe2O4 loading, the surface
be the characteristic peaks of Fe2p3/2 and Fe2p1/2, respectively [49]. The
area and pore volume decreased from 4% to 19%. In summary, CuFe2O4
satellite peak positioned at 719.2 eV confirms that the oxidation state of
successfully occupied micropores and mesopores below 6 nm.
Fe in CFOW-20 is Fe3+ [30,31]. All the above results prove the CuFe2O4
The XRD patterns of WAC and these as-prepared samples are
exists in CFOW-20.
compared in Fig. 3. Two broad peaks are seen at around 26◦ and 43◦
corresponding to the diffraction peaks of the (0 0 2) and (1 0 0) planes of
3.2. Evaluation of the H2S removal performance
the amorphous carbon material, respectively [24]. The CuFe2O4 phase
(PDF#34–0425) can be examined from the characteristic peaks of the
Fig. 5 displays the H2S breakthrough capacities of the prepared ad­
diffraction patterns of CFOW-25 and correspond to the (1 0 3), (2 1 1),
sorbents, and detailed data are listed in Table S1 (in Supplementary

Fig. 4. XPS spectra of C1s (a), O1s (b), Cu2p (c) and Fe2p (d) of the CFOW-20 sample.

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S. Chen et al. Chemical Engineering Journal 431 (2022) 134097

CuFe2 O4 + 4H2 S→CuS + Fe2 S3 + 4H2 O (3)

From the calculated results, it can be seen that the actual break­
through capacity of CFOW-5, CFOW-10, CFOW-20, and CFOW-25 is
substantially higher than the stoichiometric reaction capacity (11.60,
7.85, 5.87, and 3.09 times, respectively). This implies the desulfuriza­
tion process may not only involve reactive adsorption but may also
include other processes, like catalytic oxidation.
It is reported that the high pH value of the adsorbents improves the
removal of H2S by providing an alkaline environment in which H2S can
be dissociated into HS– or S2–, which is favorable for the catalytic
oxidation of H2S [17,38-41]. The pH values of all adsorbents are illus­
trated in Table S1, decreasing marginally with growing CuFe2O4 con­
tent. After desulfurization, the pH value dropped sharply, inferring the
products contained acidic substances. Further detailed information
about the chemical composition of the exhausted samples is obtained
from XPS. Fig. 6a depicts the survey spectra of CFOW-20 and CFOW-
Fig. 5. The H2S adsorption capacity of the prepared adsorbents. 20E, and the S2s and S2p signals (circled in the red round) can be
clearly observed in the CFOW-20E. The forms of sulfur species during
the desulfurization process are examined by XPS (Fig. 6b). The gener­
Material). The raw activated carbon WAC has the lowest capacity of 89
ated sulfur species primarily comprise sulfides (S2p3/2, 161.7 eV; S2p1/2,
mg/mL-AC (214 mg/g-AC). After introducing CuFe2O4, the desulfur­
162.9 eV), element S (S2p3/2, 163.3 eV; S2p1/2, 164.5 eV), and sulfates
ization capacity of the activated carbon dramatically increased,
(S2p3/2, 167.6 eV; S2p1/2, 168.8 eV) [13,14,42-44]. The contributions of
achieving the maximum of 292 mg/mL-AC (667 mg/g-AC) for CFOW-
sulfur species to sulfides, element S, and sulfates were 4.13 at.%, 69.09
20. However, the breakthrough sulfur capacity declined as the
at.%, and 26.78 at.%, respectively.
CuFe2O4 content increased to 25 wt%. Table 1 summarizes the H2S
According to the Cu2p spectra (Fig. 6c), the binding energy of the
removal performance of desulfurizers reported in recent studies
used adsorbent shifts to lower values due to the differences in electro­
[4,6,14,32-37]. For industrial applications, fixed beds are used for
negativity between S and O atoms [12]. The observations confirmed that
desulfurization by carbon adsorbents, focusing on volumetric sulfur
CuS was formed in the exhausted adsorbents. It is worth noting that CuS
capacity. CFOW-20 is one of the adsorbents with the highest volumetric
does not have a satellite peak around 941.3 as CuO does [45]. The Fe2p
capacity, as shown in Table 1. The H2S removal capacity of alkaline
graphene aerogels is just 20 mg/mL (6.9%) higher than that of CFOW-
20. However, graphene aerogels are considerably more expensive than Table 2
activated carbon. The capacity of CFOW-20 is merely 8 mg/mL lower Pore structure parameters of the samples.
compared with the adsorption performance of Norit ROZ3 impregnated
Samples SBET (m2/ Vt (cm3/ Vmic (cm3/ Vmes (cm3/ Vmic/
with KI, which is pricey. Considering the cost performance, the g) g) g) g) Vt
comprehensive performance of CFOW-20 is superior to that of the re­
WAC 1365 0.865 0.417 0.448 0.482
ported adsorbents in industrial applications. CFOW-5 1303 0.828 0.400 0.428 0.483
CFOW-10 1233 0.785 0.381 0.404 0.485
3.3. Analysis of the H2S removal performance CFOW-20 1176 0.752 0.358 0.394 0.476
CFOW-25 1114 0.711 0.329 0.382 0.463
CFOW-5E 648 0.466 0.159 0.307 0.341
In order to better comprehend the H2S removal process, the stoi­
CFOW- 577 0.434 0.128 0.306 0.295
chiometric reaction capacity of the adsorbents is calculated based on the 10E
content of the active phase, as shown in Fig. 5 and Table S1. The stoi­ CFOW- 277 0.264 0.008 0.256 0.030
chiometric reaction between CuFe2 O4 and H2S, excluding the oxidation 20E
CFOW- 555 0.404 0.129 0.275 0.319
reaction of H2S, is expected to take place as follows:
25E

Table 1
H2S removal capacities of adsorbents at experimental conditions.
Samples Conditions H2S breakthrough capacity Costs Reference

mg/mL mg/g

CFOW-20 H2S: 10000 ppm; O2: 21%; RH: 80%; Room temperature 292 667 $a This work
Alkaline graphene aerogels H2S: 1000 ppm; O2: 1%; RH: 80%; Temperature: 30 ◦ C 310 3190 $$$$a (Pan et al., 2020)
ZnO/GO H2S: 1000 ppm; O2: 21%; RH: 70%; Room temperature 43 115 $$$$a (Mabayoje et al., 2013)
copper (hydr) oxychlorides/Gr H2S: 1000 ppm; O2: 21%; RH: 75%; Room temperature 42 160 $$$$a (Mabayoje et al., 2012)
Norit ROZ3 H2S: 10000 ppm; O2: 21%; RH: 80%; Room temperature 300b 380b $$$a
Darco H2S H2S: 10000 ppm; O2: 21%; RH: 80%; Room temperature 200b 600b $$a
CuO/AC H2S: 3000 ppm; O2: 21%; RH: 80%; Room temperature 249c 497 $a (Nguyen-Thanh & Bandosz, 2005)
MgO/AC H2S: 10000 ppm; O2: 21%; RH: 80%; Temperature: 25℃ 138c 275 $a (Siriwardane et al., 2017)
N-doped/AC H2S: 3000 ppm; O2: 21%; RH: 80%; Temperature: 25℃ 110 276 $a (Bandosz, 2002)
ZnFe2O4/AC H2S: 1000 ppm; O2: 21%; RH: 70%; Room temperature 85c 170 $a (Yang, de Falco, et al., 2020)
Cu0.5Zn0.5/AC H2S: 100 ppmv; O2: 2500 ppmv; RH: 50%; Room temperature 59c 118 $a (Cimino et al., 2020)
ZnO/SiO2 H2S: 1000 ppm; O2: 21%; RH: 55%; Temperature: 25℃ 436 $a (Wang et al., 2008)
a
$, $$, $$$, and $$$$ stand for low, medium, expensive, and very high prices, respectively.
b
According to the product specification of the manufacturer.
c
Volumetric sulfur capacity is calculated according to the specific gravity of activated carbon 0.5, which is higher than the general value.

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S. Chen et al. Chemical Engineering Journal 431 (2022) 134097

Fig. 6. XPS survey spectra of the CFOW-20 and CFOW-20E (a); XPS spectra of S2p (b), Cu2p (c) and Fe2p (d) of CFOW-20E.

comes from FeOOH, which may be generated by oxidation of FeS and

FeS2 in humidified air (Eq.(5)). Similar results are obtained by Yang
et al., Cao et al., and Wang et al. [12,46,47]. It is worth noting that
FeOOH can also react with H2S to generate Fe2S3 and H2O (Eq.(6)) [46],
causing the reactions (Eq.(4) and Eq.(5)) to occur again. This led to a
chain reaction, eventually forming more elemental sulfur. The chain
reaction is a crucial reason for the remarkable H2S removal capacity of
the adsorbents. The plausible reaction mechanism is depicted in Fig. 9,
and the reactions involved are as follows:
Fe2 S3 →FeS + FeS2 (4)

3
FeS + FeS2 + O2 + H2 O→2 FeOOH + 3S (5)
2

2 FeOOH + 3 H2 S→Fe2 S3 + 4 H2 O (6)

Fig. 7 shows the TPD profile for the reference samples prepared by
impregnating CuSO4 and Fe2(SO4)2 on the wood-based activated carbon
before the adsorption of H2S. It is observed that the decomposition of
CuSO4 on the WAC starts at 200 ◦ C and centers at 350 ◦ C. The desorption
Fig. 7. SO2 release from the samples of CuSO4 and Fe2(SO4)2 impregnated on temperature of Fe2(SO4)2 impregnated on the WAC ranges from 300 ◦ C
the WAC. to 500 ◦ C. The breakdown temperature of CuSO4 was confirmed to be
between 550 and 700 ◦ C [48]. The decomposition temperature of
core energy level spectrum of the samples before and after the desul­ Fe2(SO4)2 is in the range of 625 ~ 710 ◦ C [49]. After the CuSO4 and
furization (Fig. 6d) reveals that the peaks of Fe2p3/2 and Fe2p1/2 in Fe2(SO4)2 were loaded on the WAC separately, the decomposition
CFOW-20E are consistent with fresh adsorbent. This confirms that the temperature of them decreased between 200 and 300 ◦ C, presumably
oxidation state of Fe in CFOW-20E is still Fe3+. Fe2S3 is well recognized due to the strong interaction between sulfates and the activated carbon
to be thermodynamically unstable [12,46]. Thus, even at ambient to promote the decomposition of sulfates [48,50].
temperature, Fe2S3 may easily decompose into FeS and FeS2 (Eq.(4)). As Additional information about the products of H2S oxidation is ob­
a result, there is a reason to believe that the Fe3+ detected in CFOW-20E tained from the analysis of the thermal behavior of samples in an inert

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Fig. 8. TG and DTG curves of the adsorbents in nitrogen before (a, b) and after desulfurization (c, d).

Fig. 9. Proposed reaction mechanism of H2S over the CuFe2O4/WAC.

atmosphere. The TG–DTG curves are exhibited in Fig. 8. For comparison, the decomposition of oxygen-containing groups. From the XPS analysis,
the original activated carbon WAC data is also included, and minuscule it can be inferred that the sulfide generated is mainly copper sulfide. The
weight loss is observed in the region of 100 ~ 900 ◦ C. The TG–DTG thermogravimetric analysis of CuS is shown in Fig. S7 (in the Supple­
curves of the CuFe2O4-based adsorbents are given in Fig. 8(a, b). The mentary Material). It can be seen that the decomposition temperature of
weight loss under 100 ◦ C is related to the removal of physically adsorbed CuS is in the range of 150 ~ 500 ◦ C. For the exhausted samples, as shown
H2O, while the weight loss between 600 and 900 ◦ C is concerned with in Fig. 8(c, d), the desorption temperatures of the sulfur species are

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observed between 150 and 500 ◦ C. In Fig. 8d, two peaks are clearly
visible. The decomposition of CuS occurs into two peaks, but the content
of CuS is quite low, as inferred from the XPS analysis where the
contribution of sulfur species to sulfide is only 4.13 at.%. The desorption
of H2SO4, CuSO4 and the removal of elemental sulfur from the largest
pores may be in the first peak (150 ~ 290 ◦ C). The second peak (290 ~
500 ◦ C) is mainly attributed to the desorption of elemental sulfur [5,7].
According to the results of the TPD test, the second peak may also be
partly attributed to the decomposition of CuSO4 and Fe2(SO4)2.
The results of XPS and the thermogravimetric analysis show that the
desulfurization products comprise sulfide, elemental sulfur, and sulfate.
Elemental sulfur is the predominant offspring. Therefore, in addition to
Eq.(5), elemental sulfur is also produced in Eq.(7). The alkaline envi­
ronment can enhance the decomposition of H2S into HS– or S2–. The
resulting HS– or S2– can be oxidized to elemental sulfur [4,7,17,43].
What’s more, the formation of sulfates may be attributed to the oxida­
tion of FeS2 (Eq.(8)) and/or elemental S (Eq.(9) and (10)) [36,51,52].
The possible reaction mechanism of H2S over CuFe2O4/WAC is depicted
in Fig. 9. The reaction equations are as follows:
Fig. 10. The PSDs of the carbon support, fresh and exhausted adsorbents.
2 H2 S + O2 →2 S + 2 H2 O (7)

Fig. 11. The deactivation mechanism of H2S over the CuFe2O4/WAC. (B and A stand for before and after desulfurization, respectively; 1, 2, 3, 4, 5, 6 stand for the
pore sizes of 0 ~ 1 nm, 1 ~ 2 nm, 2 ~ 3 nm, 3 ~ 4 nm, 4 ~ 5 nm, 5 ~ 6 nm, respectively).

8
S. Chen et al. Chemical Engineering Journal 431 (2022) 134097

which may be the one of the reasons for a slight decrease in the regen­
eration performance of samples. Fig. 12 exhibits the results of the three
cycles of adsorption/regeneration (denoted as R1, R2, and R3, respec­
tively). It can be seen that the regeneration efficiency of CFOW-20 was
quite well after two cycles of thermal regeneration, with a 7% reduction.

4. Conclusion

CuFe2O4 loaded on activated carbon can be used to provide an effi­

cient desulfurizer that can remove a substantial amount of H2S from
humidified air at room temperature. Wood-based activated carbon can
effectively disperse the active phase (CuFe2O4). The adsorbent CFOW-20
exhibits the best adsorption performance, reaching 292 mg/mL (667
mg/g), which is 5.87 times of the stoichiometric reaction capacity. The
result revealed that the desulfurization process involved both reactive
adsorption and catalytic oxidation. Moreover, because iron sulfide
species are not detected in the exhausted adsorbents, FeOOH may be
Fig. 12. The regeneration performance of CFOW-20. formed as an intermediate during the desulfurization process, which
plays a catalytic role and causes a chain reaction to produce more
elemental S. In addition to the chemical characteristics of the active
4 FeS2 + 15 O2 + 2 H2 O→2 Fe2 (SO4 )3 + 2 H2 SO4 (8) phase, the structural properties of adsorbents, particularly the volume of
pores below 6 nm, are also crucial for the removal performance of H2S,
3 S + 6 O2 + H2 O + CuFe2 O4 →Fe2 (SO4 )3 + CuSO4 + H2 O (9) because a high volume of pores smaller than 6 nm can improve catalyst
dispersion, provide adsorption centers, and store oxidation products.
9
3 S+ O2 + H2 O + 2 FeOOH→ Fe2 (SO4 )3 + 2 H2 O (10) The desulfurization products of all adsorbents comprised of sulfide,
2
elemental S, and sulfates. The primary desulfurization product of CFOW-
To determine the deactivation mechanism, the textural characteris­ 20 was elemental S. Further, the CFOW-20 adsorbent is regenerated at
tics of the exhausted adsorbents were evaluated. All exhausted samples 500 ◦ C, and its H2S removal capacity does not considerably diminish
show similar isotherms with the fresh samples, but the amount of N2 after two adsorption/regeneration cycles, which is critical for industrial
adsorbed dramatically reduces (Fig. S8 of Supplementary Material). applications.
CFOW-20 has the best adsorption performance, and its pores volume
below 2.5 nm is nearly zero (Fig. S9 of Supplementary Material). The
CRediT authorship contribution statement
detailed structural parameters are summarized in Table 2. Compared
with the fresh adsorbents, the surface area and pore volume of all used
Shanshan Chen: Conceptualization, Data curation, Formal analysis,
adsorbents significantly decreased about 43 ~ 77%, which may be filled
Investigation, Writing – original draft, Writing – review & editing. Yiyue
or blocked by the desulfurization products. Thus, CFOW-20 was selected
Guo: Formal analysis, Validation. Jianan Zhang: Methodology, Formal
for detailed analysis to ascertain a possible deactivation mechanism due
analysis, Validation. Yingchun Guo: Formal analysis, Validation.
to the best adsorption performance. We found that CuFe2O4 was mainly
Xiaoyi Liang: Supervision, Writing – review & editing.
loaded in pores smaller than 6 nm (Fig. 2), and only the pore volume of
less than 6 nm pores decreased in CFOW-20E compared to the same
pores of fresh adsorbent (Fig. 10). Assume that the deposition of Declaration of Competing Interest
CuFe2O4 in the pores is in a homogeneous monolayer, as shown in
Fig. 11. After desulfurization, the pores smaller than 3 nm are almost The authors declare that they have no known competing financial
zero, mainly because the pores filled by the products (Fig. 11A1, A2, and interests or personal relationships that could have appeared to influence
A3). In the pore sizes of 3 ~ 6 nm (Fig. 11A4, A5, and A6), the desul­ the work reported in this paper.
furization products are deposited in the pores but do not fill the entire
pores. The products cover the active sites of the adsorbents, which re­ Appendix A. Supplementary data
stricts the approach of H2S to reach the active sites so that the catalytic
oxidation of hydrogen sulfide is terminated, and no more products can Supplementary data to this article can be found online at https://doi.
be generated. org/10.1016/j.cej.2021.134097.

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