MoS2/GQDs催化剂的制备及微生物电解池的产氢性能研究

doi:10.13208/j.electrochem.200725

摘要/Abstract

摘要：

通过水热法合成了一系列MoS₂/GQDs复合材料,并制成碳基复合电极。利用电化学测试手段挑选出最佳电极后用于微生物电解池（MEC）阴极的产氢性能研究。实验结果显示： Na₂MoO₄、半胱氨酸和GQDs的最佳原料配比为375:600:1,制备出的MoS₂/GQDs呈现明显的爆米花样纳米片结构,片层厚度在10 nm左右,当碳纸负载量为1.5 mg·cm^-2时,MoS₂/GQDs碳纸电极的析氢催化能力最佳。在MEC产氢实验中,MoS₂/GQDs阴极MEC的产气量、氢气产率、库仑效率、整体氢气回收率、阴极氢气回收率、电能回收率和整体能量回收率分别为51.15±3.15 mL·cycle^-1、0.401±0.032 m³H₂·m³d^-1、91.16±0.054%、66.64±5.39%、72.44±2.60%、217.26±7.42%和77.37±1.50%,均略高于Pt/C阴极MEC或与之媲美。另外,MoS₂/GQDs具有良好的长期稳定性,且价格便宜,有利于实际应用。

关键词: MoS₂/GQDs, 碳基电极, 微生物电解池, 产氢

Abstract:

Microbial electrolysis cell (MEC) is a relatively new bioelectrochemical technology that produces H₂ and meanwhile treats organic wastewater. Cathode hydrogen evolution catalyst plays a key role in MEC. The doping of Graphene Quantum Dots (GQDs) into MoS₂ nanosheets can improve the catalytic activity of MoS₂ by creating abundant defect sites both in the edge plane and the basal plane, as well as enhancing the electrical conductivity. In this paper, using Na₂MoO₄, cysteine and GQDs as raw materials, a series of MoS₂/GQDs composites were firstly synthesized via hydrothermal method, and then loaded on the carbon-based electrode. The optimal electrode was selected by electrochemical testing methods and used as a cathode of MEC to research the hydrogen production capacity. SEM image showed that the MoS₂/GQDs composite exhibited a popcorn-like nanosheet structure and the thickness of each nanosheet was about 10 nm. The specific surface area of MoS₂/GQDS composite reached 67.155 m²·g^-1, which was 16 times of the specific surface area of MoS₂ (4.197 m²·g^-1). TEM image showed that some lattice fringes representing GQDs were intermixed with lattice fringes representing MoS₂, which indicated that GQDs were well embedded in MoS₂. EDS results showed that the MoS₂/GQDS composite contained Mo, S, C and O, and the atomic ratio of Mo: S: C: O = 1:2.5:1.9:1.2, indicating that the majority of Mo and S in the composite existed in the form of MoS₂, while a part of S existed in the form of SO_x. The LSV data of MoS₂/GQDs carbon paper electrode showed that the synthesized MoS₂/GQDs composite (2#) had the best catalytic activity toward hydrogen evolution when the raw material ratio of Na₂MoO₄, cysteine and GQDs was 375:600:1 with the optimum load of 1.5 mg·cm^-2. The Tafel slope of MoS₂/GQDs electrode (2#, 1.5 mg·cm^-2) was found to be 44.3 mV·dec^-1, lower than that of pure MoS₂ electrode, which indicated that the doping of GQDs into MoS₂ nanosheets made the electron transport more efficiently and the interfacial resistance was significantly reduced. In the MEC tests, the maximum hydrogen current density of MoS₂/GQDS cathode (2#, 1.5 mg·cm^-2) MEC reached 14.70 ± 0.80 A·m^-2, which was comparable to that of Pt/C cathode MEC (14.58 ± 0.92 A·m^-2), indicating that MoS₂/GQDS had a good catalytic activity for hydrogen evolution. The gas production, hydrogen production rate, coulombic efficiency, hydrogen recovery efficiency, cathodic hydrogen recovery efficiency, electrical and overall energy recovery efficiencies of MoS₂/GQDs cathode (2#, 1.5 mg·cm^-2) MEC were, respectively, 51.15±3.15 mL·cycle^-1, 0.40±0.032 m³H₂·m^-3d^-1, 91.16±0.054%, 66.64±5.39%, 72.44±2.60%, 217.26±7.42% and 77.37±1.50%, which were slightly higher than or comparable to those of Pt/C cathode MEC. In addition, MoS₂/GQDs enjoyed good stability and price advantage, which might promote the practical application of MECs.

Key words: MoS₂/GQDs, carbon-based electrode, microbial electrolysis cell, hydrogen production

代红艳, 杨慧敏, 刘宪, 宋秀丽, 梁镇海. MoS₂/GQDs催化剂的制备及微生物电解池的产氢性能研究[J]. 电化学（中英文）, 2021, 27(4): 429-438.

Hong-Yan Dai, Hui-Min Yang, Xian Liu, Xiu-Li Song, Zhen-Hai Liang. Preparation and Electrochemical Evaluation of MoS₂/Graphene Quantum Dots as a Catalyst for Hydrogen Evolution in Microbial Electrolysis Cell[J]. Journal of Electrochemistry, 2021, 27(4): 429-438.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200725

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I4/429

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参考文献 44

[1]	Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future[J]. Nature, 2012, 488(7411): 294-303. doi: 10.1038/nature11475 URL
[2]	Turner J A. Sustainable hydrogen production[J]. Science, 2004, 305(5686): 972-974. doi: 10.1126/science.1103197 URL
[3]	Liu H, Grot S, Logan B E. Electrochemically assisted microbial production of hydrogen from acetate[J]. Environ. Sci. Technol., 2005, 39(11): 4317-4320. doi: 10.1021/es050244p URL
[4]	Kundu A, Sahu J N, Redzwan G, Hashim M A. An overview of cathode material and catalysts suitable for generating hydrogen in microbial electrolysis cell[J]. Int. J. Hydrog. Energy, 2013, 38(4): 1745-1757. doi: 10.1016/j.ijhydene.2012.11.031 URL
[5]	De Silva Muňoz L, Bergel A, Féron D, Basseguy R. Hydrogen production by electrolysis of a phosphate solution on a stainless steel cathode[J]. Int. J. Hydrog. Energy, 2010, 35(16): 8561-8568. doi: 10.1016/j.ijhydene.2010.05.101 URL
[6]	He B H, Chen L, Jing M J, Zhou M J, Hou Z H, Chen X B. 3D MoS₂-rGO@Mo nanohybrids for enhanced hydrogen evolution: The importance of the synergy on the Volmer reaction[J]. Electrochim. Acta, 2018, 283: 357-365. doi: 10.1016/j.electacta.2018.06.168 URL
[7]	Wu Z Z, Fei H, Wang D Z. MoS₂/Cu₂O nanohybrid as a highly efficient catalyst for the photoelectrocatalytic hydrogen generation[J]. Mater. Lett., 2019, 256: 126622. doi: 10.1016/j.matlet.2019.126622 URL
[8]	Xiang Z C, Zhang Z, Xu X J, Zhang Q, Yuan C W. MoS₂ nanosheets array on carbon cloth as a 3D electrode for highly efficient electrochemical hydrogen evolution[J]. Carbon, 2016, 98: 84-89. doi: 10.1016/j.carbon.2015.10.071 URL
[9]	Li G Q, Zhang D, Qiao Q, Li G Q, Zhang D, Qiao Q, Yu Y F, Peterson D, Zafar A, Kumar R, Curtarolo S, Hunte F, Shannon S, Zhu Y M, Yang W T, Cao L Y. All the catalytic active sites of MoS₂ for hydrogen evolution[J]. J. Am. Chem. Soc., 2016, 138(51): 16632-16638. doi: 10.1021/jacs.6b05940 URL
[10]	Guo J X, Zhu H F, Sun Y F, Tang L, Zhang X. Doping MoS₂ with graphene quantum dots: structural and electrical engineering towards enhanced electrochemical hydrogen evolution[J]. Electrochim. Acta, 2016, 211: 603-610. doi: 10.1016/j.electacta.2016.05.148 URL
[11]	Laursen A B, Kegnaes S, Dahl S, Chorkendorff I. Molybdenum sulfides efficient and viable materials for electro- and photoelectrocatalytic hydrogen evolution[J]. Energy Environ. Sci., 2012, 5(2): 5577-5591. doi: 10.1039/c2ee02618j URL
[12]	Kong D S, Wang H T, Cha J J, Pasta M, Koski K J, Yao J, Cui Y. Synjournal of MoS₂ and MoSe₂ films with vertically aligned layers[J]. Nano Lett., 2013, 13(3): 1341-1347. doi: 10.1021/nl400258t URL
[13]	Dai H Y(代红艳), Yang H M(杨慧敏), Liu X(刘宪), Jian X(简选), Guo M M(郭敏敏), Cao L L(曹乐乐), Liang Z H(梁镇海). Preparation and electrochemical evaluation of MoS₂/graphene as a catalyst for hydrogen evolution in microbial electrolysis cell[J]. Chem. J. Chinese U.(高等学校化学学报), 2018, 39(2): 351-358.
[14]	Li F, Li J, Lin X Q, Li X Z, Fang Y Y, Jiao L X, An X C, Fu Y, Jin J, Li R. Designed synjournal of multi-walled carbon nanotubes@Cu@MoS₂ hybrid as advanced electrocatalyst for highly efficient hydrogen evolution reaction[J]. J. Power Sources, 2015, 300: 301-308. doi: 10.1016/j.jpowsour.2015.09.084 URL
[15]	Hu W H, Han G Q, Liu Y R, Dong B, Chai Y M, Liu Y Q, Liu C G. Ultrathin MoS₂-coated carbon nanospheres as highly efficient electrocatalyts for hydrogen evolution reaction[J]. Int. J. Hydrog. Energy, 2015, 40(20): 6552-6558. doi: 10.1016/j.ijhydene.2015.03.150 URL
[16]	Ge P Y, Scanlon M D, Peljo P, Bian X J, Vubrel H, O'Neill A, Coleman J N, Cantoni M, Hu X L, Kontturi K, Liu B H, Girault H H. Hydrogen evolution across nano-schottky Junctions at carbon supported MoS₂ catalysts in biphasic liquid systems[J]. Chem. Comm, 2012, 48(52): 6484-6486. doi: 10.1039/c2cc31398g URL
[17]	Wang P C, Wan L, Lin Y Q, Wang B G. MoS₂ supported CoS₂ on carbon cloth as a high performance electrode for hydrogen evolution reaction[J]. Int. J. Hydrog. Energy, 2019, 44(31): 16566-16574. doi: 10.1016/j.ijhydene.2019.04.195 URL
[18]	Guo Y X, Zhang X Y, Zhang X P, You T Y. Defect- and S-rich ultrathin MoS₂ nanosheet embedded N-doped carbon nanofibers for efficient hydrogen evolution[J]. J. Mater. Chem. A, 2015, 3(31): 15927-15934. doi: 10.1039/C5TA03766B URL
[19]	Karunadasa H I, Montalvo E, Sun Y J, Majda M, Long J R, Chang C J. A molecular MoS₂ edge site mimic for catalytic hydrogen generation[J]. Science, 2012, 335(6069): 698-702. doi: 10.1126/science.1215868 URL
[20]	Wu L Q, Xu X B, Zhao Y Q, Zhang K Y, Sun Y, Wang T T, Wang Y Q, Zhong W, Du Y W. Mn doped MoS₂/reduced graphene oxide hybrid for enhanced hydrogen evolution[J]. Appl. Surf. Sci., 2017, 425: 470-477. doi: 10.1016/j.apsusc.2017.06.223 URL
[21]	Yan Y, Xia B Y, Ge X M, Liu Z L, Wang J Y, Wang X. Ultrathin MoS₂ nanoplates with rich active sites as highly efficient catalyst for hydrogen evolution[J]. ACS Appl. Mater. Interfaces, 2013, 5(24): 12794-12798. doi: 10.1021/am404843b URL
[22]	Xie J F, Zhang H, Li S, Wang R X, Sun X, Zhou M, Zhou J F, Lou X W, Xie Y. Defect-rich MoS₂ ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution[J]. Adv. Mater., 2013, 25(40): 5807-5813. doi: 10.1002/adma.v25.40 URL
[23]	Antonios K. Graphene quantum dots: In the crossroad of graphene, quantum dots and carbogenic nanoparticles[J]. Curr. Opin. Colloid Interface Sci., 2015, 20(5-6): 354-361. doi: 10.1016/j.cocis.2015.11.001 URL
[24]	Dai H Y(代红艳), Yang H M(杨慧敏), Liu X(刘宪), Song X L(宋秀丽), Liang Z H(梁镇海). Hydrogen production of microbial electrolysis cell using scrap metal net as cathode and the analysis of microbial community structure in anode[J]. J. Electrochem.(电化学), 2019, 25(6): 773-780.
[25]	Li Z W, Ye R Q, Feng R, Kang Y M, Zhu X, Tour J M, Fang Z Y. Graphene quantum dots doping of MoS₂ monolayers[J]. Adv. Mater., 2015, 27(35): 5235-5240. doi: 10.1002/adma.201501888 URL
[26]	Zhao X, Zhu H, Yang X R. Amorphous carbon supported MoS₂ nanosheets as effective catalysts for electrocatalytic hydrogen evolution[J]. Nanoscale, 2014, 6(18): 10680-10685. doi: 10.1039/C4NR01885K URL
[27]	Chao D L, Zhu C R, Xia X H, Liu J L, Zhang X, Wang J, Liang P, Lin J Y, Zhang H, Shen Z X, Fan H J. Graphene quantum dots coated VO₂ arrays for highly durable electrodes for Li and Na ion batteries[J]. Nano Lett., 2015, 15(1): 565-573. doi: 10.1021/nl504038s URL
[28]	Wang C X, Jin J L, Sun Y Y, Yao J R, Zhao G Z, Liu Y Q. In-situ synjournal and ultrasound enhanced adsorption properties of MoS₂/graphene quantum dot nanocomposite[J]. Chem. Eng. J., 2017, 327: 774-782. doi: 10.1016/j.cej.2017.06.163 URL
[29]	Miao J W, Xiao F X, Yang H B, Khoo S Y, Chen J Z, Fan Z X, Hsu Y Y, Chen H M, Zhang H, Liu B. Hierarchical Ni-Mo-S nanosheets on carbon fiber cloth: A flexible electrode for efficient hydrogen generation in neutral electrolyte[J]. Sci. Adv., 2015, 1(7): e1500259. doi: 10.1126/sciadv.1500259 URL
[30]	Guo J X, Li F F, Sun Y F, Zhang X, Tang L. Oxygen-incorporated MoS₂ ultrathin nanosheets grown on graphene for efficient electrochemical hydrogen evolution[J]. J. Power Sources, 2015, 291: 195-200. doi: 10.1016/j.jpowsour.2015.05.034 URL
[31]	Xie J F, Zhang J J, Li S, Grote F, Zhang X D, Zhang H, Wang R X, Lei Y, Pan B C, Xie Y. Controllable disorder engineering in oxygen-incorporated MoS₂ ultrathin nano-sheets for efficient hydrogen evolution[J]. J. Am. Chem. Soc., 2013, 135(47): 17881-17888. doi: 10.1021/ja408329q URL
[32]	Zhao S Y, Li C X, Wang L P, Liu N Y, Qiao S, Liu B B, Huang H, Liu Y, Kang Z H. Carbon quantum dots modified MoS₂ with visible-light-induced high hydrogen evolution catalytic ability[J]. Carbon, 2016, 99: 599-606. doi: 10.1016/j.carbon.2015.12.088 URL
[33]	Lu Y Z, Jiang Y Y, Wei W T, Wu H B, Liu M M, Niu L, Chen W. Novel blue light emitting graphene oxide nanosheets fabricated by surface functionalization[J]. J. Mater. Chem., 2012, 22(7): 2929-2934. doi: 10.1039/C1JM14174K URL
[34]	Liu M M, Chen W. Green synjournal of silver nanoclusters supported on carbon nanodots: enhanced photoluminescence and high catalytic activity for oxygen reduction reaction[J]. Nanoscale, 2013, 5(24): 12558-12564. doi: 10.1039/c3nr04054b URL
[35]	Hu W H, Shang X, Han G Q, Dong B, Liu Y R, Li X, Chai Y M, Liu Y Q, Liu C G. MoS_x supported graphene oxides with different degree of oxidation as efficient electrocatalysts for hydrogen evolution[J]. Carbon, 2016, 100: 236-242. doi: 10.1016/j.carbon.2016.01.019 URL
[36]	Yan Y, Ge X M, Liu Z L, Wang J Y, Lee J M, Wang X. Facile synjournal of low crystalline MoS₂ nanosheet-coated CNTs for enhanced hydrogen evolution reaction[J]. Nanoscale, 2013, 5(17): 7768-7771. doi: 10.1039/c3nr02994h URL
[37]	Zheng X L, Xu J B, Yan K Y, Wang H, Wang Z L. Space-confined growth of MoS₂ nanosheets within graphite: the layered hybrid of MoS₂ and graphene as an active catalyst for hydrogen evolution reaction[J]. Chem. Mater., 2014, 26(7): 2344-2353. doi: 10.1021/cm500347r URL
[38]	Merki D, Hu X L. Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts[J]. Energy Environ. Sci., 2011, 4(10): 3878-3888. doi: 10.1039/c1ee01970h URL
[39]	Li Y G, Wang H L, Xie L M, Liang Y Y, Hong G S, Dai H J. MoS₂ nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction[J]. J. Am. Chem. Soc., 2011, 133(19): 7296-7299. doi: 10.1021/ja201269b URL
[40]	Kong D S, Wang H T, Lu Z Y, Cui Y. CoSe₂ nanoparticles grown on carbon fiber paper: an efficient and stable electrocatalyst for hydrogen evolution reaction[J]. J. Am. Chem. Soc., 2014, 136(13): 4897-4900. doi: 10.1021/ja501497n URL
[41]	Dai H Y, Yang H M, Liu X, Jian X, Liang Z H. Electrochemical evaluation of nano-Mg(OH)₂/graphene as a catalyst for hydrogen evolution in microbial electrolysis cell[J]. Fuel, 2016, 174: 251-256. doi: 10.1016/j.fuel.2016.02.013 URL
[42]	Tokash J C, Logan B E. Electrochemical evaluation of molybdenum disulfide as a catalyst for hydrogen evolution in microbial electrolysis cells[J]. Int. J. Hydrog. Energy, 2011, 36(16): 9439-9445. doi: 10.1016/j.ijhydene.2011.05.080 URL
[43]	Su M, Wei L L, Qiu Z Z, Wang G, Shen J Q. Hydrogen production in single chamber microbial electrolysis cells with stainless steel fiber felt cathodes[J]. J. Power Sources, 2016, 301: 29-34. doi: 10.1016/j.jpowsour.2015.09.108 URL
[44]	Wang A J, Liu W Z, Cheng S A, Xing D F, Zhou J H, Logan B E. Source of methane and methods to control its formation in single chamber microbial electrolysis cells[J]. Int. J. Hydrog. Energy, 2009, 34(9): 3653-3658. doi: 10.1016/j.ijhydene.2009.03.005 URL

	Q_gas/(mL·cycle^-1)	H₂/%	CH₄/%	CO₂/%	Q_H2/(m³H₂·m³d^-1)
MoS₂/GQDs	51.15±3.15	62.57±1.21	8.18±1.60	29.25±0.39	0.401±0.032
Pt/C	48.85±4.55	60.29±4.01	10.70±2.10	28.36±4.76	0.377±0.052
PC	3.75±0.55	43.71±1.41	3.97±0.74	51.40±1.60	0.021±0.004
	R_CE/%	R_H2/%	R_cat/%	η_W/%	η_W+S/%
MoS₂/GQDs	91.16±0.054	66.64±5.39	72.44±2.60	217.26±7.42	77.37±1.50
Pt/C	83.19±11.77	62.75±8.67	71.40±9.03	228.39±18.91	83.46±10.16
PC	19.18±2.97	3.48±0.61	17.41±2.26	45.60±4.90	3.97±0.55

MoS₂/GQDs催化剂的制备及微生物电解池的产氢性能研究

Preparation and Electrochemical Evaluation of MoS₂/Graphene Quantum Dots as a Catalyst for Hydrogen Evolution in Microbial Electrolysis Cell

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Metrics

Serial & number	A/mL	B/mL
1#	60	0
2#	45	15
3#	36	24