Citation: Pingping HAO, Fangfang LI, Yawen WANG, Houfen LI, Xiao ZHANG, Rui LI, Lei WANG, Jianxin LIU. Hydrogen production performance of the non-platinum-based MoS₂/CuS cathode in microbial electrolytic cells[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(9): 1811-1824. doi: 10.11862/CJIC.20240054 shu

Hydrogen production performance of the non-platinum-based MoS₂/CuS cathode in microbial electrolytic cells

Pingping HAO ¹ ,
Fangfang LI ¹ ,
Yawen WANG ¹ ,
Houfen LI ² ,
Xiao ZHANG ² ,
Rui LI ^{1, 2} ,
Lei WANG ^3,, ,
Jianxin LIU ^1,,

1.
College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
2.
College of Environmental Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
3.
Shanxi Province Cancer Hospital, Shanxi Hospital Affiliated to Cancer Hospital, Chinese Academy of Medical Sciences, Cancer Hospital Affiliated to Shanxi Medical University, Taiyuan 030013, China

Corresponding author: Lei WANG, 56218605@qq.com Jianxin LIU, liujx0519@163.com
Received Date: 18 February 2024
Revised Date: 11 July 2024

Figures(9)

MoS₂/CuS composite catalysts were successfully synthesized using a one-step hydrothermal method with sodium molybdate dihydrate, thiourea, oxalic acid, and copper nitrate trihydrate as raw materials. The hydrogen production performance of MoS₂/CuS prepared with different molar ratios of Mo to Cu precursors (n_Mo∶n_Cu) as cathodic catalysts was investigated in the two-chamber microbial electrolytic cell (MEC). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscope (TEM), linear scanning voltammetry (LSV), electrochemical impedance analysis (EIS), and cyclic voltammetry (CV) were used to characterize the synthesized catalysts for testing and analyzing the hydrogen-producing performance. The results showed that the hydrogen evolution performance of MoS₂/CuS-20% (n_Mo∶n_Cu=5∶1) was better than that of platinum (Pt) mesh, and the hydrogen production rate of MoS₂/CuS-20% as a cathode in MEC was (0.203 1±0.023 7) m_H₂³·m^-3·d^-1 for 72 h at an applied voltage of 0.8 V, which was slightly higher than that of Pt mesh of (0.188 6±0.013 4) m_H₂³·m^-3·d^-1. The addition of a certain amount of CuS not only regulates the electron transfer ability of MoS₂ but also increases the density of active sites.
- microbial electrolysis cell,
- hydrogen evolution reaction,
- MoS₂/CuS composite catalyst,
- Pt mesh
1. [1]
  Li Y F, Ren N Q, Yang C P, Wang A J, Zadsar M, Li J Z, Hu L J. Molecular characterization and hydrogen production of a new species of anaerobe[J]. J. Environ. Sci. Health, 2005,40:1929-1938. doi: 10.1080/10934520500184483
2. [2]
  Ren N, Li J Z, Li B K, Wang Y, Liu S R. Biohydrogen production from molasses by anaerobic fermentation with a pilot-scale bioreactor system[J]. Int. J. Hydrog. Energy, 2006,31:2147-2157. doi: 10.1016/j.ijhydene.2006.02.011
3. [3]
  Kapdan I K, Kargi F. Bio-hydrogen production from waste materials[J]. Enzyme Microb. Technol., 2006,38:569-582. doi: 10.1016/j.enzmictec.2005.09.015
4. [4]
  Wang J P, Song Y N, Hu J, Li Y, Wang Z Y, Yang P, Wang G, Ma Q, Che Q D, Dai Y, Huang B B. Photocatalytic hydrogen evolution on P-type tetragonal zircon BiVO₄[J]. Appl. Catal. B-Environ., 2019,251:94-101. doi: 10.1016/j.apcatb.2019.03.049
5. [5]
  Zhang B B, Dong G J, Wang L, Zhang Y J, Ding Y, Bi Y P. Efficient hydrogen production from MIL-53(Fe) catalyst-modified Mo: BiVO₄ photoelectrodes[J]. Catal. Sci. Technol., 2017,7:4971-4976. doi: 10.1039/C7CY01765K
6. [6]
  Guan X, Zhou Z, Luo P, Wu F S, Dong S J. Effects of preparation method on the hydrolytic hydrogen production performance of Al-rich alloys[J]. J. Alloy. Compd., 2019,796:210-220. doi: 10.1016/j.jallcom.2019.05.053
7. [7]
  Logan B E, Call D, Cheng S, Hamelers H V M, Sleutels T H J A, Jeremiasse A W, Rozendal R A. Microbial electrolysis cells for high yield hydrogen gas production from organic matter[J]. Environ. Sci. Technol., 2008,42(23):8630-8640. doi: 10.1021/es801553z
8. [8]
  DAI H Y, YANG H M, LIU X, JIAN X, GUO M M, CAO L L, YANG Z H. Preparation of MoS₂/graphene composite cathode materials and hydrogen production performance catalyzed by microbial electrolytic cell[J]. Chem. J. Chinese Universities, 2018,39(2):351-358.
9. [9]
  Geelhoed J S, Hamelers H V M, Stams A J M. Electricity-mediated biological hydrogen production[J]. Curr. Opin. Microbiol., 2010,13:307-315. doi: 10.1016/j.mib.2010.02.002
10. [10]
  Savla N, Guin M, Pandit S, Malik H, Khilari S, Mathuriya A S, Gupta P K, Thapa B S, Bobba R, Jung S P. Recent advancements in the cathodic catalyst for the hydrogen evolution reaction in microbial electrolytic cells[J]. Int. J. Hydrog. Energy, 2022,47:15333-15356. doi: 10.1016/j.ijhydene.2022.03.058
11. [11]
  Ivanov I, Ahn Y T, Poirson T, Hickner M A, Logan B E. Comparison of cathode catalyst binders for the hydrogen evolution reaction in microbial electrolysis cells[J]. Int. J. Hydrog. Energy, 2017,42:15739-15744.
12. [12]
  Zhang H, Meng G, Wei T R, Ding J Y, Liu Q, Luo J, Liu X J. Co doping promotes the alkaline overall seawater electrolysis performance over MnPSe₃ nanosheets[J]. Chem. Commun., 2023,59:12144-12147.
13. [13]
  Liu W X, Niu X X, Tang J W, Liu Q, Luo J, Liu X J, Zhou Y T. Energy-efficient anodic reactions for sustainable hydrogen production via water electrolysis[J]. Chem. Synth., 2023,344.
14. [14]
  Qin Y J, Cao H J, Liu Q, Yang S Q, Feng X C, Wang H, Lian M L, Zhang D X, Wang H, Luo J, Liu X J. Multi-functional layered double hydroxides supported by nanoporous gold toward overall hydrazine splitting[J]. Front. Chem. Sci. Eng., 2023,18(1)6.
15. [15]
  Liu B, Zhao W J, Ding Z J, Verzhbitskiy I, Li L J, Lu J P, Chen J Y, Eda G, Loh K P. Engineering bandgaps of monolayer MoS₂ and WS₂ on fluoropolymer substrates by electrostatically tuned many-body effects[J]. Adv. Mater., 2016,28(30):6457-6464.
16. [16]
  Naylor C H, Kybert N J, Schneier C, Xi J, Romero G, Saven J G, Liu R Y, Johnson A T C. Scalable production of molybdenum disulfide based biosensors[J]. ACS Nano, 2016,10(6):6173-6179.
17. [17]
  Hwang J H, Fahad S, Ryu H, Rodriguez K L, Domingo J S, Kushima A, Lee W H. Recycling urine for bioelectrochemical hydrogen production using a MoS₂ nano carbon coated electrode in a microbial electrolysis cell[J]. J. Power Sources, 2022,527231209.
18. [18]
  Zhou M, Zhang R, Huang M A, Lu W, Song S L, Melancon M P, Tian M, Liang D, Li C. A chelator-free multifunctional[⁶⁴Cu] CuS nanoparticle platform for simultaneous micro-PET/CT imaging and photothermal ablation therapy[J]. J. Am. Chem. Soc., 2010,132:15351-15358.
19. [19]
  Basu M, Sinha A K, Pradhan M, Sarkar S, Negishi Y, Govind , Pal T. Evolution of hierarchical hexagonal stacked plates of CuS from liquid-liquid interface and its photocatalytic application for oxidative degradation of different dyes under indoor lighting[J]. Environ. Sci. Technol., 2010,44:6313-6318.
20. [20]
  Chunga J S, Sohnb H J. Electrochemical behaviors of CuS as a cathode material for lithium secondary batteries[J]. J. Power Sources, 2002,108:226-231.
21. [21]
  Kim W B, Lee S H, Cho M, Lee Y. Facile and cost-effective CuS dendrite electrode for non-enzymatic glucose sensor[J]. Sensors Actuat. B: Chem., 2017,249:161-167.
22. [22]
  Wu X Q, Huang D D, Wu Y P, Zhao J, Liu X, Dong W W, Li S, Li D S, Li J R. In situ synthesis of nano CuS-embedded MOF hierarchical structures and application in dye adsorption and hydrogen evolution reaction[J]. ACS Appl. Energy Mater., 2019,2:5698-5706.
23. [23]
  Wang Y C, Chao D L, Wang Z Z, Ni J F, Li L. An energetic CuS-Cu battery system based on CuS nanosheet arrays[J]. ACS Nano, 2021,15:5420-5427.
24. [24]
  Liu S Q, Wen H R, Ying G, Zhu Y W, Fu X Z, Sun R, Wong C P. Amorphous Ni(OH)₂ encounter with crystalline CuS in hollow spheres: A mesoporous nano-shelled heterostructure for hydrogen evolution electrocatalysis[J]. Nano Energy, 2018,44:7-14.
25. [25]
  SHI Q P, CHENG Y Z, HUANG T, SUN Q, XIA B Y. Determination of sodium acetate for sewage treatment by spectrophotometric method[J]. Energy and Environment, 2002,5:78-80.
26. [26]
  Dong Z S, Zhao Y, Fan L, Wang Y X, Wang J W, Zhang K. Simultaneous sulfide removal and hydrogen production in a microbial electrolysis cell[J]. Int. J. Electrochem. Sci., 2017,12:10553-10566.
27. [27]
  Kim M, Anjum M A R, Choi M, Jeong H Y, Choi S H, Park N, Lee J S. Covalent 0D-2D heterostructuring of Co₉S₈-MoS₂ for enhanced hydrogen evolution in all pH electrolytes[J]. Adv. Funct. Mater., 2020,302002536.
28. [28]
  Kim M S, Tran D T, Nguyen T H, Dinh V A, Kim N H, Lee J H. Ni single atoms and Ni phosphate clusters synergistically triggered surface-functionalized MoS₂ nanosheets for high-performance freshwater and seawater electrolysis[J]. Energy Environ. Mater., 2022,5:1340-1349.
29. [29]
  Zhou Q S, Feng J R, Peng X W, Zhong L X, Sun R C. Porous carbon coupled with an interlaced MoP-MoS₂ heterojunction hybrid for efficient hydrogen evolution reaction[J]. J. Energy Chem., 2020,45:45-51.
30. [30]
  Zhang X, Jia F F, Song S X. Recent advances in structural engineering of molybdenum disulfide for electrocatalytic hydrogen evolution reaction[J]. Chem. Eng. J., 2021,405127013.
31. [31]
  Lu Z Y, Li Y J, Lei X D, Liu J F, Sun X M. Nanoarray based "superaerophobic" surfaces for gas evolution reaction electrodes[J]. Mater. Horiz., 2015,2:294-298.
32. [32]
  An L, Huang L, Zhou P P, Yin J, Liu H Y, Xi P X. A self-standing high-performance hydrogen evolution electrode with nanostructured NiCo₂O₄/CuS heterostructures[J]. Adv. Funct. Mater., 2015,25:6814-6822.
33. [33]
  Li F J, Liu W F, Sun Y, Ding W J, Cheng S A. Enhancing hydrogen production with Ni-P coated nickel foam as cathode catalyst in single chamber microbial electrolysis cells[J]. Int. J. Hydrog. Energy, 2017,42:3641-3646.
34. [34]
  Liu L, Liu X L, Jiao S L. CuS@defect-rich MoS₂ core-shell structure for enhanced hydrogen evolution[J]. J. Colloid Interface Sci., 2020,564:77-87.
35. [35]
  Ren X, Wu D, Ge R X, Sun X, Ma H M, Yan T, Zhang Y, Du B, Wei Q, Chen L. Self-supported CoMoS₄ nanosheet array as an efficient catalyst for hydrogen evolution reaction at neutral pH[J]. Nano Res., 2018,11:2024-2033.
36. [36]
  Liu W Z, Wang A J, Ren N Q, Zhao X Y, Liu L H, Yu Z G, Le D J. Electrochemically assisted biohydrogen production from acetate[J]. Energy Fuel, 2008,22:159-163.
37. [37]
  Kiely P D, Cusick R, Call D F, Selembo P A, Regan J M, Logan B E. Anode microbial communities produced by changing from microbial fuel cell to microbial electrolysis cell operation using two different wastewaters[J]. Bioresour. Technol., 2011,102:388-394.
38. [38]
  Liu W Z, Wang A J, Sun D, Ren N Q, Zhang Y Q, Zhou J Z. Characterization of microbial communities during anode biofilm reformation in a two-chambered microbial electrolysis cell (MEC)[J]. J. Biotechnol., 2012,157:628-632.
39. [39]
  Shannon B C E. A mathematical theory of communication[J]. Bell System Technical Journal., 1948,27:379-423.
40. [40]
  Shannon B C E. A mathematical theory of communication[J]. Bell System Technical Journal., 1948,27:623-656.
41. [41]
  Fykse E M, Aarskaug T, Madslien E H, Dybwad M. Microbial community structure in a full-scale anaerobic treatment plant during start-up and first year of operation revealed by high-throughput 16S rRNA gene amplicon sequencing[J]. Bioresour. Technol., 2016,222:380-387.
42. [42]
  Cho S K, Jeong M W, Choi Y K, Shin J, Shin S G. Effects of low-strength ultrasonication on dark fermentative hydrogen production: Start-up performance and microbial community analysis[J]. Appl. Energy, 2018,219:34-41.
43. [43]
  Liu Z D, Zhang C, Wang L J, He J W, Li B M, Zhang Y H, Xing X H. Effects of furan derivatives on biohydrogen fermentation from wet steam-exploded cornstalk and its microbial community[J]. Bioresour. Technol., 2015,175:152-159.
44. [44]
  Vesga-Baron A, Etchebehere C, Schiappacasse M C, Chamy R, Tapia-Venegas E. Controlled oxidation-reduction potential on dark fermentative hydrogen production from glycerol: Impacts on metabolic pathways and microbial diversity of an acidogenic sludge[J]. Int. J. Hydrog. Energy, 2021,46:5074-5084.
1. [1]
  Weiping Xiao , Yuhang Chen , Qin Zhao , Danil Bukhvalov , Caiqin Wang , Xiaofei Yang . Constructing the synergistic active sites of nickel bicarbonate supported Pt hierarchical nanostructure for efficient hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(12): 110176-. doi: 10.1016/j.cclet.2024.110176
2. [2]
  Hongliang Zeng , Yuan Ji , Jinfeng Wen , Xu Li , Tingting Zheng , Qiu Jiang , Chuan Xia . Pt nanocluster-catalyzed hydrogen evolution reaction: Recent advances and future outlook. Chinese Chemical Letters, 2025, 36(3): 109686-. doi: 10.1016/j.cclet.2024.109686
3. [3]
  Junan Pan , Xinyi Liu , Huachao Ji , Yanwei Zhu , Yanling Zhuang , Kang Chen , Ning Sun , Yongqi Liu , Yunchao Lei , Kun Wang , Bao Zang , Longlu Wang . The strategies to improve TMDs represented by MoS₂ electrocatalytic oxygen evolution reaction. Chinese Chemical Letters, 2024, 35(11): 109515-. doi: 10.1016/j.cclet.2024.109515
4. [4]
  Jing Cao , Dezheng Zhang , Bianqing Ren , Ping Song , Weilin Xu . Mn incorporated RuO₂ nanocrystals as an efficient and stable bifunctional electrocatalyst for oxygen evolution reaction and hydrogen evolution reaction in acid and alkaline. Chinese Chemical Letters, 2024, 35(10): 109863-. doi: 10.1016/j.cclet.2024.109863
5. [5]
  Lizhang Chen , Yu Fang , Mingxin Pang , Ruoxu Sun , Lin Xu , Qixing Zhou , Yawen Tang . Interfacial engineering of core/satellite-structured RuP/RuP2 heterojunctions for enhanced pH-universal hydrogen evolution reaction. Chinese Journal of Structural Chemistry, 2025, 44(1): 100461-100461. doi: 10.1016/j.cjsc.2024.100461
6. [6]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
7. [7]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
8. [8]
  Xi YANG , Chunxiang CHANG , Yingpeng XIE , Yang LI , Yuhui CHEN , Borao WANG , Ludong YI , Zhonghao HAN . Co-catalyst Ni₃N supported Al-doped SrTiO₃: Synthesis and application to hydrogen evolution from photocatalytic water splitting. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 440-452. doi: 10.11862/CJIC.20240371
9. [9]
  Yongwei ZHANG , Chuang ZHU , Wenbin WU , Yongyong MA , Heng YANG . Efficient hydrogen evolution reaction activity induced by ZnSe@nitrogen doped porous carbon heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 650-660. doi: 10.11862/CJIC.20240386
10. [10]
  Guoliang Gao , Guangzhen Zhao , Guang Zhu , Bowen Sun , Zixu Sun , Shunli Li , Ya-Qian Lan . Recent advancements in noble-metal electrocatalysts for alkaline hydrogen evolution reaction. Chinese Chemical Letters, 2025, 36(1): 109557-. doi: 10.1016/j.cclet.2024.109557
11. [11]
  Chenhao Zhang , Qian Zhang , Yezhou Hu , Hanyu Hu , Junhao Yang , Chang Yang , Ye Zhu , Zhengkai Tu , Deli Wang . N-doped carbon confined ternary Pt₂NiCo intermetallics for efficient oxygen reduction reaction. Chinese Chemical Letters, 2025, 36(3): 110429-. doi: 10.1016/j.cclet.2024.110429
12. [12]
  Minying Wu , Xueliang Fan , Wenbiao Zhang , Bin Chen , Tong Ye , Qian Zhang , Yuanyuan Fang , Yajun Wang , Yi Tang . Highly dispersed Ru nanospecies on N-doped carbon/MXene composite for highly efficient alkaline hydrogen evolution. Chinese Chemical Letters, 2024, 35(4): 109258-. doi: 10.1016/j.cclet.2023.109258
13. [13]
  Yaoyin Lou , Xiaoyang Jerry Huang , Kuang-Min Zhao , Mark J. Douthwaite , Tingting Fan , Fa Lu , Ouardia Akdim , Na Tian , Shigang Sun , Graham J. Hutchings . Stable core-shell Janus BiAg bimetallic catalyst for CO₂ electrolysis into formate. Chinese Chemical Letters, 2025, 36(3): 110300-. doi: 10.1016/j.cclet.2024.110300
14. [14]
  Bowen Li , Ting Wang , Ming Xu , Yuqi Wang , Zhaoxing Li , Mei Liu , Wenjing Zhang , Ming Feng . Structuring MoO₃-polyoxometalate hybrid superstructures to boost electrocatalytic hydrogen evolution reaction. Chinese Chemical Letters, 2025, 36(2): 110467-. doi: 10.1016/j.cclet.2024.110467
15. [15]
  Xiao Li , Wanqiang Yu , Yujie Wang , Ruiying Liu , Qingquan Yu , Riming Hu , Xuchuan Jiang , Qingsheng Gao , Hong Liu , Jiayuan Yu , Weijia Zhou . Metal-encapsulated nitrogen-doped carbon nanotube arrays electrode for enhancing sulfion oxidation reaction and hydrogen evolution reaction by regulating of intermediate adsorption. Chinese Chemical Letters, 2024, 35(8): 109166-. doi: 10.1016/j.cclet.2023.109166
16. [16]
  Xiangyuan Zhao , Jinjin Wang , Jinzhao Kang , Xiaomei Wang , Hong Yu , Cheng-Feng Du . Ni nanoparticles anchoring on vacuum treated Mo2TiC2Tx MXene for enhanced hydrogen evolution activity. Chinese Journal of Structural Chemistry, 2023, 42(10): 100159-100159. doi: 10.1016/j.cjsc.2023.100159
17. [17]
  Lian Sun , Honglei Wang , Ming Ma , Tingting Cao , Leilei Zhang , Xingui Zhou . Shape and composition evolution of Pt and Pt₃M nanocrystals under HCl chemical etching. Chinese Chemical Letters, 2024, 35(9): 109188-. doi: 10.1016/j.cclet.2023.109188
18. [18]
  Jiao Li , Chenyang Zhang , Chuhan Wu , Yan Liu , Xuejian Zhang , Xiao Li , Yongtao Li , Jing Sun , Zhongmin Su . Defined organic-octamolybdate crystalline superstructures derived Mo₂C@C as efficient hydrogen evolution electrocatalysts. Chinese Chemical Letters, 2024, 35(6): 108782-. doi: 10.1016/j.cclet.2023.108782
19. [19]
  Bin Dong , Ning Yu , Qiu-Yue Wang , Jing-Ke Ren , Xin-Yu Zhang , Zhi-Jie Zhang , Ruo-Yao Fan , Da-Peng Liu , Yong-Ming Chai . Double active sites promoting hydrogen evolution activity and stability of CoRuOH/Co₂P by rapid hydrolysis. Chinese Chemical Letters, 2024, 35(7): 109221-. doi: 10.1016/j.cclet.2023.109221
20. [20]
  Xinlong Zheng , Zhongyun Shao , Jiaxin Lin , Qizhi Gao , Zongxian Ma , Yiming Song , Zhen Chen , Xiaodong Shi , Jing Li , Weifeng Liu , Xinlong Tian , Yuhao Liu . Recent advances of CuSbS₂ and CuPbSbS₃ as photocatalyst in the application of photocatalytic hydrogen evolution and degradation. Chinese Chemical Letters, 2025, 36(3): 110533-. doi: 10.1016/j.cclet.2024.110533

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(586)
HTML views(134)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Hydrogen production performance of the non-platinum-based MoS2/CuS cathode in microbial electrolytic cells

Metrics

通讯作者: 陈斌, bchen63@163.com

Hydrogen production performance of the non-platinum-based MoS₂/CuS cathode in microbial electrolytic cells