Journal of Hazardous Materials 396 (2020) 122710

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Enhanced removal for H2S by Cu-ordered mesoporous carbon foam T

Junwen Qi, Guoping Wei, Xiuyun Sun, Lianjun Wang, Jiansheng Li*
Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental and Biological Engineering, Nanjing University of Science and
Technology, Nanjing, 210094, China

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Editor: Rinklebe Jörg It is of great significance to protect workers from Sulphur compounds in efficient ways during the regular overhaul or
Keywords: emergency management. Efficient adsorbent with low pressure drop is highly desired in protective equipment. In this
H2S work, Cu-ordered mesoporous carbon foams (MeCF) were prepared through the sol-gel casting and wet-impregnation
Carbon foam process. The obtained carbon foams possessed typical sponge structure with high porosity and copper particles attached
Copper on the skeleton. The characterization on morphology, structure and property illustrated that the presence of mesopores
Dispersion could effectively inhibit the growth of copper particle on MeCF. As the representative of Sulphur compounds, H2S was
Breakthrough curve selected to evaluate the protective performance. Porous copper carbon foams with moderate loading rate (3%) of
copper species exhibited longest breakthrough time and largest adsorption capacity. Compared with the microporous
foams, MeCF-3 displayed promoted protective performance with breakthrough time of 54.7 min and adsorption ca-
pacity of 27.8 mg/g. The enhancement on capabilities was attributed to small-sized copper species with high activity
and better dispersion on mesoporous structure. These results reveled that MeCF with sponge frameworks, developed
mesoporous structure and high dispersion of active species would be a promising candidate for the elimination of H2S
in personal protective equipment.

⁎
Corresponding author.
E-mail address: [email protected] (J. Li).

https://doi.org/10.1016/j.jhazmat.2020.122710
Received 9 January 2020; Received in revised form 27 March 2020; Accepted 9 April 2020
Available online 22 April 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
J. Qi, et al. Journal of Hazardous Materials 396 (2020) 122710

1. Introduction foam as sacrificial scaffold, oligomeric phenolic resol as carbon source,

and triblock copolymer as mesoporous template. Cu-microporous
Currently, abundant air pollutants were emitted into atmosphere, carbon foams were also prepared for comparison. The morphology,
which caused severe environmental problems containing acid rain, structure and property were characterized detailed. The effect of copper
photochemical smog, haze, and the rest (Huang et al., 2014; Sexton loading rate on porous structure was studied. Hydrogen sulfide was
et al., 2004). Triggered by the intake of harmful chemicals, the in- used as the representative of Sulphur compounds to evaluate the pro-
cidence of respiratory disease increased, especially lung cancer among tective performance of the carbon foams. The enhancement of meso-
citizens (Raaschou-Nielsen et al., 2013). Among the various pollutants, porous structure was carefully examined via dispersion experiment.
inorganic Sulphur compounds like SO2, H2S and CS2, were recognized Furthermore, the adsorption mechanism for H2S was investigated.
as the priority due to the bad odor and high toxicity (Feng et al., 2005).
Aside from the natural sources of Sulphur compounds from volcano 2. Experimental section
eruptions and anaerobic decay of organic matter in bogs, the anthro-
pogenic sources play a crucial role in the damage of environment in the 2.1. Reagents
developed and/or populated area (Nowicki et al., 2014). As the major
sources, the municipal facilities such as electric power plants, petro- PU (Polyurethane) foam was provided by Changzhou Daye Tengfei
chemical plants and sewage treatment plants, would suffer from acci- Foam Factory (China). Ethanol, phenol, cupric nitrate trihydrate and
dental leakage or spill out, putting workers and surrounding residents sodium hydroxide were supplied by Sinopharm Chemical Reagent Co.,
under high risk. During the regular overhaul or emergency manage- Ltd. Hydrochloric acid (37 wt%), and formaldehyde (40 wt%) were
ment on the related facilities, the suitable protective equipment should obtained from Nanjing Chemical Reagent Co., Ltd. PEO-PPO-PEO tri-
be provided to staff beyond the damage of released toxic chemicals block copolymer Pluronic F127 with a molecular weight of 12,600 was
(Bobbitt et al., 2017). The effective adsorbent, as the core part, could purchased from Sigma-Aldrich. The standard gas of H2S was purchased
determine the performance of protective equipment such as gas mask by Nanjing Shangyuan Industrial Gas Plant. Deionized water (18.2 MΩ)
and chemical protective clothing (Decoste and Peterson, 2014). purified with a Millipore Elix Water Purification system was used in all
With factors of economic and practical, porous carbon materials the experiments. All chemicals were analytical pure grade and used as
such as activated carbon (AC), were widely used as adsorbent for multi received.
kinds of contaminants in different environmental media (Mohan and
Pittman, 2007). The developed porous structure ensured the removal 2.2. Preparation of porous copper carbon foams
efficiency of air pollutants from the gas flow. However, the poor ad-
sorption behaviors for Sulphur compounds were inevitable performed Porous copper carbon foams (PCCFs) were prepared through the sol-
on the pristine carbon with the property of hydrophobic. Chemical gel casting process based on the PU foam as the sacrificial scaffold
activation, heteroatoms doping, and basic group modification were (Wang et al., 2011). The oligomeric phenolic resol used as carbon
adopted to tailor the surface property of carbon materials (Vega et al., source was prepared by the phenol-formaldehyde condensation
2013; Wan et al., 2019; Yu, Z. et al., 2015). It’s unable to enhance the method. Typically, 1.0 g Pluronic F127 and 5.0 g 20 wt% oligomeric
adsorption performance in essence, which is limited by these mod- phenolic resol were added into the bottle with 10.0 mL ethanol se-
ification methods. Considering chemical affinity of Sulphur compounds, quentially. The mixture was stirring under 40 °C for 2 h to get a trans-
especially H2S with metallic cations, porous carbon materials were parent homogeneous casting solution. After cooled down to room
usually used as the support of metallic active components. Generally, temperature, the solution was cast into a Petri dish with a piece of
metal oxides, hydroxides, or carbonates of magnesium (Siriwardane cylindrical PU foam. With the evaporation of solvent ethanol, the micell
et al., 2017), iron (Zhao et al., 2017), copper (Boutillara et al., 2019), and resin were formed and coated on the framework of PU foam. Then
zinc and their composites (Balsamo et al., 2016), were loaded onto the composite was transferred to the oven under 100 and 150 °C for the
porous carbon materials via impregnation method. Though effective further thermo-polymerization. The ordered mesoporous carbon foam
removal could be conducted, mainly microporous structure lead to the (MeCF-0) was obtained via carbonization in a tubular furnace at 700 °C
aggregation of particles and resistance of mass transfer (Wang et al., for 2 h under nitrogen with heating rate of 1 °C/min. Copper species
2014). The introduction of mesoporous structure in support could en- were introduced into carbon foam by wet impregnation method. 2.0 mL
hance the adsorption performance certified by previous work (Hussain copper nitrate solution impregnated carbon foam with weight of 0.5 g.
et al., 2012). The Cu-ordered mesoporous carbon foam was prepared after the
Apart from the structure and property, shape, hardness and other thermal treatment at 400 °C for 1 h under nitrogen. Cu-ordered meso-
physical property are also required for the practical application. The as- porous carbon foam with different copper mass ratios (0%, 1%, 2%, 3%,
synthesized porous carbon materials usually presented powder form 4%) were gained, named as MeCF-0, MeCF-1, MeCF-2, MeCF-3, MeCF-
with fine particles about 1−10 μm (Saini et al., 2011). The direct ap- 4, respectively. For comparison, a serious of Cu-microporous carbon
plication in the gas adsorption could cause high pressure drop and dust foams were prepared in the same way under the absence of triblock
diffusion in pipes, which lead to low adsorption efficiency and second copolymer, denoted as MiCF-x (x = 0, 1, 2, 3, 4).
dust pollution (Kim et al., 2014). The healthy risk like respiratory ob-
struction could be resulted when equipped for the mask or clothing. 2.3. Characterization
Hence, suitable size, morphology and light weight are highly demanded
for the carbon materials. Among various morphologies, carbon foam is Morphology and microstructure of PCCFs were observed via scan-
more attractable due to the unique properties (Rani Agrawal et al., ning electron microscopy (SEM) and transmission electron microscopy
2019). The three-dimensionally interconnected structure enabled (TEM) on FEI Quanta 250 F and JEOL JEM-2100, respectively. Crystal
plenty of active sites and short transfer path under low pressure drop. morphology of carbon and copper was examined by X-ray diffraction
With large porosity and low density, carbon foam has presented ex- (XRD) patterns on a Bruker AXS D8 advance powder diffraction system
cellent potential in the protective equipment. Referring the short- with Cu Kα radiation (λ =1.5408 Å). Porosity of PCCFs were tested
comings of traditional ones, adsorbent with low pressure drop and ex- through Nitrogen adsorption-desorption isotherms, which were carried
cellent performance for Sulphur compounds is necessary to protect out using a Micromeritics ASAP-2020. Before the test, samples need be
workers away from the risks. degassed in vacuum at 250 °C for 8 h. The specific surface area was
In this work, Cu-ordered mesoporous carbon foams were synthe- obtained based on the Brunauer-Emmett-Teller (BET) method within
sized through the sol-gel casting and wet-impregnation process with PU the relative pressure range of 0.06−0.20. The pore size distribution

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J. Qi, et al. Journal of Hazardous Materials 396 (2020) 122710

(PSD) curves were calculated from adsorption branches. The pore vo- 3. Results and discussion
lume was obtained from the adsorbed amount at relative pressure of
0.975. The X-ray photoelectron spectroscopy (XPS) measurement was 3.1. Characterization of PCCFs
conducted with a PHI Quantera II ESCA system. Raman spectra were
obtained by a LabRAM Aramis spectrometer at 532 nm. 3.1.1. Morphology characterization
Fig. 1 shows the optical images of PCCFs under different stages
during the synthesis process. From the Fig. 1a and b, the foam turned to
2.4. Adsorption experiments sepia and hard without size change after the casting and thermo-poly-
merization process. After the carbonization, the diameter and height of
Adsorption behaviors for H2S on PCCFs were examined by the flow cylindrical foam shrunk about 31 % due to the thermal shrinkage in
method (Hu et al., 2009). A piece of PCCFs was loaded in a fixed-bed pyrolysis process. Indicated by the consistent shrinkage in diameter and
reactor with size of φ10.0 mm × 10.0 mm. Quartz wool were used to height, the isotropic thermal decomposition behavior ensured the
seal the top and bottom of reactor. All the PCCFs were purified by ni- maintain of the sponge structure (Li et al., 2014). The appearance and
trogen at 100 °C for 2 h to remove the physisorbed moisture and CO2 morphology of foams were nearly remained the same except the
before H2S adsorption. After the temperature of fixed-bed reactor de- changes mentioned above.
creased and stabilized at 25 °C, the simulated gas containing 100 ppm The detailed morphology of PCCFs was examined by the SEM, and
H2S with a flow rate of 150 mL/min was introduced. An electro-che- the corresponding images were shown in Fig. 2. MiCF-0 exhibited the
mical sensor (Q-RAE PLUS PGM-2000/2020) for H2S was used to record typical interconnected skeleton networks with high porosity (Fig. 2a
the change of concentration. Breakthrough was defined as the outlet and b), which means the sponge structure of PU foam was duplicated
concentration of H2S (CA) reached 0.05 of the inlet (C0) in the stream, after the sol-gel casting process. With the introduction of triblock co-
and that adsorption time was defined as the breakthrough time. The polymer, MeCF-0 presented less uniform sponge structure, which could
equilibrium time was defined as the time of the ratio of CA/C0 reached be seen clearly in Fig. 2d and e. This phenomenon may due to the
to 0.95. The corresponding adsorption capacity of the adsorbent was complete decomposition of copolymer during the carbonization which
calculated from the breakthrough curves. resulted in the lack of carbon species to maintain the sponge structure
The temperature programmed desorption (TPD) of CO2 on PCCFs (Qiu et al., 2015). From Fig. 2g and j, when the copper species were
was conducted via a chemsorption system (Micromeritics AutoChem II introduced to carbon foams, there are nearly no changes were founded
2920). First, about 0.02 g PCCFs were purged under the helium flow on the structure of foams. The morphology and sponge structure of
(50 mL/min) at 350 °C for 60 min. When the temperature cooled to support were preserved intact except for the abundant small particles
35 °C, CO2 was introduced with flow rate of 30 mL/min. After adsorp- adhered to the skeleton of foams. It’s noteworthy that the copper oxide
tion reached equilibrium, the flow was switched to purge gas. The TPD particles were smaller with uniform distribution on MeCF-3 when
behaviors of CO2 were recorded from ambient temperature to 350 °C compared with MiCF-3. The large copper oxide particle with diameter
with a ramping rate of 10 °C/min. of about 900 nm were observed on the frameworks of MiCF in Fig. 2i
The dispersion of copper on PCCFs was also conducted through the under higher magnification. when it comes to MeCF, smaller copper
chemical system with temperature programmed reduction (TPR) (Yuan oxide particles with just 200 nm could be founded clearly. The differ-
et al., 2011). PCCFs were loaded into the reactor and pretreated at ence of particle size could be attributed to the growth inhibition of
300 °C for 60 min under argon flow with 30 mL/min. After the tem- copper particle on the mesoporous structure (Tang et al., 2016). The
perature cooled to 35 °C, the reduction gas (10 % H2-90 % Ar, 10 mL/ smaller copper particles on MeCF could result in better application
min) was introduced. The reactor was heated to 300 °C with a ramping performance due to the high activity. Furthermore, the interconnected
rate of 10 °C/min. At the same time, TCD signals were recorded along porous structure i.e. sponge structure, would provide the diffusion path
with temperature increase. The amount of hydrogen consumption was with small resistance, which is favorable in the adsorption system (Qi
denoted as X. Right after the first TPR process, the surface copper et al., 2018).
species on PCCFs were further oxidized to Cu2O by N2O at 50 °C for The microstructure of carbon foams and copper oxide particles was
30 min. Then, the second TPR process was acted in the same way with further investigated. From the TEM image (Fig. 3a), MiCF-0 exhibits the
hydrogen consumption of Y. The dispersion of Cu species (DCu) was typical amorphous microporous structure with the amorphous worm-
calculated on the following equations: DCu = X × 100%. like micropores. When the triblock copolymer was added, considerable
2Y

changes had taken place in the porous structure of MeCF-0. Compared

Fig. 1. The optical images of PU foam (a), carbon foam before (b) and after (c) carbonization.

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J. Qi, et al. Journal of Hazardous Materials 396 (2020) 122710

Fig. 2. SEM images of PCCFs: MiCF-0 (a-c), MeCF-0 (d-f), MiCF-3 (g-i) and MeCF-3 (j-l).

with MiCF-0, highly ordered arrangements of parallel channels can be 20 nm with better distribution on the matrix of mesoporous structure,
clearly observed on MeCF-0 (Fig. 3b), indicating the typical structure of consistent with the results of SEM. It should be noted that, the particle
highly ordered two-dimensional hexagonal mesostructured (Wang size obtained from SEM and TEM were quite different. The particles
et al., 2011). The copper oxide particle with size of about 50 nm was with larger size were easily observed by SEM, which indicated the ag-
observed from Fig. 3c after the introduction of 3% copper species on glomeration copper oxide particles attached on the outer surface of
MiCF. While, the smaller darker spots, i.e. copper particles were about carbon foams. For TEM, the smaller particles presented the copper

Fig. 3. TEM images of PCCFs: MiCF-0 (a), MeCF-0 (b), MiCF-3 (c) and MeCF-3 (d).

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J. Qi, et al. Journal of Hazardous Materials 396 (2020) 122710

oxide embedded in the channels and matrix. In addition, ordered strip- Scherrer formula, the size of copper oxide particles on MeCF was just
like channels structure can also be clearly noted in Fig. 3d, suggesting 19.2 nm, which is quite smaller than 48.5 nm on MiCF. The XRD results
the ordered structure keeps maintenance after loading of copper spe- suggest that the mesoporous structure could inhibit growth of copper
cies. oxide particles, in good agreement with the SEM and TEM observations
(Wang et al., 2019).

3.1.2. XRD analysis

Fig. 4a shows the small-angle XRD patterns of carbon foams. No 3.1.3. Porous structure characterization
obvious peak was founded on the patterns of microporous carbon foams The porous structure was fully examined by the physical adsorption
from Fig. 4a. In contrary, in the patterns of MeCF-0 and MeCF-3, the with nitrogen as the adsorbate. The nitrogen adsorption/desorption
typical small-angle diffraction peaks were observed, indicating the isotherms of PCCFs and the corresponding PSD curves were shown in
highly ordered mesostructured on these carbon foams. With the slight Fig. 5. MiCF-0 and MiCF-3 exhibited the type I adsorption isotherms,
decrease of diffraction peak intensity, the mesoporous structure of suggesting the typical microporous structure. It’s noticed that the
carbon foams was still well preserved after the introduction of 3% amount of nitrogen adsorbed decreased a little after the loading of
copper species. Compared with the support mesoporous carbon foam, copper. This phenomenon could result in a slight decrease on surface
the diffraction peak of MeCF-3 presented a small right shift from 2θ of area and pore volume. As for the MeCF, the adsorption/desorption
1.035° to 1.042°. According to Bragg relation, D-spacing of (100) plane isotherm is quite different with MiCF. MeCF-0 displayed the typical
were 8.53 and 8.47 nm, respectively (Pourazadi et al., 2013). The unit type Ⅳ curves with obvious H1 hysteresis loops, representative char-
cell parameter of MeCF-3 was calculated to be 9.85 nm, smaller than acter of mesoporous materials (Wang et al., 2019). The abrupt change
that of MeCF-0, which was in accordance with the result from TEM of isotherm in relative pressure from 0.4 to 0.7 is due to the capillary
images. This phenomenon suggested the occupation of copper species condensation of large amount nitrogen molecules in mesopores, in-
onto mesopores (Qie et al., 2015). In other words, the copper species dicating regular mesopore structure with uniform pore size distribution
were successfully incorporated into the mesoporous structure of carbon on MeCF-0. This ordered mesopore structure of MeCF-0 was similar
foam. with the result of previous work without foam template (Li et al., 2014),
From Fig. 4b, two broad peaks at 23° and 44° were clearly observed, revealing that PU foam have limited impact on the sol-gel casting
corresponding to the amorphous dispersion diffraction peaks of dis- process except the function of sacrificial scaffold. After the introduction
ordered graphitic carbon materials (Yu, X. et al., 2015). After the im- of active component, MeCF-3 still presented the similar shape of iso-
pregnation process and thermal treatment, MiCF-3 and MeCF-3 both therm. The remaining of hysteresis loops means that the loading of
presented the typical diffraction peaks at 37.0° and 42.6°, which as- copper did not damage the mesoporous structure.
signed to the (111) and (200) crystal planes of copper oxide, respec- Based on the BET method, the specific surface area of MiCF-0, MiCF-
tively (Pawar et al., 2016). However, under the same loading rate, the 3, MeCF-0 and MeCF-3 are 509, 485, 643 and 618 m2/g, respectively
intensity of the diffraction peaks is obviously different on the micro- (Table 1). Different with MiCF, the pore volume increased after the
porous and mesoporous structure. This phenomenon may be due to the loading process. This may due to the decomposition of several carbon
difference of dispersion of copper oxide. The strong diffraction peaks of matrix and generation of mesopores and macropores during the post
MiCF-3 may be resulted from the large copper oxide particles, which thermal treatment of composite. From Fig. 5b, the PSD curves for MiCF-
were formed by the agglomeration of copper oxide on support. For 0 and MiCF-3 are nearly coincided without any distribution in the
MeCF-3, the weak diffraction peaks of planes, resulting from the small mesoporous region. While, MeCF-0 and MeCF-3 exhibit similar dis-
particle of copper oxide, indicated that the copper species presented a tributions with a sharp peak centered around 3.7 nm, indicating the
better dispersion on mesoporous carbon foam. Based on the Debye- uniform mesoporous structure. It’s noteworthy that there is a left shift

Fig. 4. Small-angle (a) and Wide-angle (b) XRD patterns of PCCFs.

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J. Qi, et al. Journal of Hazardous Materials 396 (2020) 122710

Fig. 5. Nitrogen adsorption/desorption isotherms (a) and PSD curves (b) of PCCFs.

Table 1 that the promotion was greater with the increase of copper species
The structural parameters of PCCFs. when compared with MiCF. This phenomenon indicated that the copper
Sample SBET(m2/g) Vtotal(cm3/g) Vmicro(cm3/g) Vmeso(cm3/g) D(nm)
species on MeCF presented better utilization and higher reaction ac-
tivity with H2S. Not surprisingly, the best adsorption performance was
MiCF-0 509 0.237 0.217 0.020 – observed on the MeCF-3 with breakthrough time of 54.7 min and ad-
MiCF-3 485 0.233 0.207 0.026 – sorption capacity of 27.8 mg/g, which is comparable with other ad-
MeCF-0 643 0.411 0.140 0.271 3.99
MeCF-3 618 0.424 0.137 0.287 3.55
sorbents in literatures (Li et al., 2016; Mabayoje et al., 2012; Yu et al.,
2015a,b; Yu et al., 2016).
For the further comparison of the adsorption performance on PCCFs
on PSD curves of MeCF after the copper loading. The pore size of MeCF with different structures, the adsorption breakthrough curves for H2S
decreased from 3.99 nm for MeCF-0 to 3.55 nm for MeCF-3, which were on MiCF-3, MeCF-3 and corresponding supports were shown in Fig. 6
consistent with previous XRD and TEM results. In addition, the pore more intuitively. The adsorption behavior on MeCF-0 was much better
size and surface area decreased along with the increase of copper than that on MiCF-0. The breakthrough time and adsorption capacity
loading rate (Fig. S1 and Table S1), which were caused by the occu- increased from 0.1 min and 0.2 mg/g to 1.6 min and 3.6 mg/g, respec-
pation of copper oxide in the mesoporous structure. tively (Table 2). This may be due to the difference on structure and/or
property between MiCF-0 and MeCF-0 caused by the introduction of
3.2. Adsorption studies triblock copolymer. After loading of 3% copper species, MiCF-3 pre-
sented enhanced performance with breakthrough time of 7.0 min and
Considering the reality of the protection equipment, the functional adsorption capacity of 12.8 mg/g. However, under the same conditions,
materials, i.e. PCCFs in this work, were always loaded into a filter to the adsorption performance on MeCF-3 was several multiples of that on
form the adsorption bed for toxic molecules. The flow-through method MiCF-3. On the premise of deducting the adsorption performance of the
was adopted to evaluate the protective performance of filter for H2S support, the contribution of copper species was checked on the material
under similar conditions. The obtained breakthrough curves were used balance. The adsorption capacity of copper species on MeCF-3 was 1.9
to investigate the dynamic adsorption behaviors (Hu et al., 2009). times of that on MiCF-3.

3.2.1. Adsorption performance

The adsorption experiments of H2S on PCCFs with different struc-
tures and compositions were carried out. The adsorption curves for H2S
on PCCFs were shown in Fig. S3, and the corresponding results were
listed in Table S2. As for the pristine microporous carbon foams, poorly
adsorption behavior was observed with the shortest breakthrough time
of 0.1 min. After the loading of copper species, the breakthrough curves
shifted right, indicating the better adsorption performance with pro-
longed breakthrough and equilibration time. Along with the increase-
ment of copper species introduced, longer breakthrough and equili-
bration time were clearly observed in Fig. S3a. When 3% copper species
were introduced, MiCF-3 exhibited the longest breakthrough and
equilibration time with 7.0 and 112 min, indicating the largest ad-
sorption capacity of 12.8 mg/g. However, there is a decline of adsorp-
tion breakthrough time when the loading rate of copper species reached
to 4%, which the breakthrough curve was nearly overlapped with the
one of MiCF-2. There is an obvious decrease on the adsorption perfor-
mance with breakthrough time of 6.7 min, equilibration time of 68 min
and adsorption capacity of 7.8 mg/g.
When it comes to mesoporous carbon foams, the similar phenom-
enon was obtained (Fig. S3b). The prolonged breakthrough curves were
detected on MeCF with higher copper loading rate. It should be noticed Fig. 6. The adsorption curves for H2S on PCCFs.

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J. Qi, et al. Journal of Hazardous Materials 396 (2020) 122710

Table 2 Table 3
The dynamic adsorption parameters of H2S on PCCFs. Desorption results calculated from CO2-TPD curves of MiCF-0 and MeCF-0.
Sample Breakthrough time Equilibration time Adsorption capacity Sample Desorption temperature (oC) Peak area (a.u.)
(min) (min) (mg H2S/g CF)
MiCF-0 68 0.0049
MiCF-0 0.1 2 0.2 MeCF-0 75 0.0139
MiCF-3 7.0 112 12.8
MeCF-0 1.6 60 3.6
MeCF-3 54.7 290 27.8
understand the adsorption mechanisms, MiCF-3 and MeCF-3 before and
after H2S adsorption were selected to analysis the quantities and types
of copper species through XPS. The high-resolution XPS spectra and
To test the reusability of the adsorbent, MeCF-3 was regenerated by
corresponding deconvoluted spectra of copper were shown in Fig. 8.
thermal treatment at 200 °C in air flow. The regenerated MeCF-3 was
The Cu2p peak could be deconvoluted into three peaks at different
subjected to further adsorption-desorption cycles for H2S. As shown in
binding energies: Cu2O (932.6 eV), CuO (933.9 eV), and CuS
Fig. S4, stable dynamic adsorption behaviors were clearly founded in
(932.3 eV), respectively (Lin et al., 2007; Qi et al., 2019). Before the
four cycles with similar breakthrough time. After four cycles, adsorp-
adsorption of H2S, copper species in MiCF-3 and MeCF-3 were mainly
tion capacity for H2S on MeCF-3 still reached 22.4 mg/g, indicating
CuO. Based on the deconvoluted spectra, the ratio of CuO in MiCF-3 is
good reusability of adsorbent. This enhanced performance could be
nearly 45 %, due to the partial reaction when exposed in the air. The
ascribed to the smaller copper oxide particles on mesoporous structure,
rest is assigned as Cu2O consisted with the XRD results. However, the
which was consistent with the characterization results.
proportion of CuO in MeCF-3 is nearly 72 %, which may be ascribed to
high reaction activity of copper species on mesoporous structures. After
3.2.2. CO2-TPD
adsorption process, the copper species have an obvious change. The
The temperature programmed desorption experiment is an effective
existence of CuS peak around 932.3 eV indicated that the adsorption of
way to analysis the surface chemical property of functional materials,
H2S depends on its chemical reaction with copper oxide. The ratio of
which could determine the removal performance for the pollutants. In
CuS increased to 19.8 % in MiCF-3 and 35.1 % in MeCF-3. Compared
order to clarify the difference on adsorption performance between
with MiCF-3, mesoporous structure could result in higher reaction ac-
MiCF-0 and MeCF-0, CO2 was used as the acidic probe to evaluate the
tivity between copper species and H2S, which was confirmed by the
surface alkaline strength of supports. The CO2-TPD curves are shown in
adsorption investigation.
Fig. 7, and the corresponding results are listed in Table 3.
Fig. S5 shows the wide-angle XRD patterns of PCCFs after adsorp-
The broad desorption peaks around 70 °C were clearly observed in
tion of H2S. It can be clearly found that the diffraction peak around
Fig. 7. When the samples were heated at temperature over 150 °C, the
37.0° has disappeared for both MiCF-3 and MeCF-3, indicating the
TCD signal curves approached to the baseline with nearly no obvious
chemical reaction has occurred during the adsorption. However, the
CO2 desorption peaks. This could be contributed to the completely
weak peak at 42.6° was still observed on MiCF-3, which may be due to
desorption of CO2 under low temperature, indicated the weak interac-
the lower reaction activity of copper species on microporous structure.
tion between CO2 and supports. From Fig. 7 and Table 3, the higher
Besides that, the retention of broad peaks at 25° and 44° reflected no
desorption temperature was presented on MeCF with 75 °C. what’s
adverse effect on the carbon matrix during the adsorption.
more, the amount of adsorbed CO2 on MeCF-0 is about 2.8 times of that
The transformation of copper oxide on MeCF-3 was also studied by
on MiCF-0. The desorption behavior demonstrated that MeCF-0 ex-
Raman spectroscopy, as shown in Fig. 9a. From the Raman spectrum of
hibited stronger interaction with CO2 and more alkaline sites for the
MeCF-3, the phonon peak at 295 cm−1 was assigned to the crystalline
adsorption of acidic molecules when compared with MiCF-0. This result
CuO (Levitskii et al., 2015), which consisted with XRD results. After
also provides a compelling evidence for the difference of adsorption
H2S introduced, the intensity of CuO band decreased. In the meantime,
behavior on the support.
the new band located at 467 cm−1 appeared, associated with the SeS
stretching mode in CuS (Kumar and Nagarajan, 2011). This phenom-
3.2.3. Adsorption mechanisms for H2S enon illustrated that copper oxide with high activity could convert to
To further investigate the transformation of copper species to

Fig. 7. The CO2-TPD curves of MiCF-0 and MeCF-0.

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J. Qi, et al. Journal of Hazardous Materials 396 (2020) 122710

Fig. 8. The high-resolution XPS spectra of Cu2p before and after H2S adsorption: MiCF-3 (a) and MeCF-3 (b).

CuS, which resulted in the excellent adsorption performance for H2S. MiCF-3 and MeCF-3 presented different reduction behaviors. For the
Fig. 9b showed the elemental mapping scanning spectra of C, Cu and S first TPR test, the reduction peak at 151 °C for the MiCF-3 was attrib-
and corresponding SEM image of MeCF-3 after H2S adsorption. The uted to the reduction from Cu2O to Cu. But on MeCF-3, the main re-
outline of copper signals coincides with bright particles on skeleton of duction peak was located at about 130 °C with a shoulder peak at
foam. After H2S adsorption, the particles became rougher and bigger 150 °C. The copper species on mesoporous structure could be reduced
compared with Fig. 2l, which caused by the transformation of partial under lower temperature, meaning the higher chemical activity (Kim
copper oxide to copper sulphide. It could be also noticed that sulphur and Ihm, 2007). When it comes to the second TPR test, the similar
signals nearly overlapped with copper under same distribution, which behaviors were also detected. The decrease of reduction temperature
further confirmed the interactions between copper oxide and H2S was resulted from the high activity and dispersion of copper species on
during the adsorption process. mesoporous structure (Abdullah et al., 2006; Dow and Huang, 1996).
For the further explanation of the difference in adsorption capacity From Table 4, the first H2-TPR hydrogen consumption X of MiCF-3
of H2S on the loaded porous carbon with different structure, the fine and MeCF-3 is approximately equal with the same loading rate. How-
structures were carefully analyzed through SEM, TEM, XRD and other ever, there is a fairly difference in hydrogen consumption of second H2-
characterizations. The mesoporous structure on carbon foams promoted TPR test. According to the equation, the dispersion of copper species on
the dispersion to form copper particles with smaller size and higher different carriers was 21.2 % for MiCF-3 and 31.4 % for MeCF-3, re-
activity. In order to make the results more convincing at the macro- spectively. The dispersion of copper species on mesoporous carbon
scopic scale, the test on dispersion and activity of copper species was foam is better than that on microporous carbon foam, which is con-
carried out. sistent with the previous results of XRD, SEM and TEM. This dispersion
H2-TPR test has been widely used to evaluate the redox ability of result confirmed that the mesoporous structure could promote the
functional materials. For copper-based carbon materials, different dis- dispersion of copper species, inhibit the growth of particle size, improve
persion states could be obtained through the evaluation of redox the activity of active components and enhance the removal perfor-
properties through H2-TPR test coupled with N2O treatment (Yuan mance for H2S and others, effectively.
et al., 2011). From the TPR curves in Fig. 10, the copper species on

Fig. 9. Raman spectra of MeCF-3 before and after H2S adsorption (a) and the elemental mapping scanning spectra of MeCF-3 after H2S adsorption (b).

8
J. Qi, et al. Journal of Hazardous Materials 396 (2020) 122710

Fig. 10. The H2-TPR curves of MiCF-3 and MeCF-3.

Table 4 Writing - review & editing. Guoping Wei: Investigation. Xiuyun Sun:
Dispersion of Cu calculated from H2-TPR curves of MiCF-3 and MeCF-3. Investigation. Lianjun Wang: Methodology. Jiansheng Li:
Sample X (cm3/g) Y (cm3/g) DCu (%) Conceptualization, Writing - review & editing, Validation.

MiCF-0 6.70 0.71 21.2 Declaration of Competing Interest

MeCF-0 6.50 1.02 31.4

We declare that we do not have any commercial or associative in-

4. Conclusions terest that represents a conflict of interest in connection with the work
submitted.
In summary, Cu-ordered mesoporous carbon foams were prepared
through the sol-gel casting and wet-impregnation process with PU foam Acknowledgements
as sacrificial scaffold, oligomeric phenolic resol as carbon source, and
triblock copolymer as mesoporous template. The obtained carbon The authors acknowledge financial support from the National
foams possessed typical sponge structure with high porosity and copper Natural Science Foundation of China (51678307), National Key
particles attached on the skeleton. The XRD, SEM and TEM results il- Research and Development Program of China (No. 2019YFC0408302),
lustrated that the presence of mesopores could effectively inhibit the the Fundamental Research Funds for the Central Universities
growth of copper particle on mesoporous carbon foams. Based on the (30919011209), Open Fund of Jiangsu Engineering Laboratory for
adsorption behaviors for H2S, PCCFs with moderate loading rate (3%) Environment Functional Materials (JSEFM201805), Open Project
of copper species exhibited longest breakthrough time and largest ad- Program of Provincial Key Laboratory of Clean Energy Materials,
sorption capacity. Compared with MiCF-3, MeCF-3 displayed promoted LongYan University (QJNY-201801) and the priority academic program
protective performance for H2S with breakthrough time of 54.7 min and development of Jiangsu higher education institutions.
adsorption capacity of 27.8 mg/g. The enhancement on capabilities was
attributed to small-sized copper species with high activity and better Appendix A. Supplementary data
dispersion on mesoporous structure, which was thoroughly confirmed
by XPS and H2-TPR results. In general, PCCFs with sponge frameworks, Supplementary material related to this article can be found, in the
developed mesoporous structure and high dispersion of active species online version, at doi:https://doi.org/10.1016/j.jhazmat.2020.122710.
would be a promising candidate for the elimination of H2S in personal
protective equipment. References

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