•  
  •  
 

Ze-xing WU, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China;
Jie WANG, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China;
Jun-po GUO, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China;
Jing ZHU, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China;
De-li WANG, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China;

Corresponding Author

De-li WANG(wangdl81125@hust.edu.cn)

Abstract

Electrochemical catalytic production of hydrogen has been considered as a promising and sustainable strategy for clean and renewable energy technologies. Molybdenum-based non noble metal catalysts for the hydrogen evolution reaction have attracted extensive attention due to its effective catalytic performance. In this review, the recent progresses in molybdenum-carbide, phosphide, nitride and sulfide electrocatalysts are presented. In addition, the strategies to improve the catalytic performance are analyzed and the prospects for the future development trends are expected.

Graphical Abstract

Keywords

hydrogen evolution reaction, electrocatalysis, molybdenum-based materials, nanoparticles

Publication Date

2016-04-28

Online Available Date

2016-03-07

Revised Date

2016-01-27

Received Date

2015-12-10

References

[1] Anxolabéhère-Mallart E, Costentin C, Fournier M, et al. Boron-capped tris(glyoximato) cobalt clathrochelate as a precursor for the electrodeposition of nanoparticles catalyzing H2 evolution in water[J]. Journal of the American Chemical Society, 2012, 134(14): 6104-6107.

[2] Dresselhaus M S, Thomas I L. Alternative energy technologies[J]. Nature, 2001, 414(6861): 332-337.

[3] Turner J A. Sustainable hydrogen production[J]. Science, 2004, 305(5686): 972-974.

[4] Zou X X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting[J]. Chemical Society Reviews, 2015, 44: 5148-5180.

[5] Rostrup-Nielsen J R, Nielsen R. Fuels and energy for the future: The role of catalysis[J]. Catalysis Reviews, 2004, 46(3/4): 247-270.

[6] Cortright R D, Davda R R, Dumesic J A. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water[J]. Nature, 2002, 418(6901): 964-967.

[7] Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode[J]. Nature, 1972, 238: 37.

[8] Subbaraman R, Tripkovic D, Strmcnik D, et al. Enhancing hydrogen evolution activity in water splitting by tailoring Li+-Ni (OH)2-Pt interfaces[J]. Science, 2011, 334(6060): 1256-1260.

[9] Stephens I E L, Chorkendorff I. Minimizing the use of Platinum in hydrogen-evolving electrodes[J]. Angewandte Chemie International Edition, 2011, 50(7): 1476-1477.

[10] Cheng L, Huang W J, Gong Q F, et al. Ultrathin WS2 nanoflakes as a high-performance electrocatalyst for the hydrogen evolution reaction[J]. Angewandte Chemie International Edition 2014, 53(30): 7860-7863.

[11] Jiang P, Liu Q, Liang Y H, et al. A cost-effective 3D hydrogen evolution cathode with high catalytic activity: FeP nanowire array as the active phase[J]. Angewandte Chemie International Edition, 2014, 53(47): 12855-12859.

[12] Morales-Guio C G, Stern L-A, Hu X L. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution[J]. Chemical Society Reviews, 2014, 43(18): 6555-6569.

[13] Bockris J O’M, Potter E C. The mechanism of the cathodic hydrogen evolution reaction[J]. Journal of the Electrochemical Society, 1952, 99(4): 169-186.

[14] Sheng W C, Gasteiger H A, Shao-Horn Y. Hydrogen oxidation and evolution reaction kinetics on platinum: acid vs alkaline electrolytes[J]. Journal of the Electrochemical Society, 2010, 157(11): B1529-B1536.

[15] Hinnemann B, Moses P G, Bonde J, et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution[J]. Journal of the American Chemical Society, 2005, 127(15): 5308-5309.

[16] Choi W I, Wood B C, Schwegler E, et al. Site-dependent free energy barrier for proton reduction on MoS2 edges[J]. The Journal of Physical Chemistry C, 2013, 117(42): 21772-21777.

[17] Nørskov J K, Bligaard T, Logadottir A, et al. Trends in the exchange current for hydrogen evolution[J]. Journal of the Electrochemical Society, 2005, 152(3): J23-J26.

[18] Greeley J, Jaramillo T F, Bonde J, et al. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution[J]. Nature Materials, 2006, 5(11): 909-913.

[19] Callejas J F, Read C G, Popczun E J, et al. Nanostructured Co2P electrocatalyst for the hydrogen evolution reaction and direct comparison with morphologically equivalent CoP[J]. Chemistry of Materials, 2015, 27(10): 3769-3774.

[20] Zhang H C, Li Y J, Zhang G X, et al. A metallic CoS2 nanopyramid array grown on 3D carbon fiber paper as an excellent electrocatalyst for hydrogen evolution[J]. Journal of Materials Chemistry A, 2015, 3(12): 6306-6310.

[21] Chen W F, Muckerman J T, Fujita E. Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts[J]. Chemical Communications, 2013, 49(79): 8896-8909.

[22] Kitchin J R, Nørskov J K, Barteau M A, et al. Trends in the chemical properties of early transition metal carbide surfaces: A density functional study[J]. Catalysis Today, 2005, 105(1): 66-73.

[23] Nørskov J K, Abild-Pedersen F, Studt F, et al. Density functional theory in surface chemistry and catalysis[J]. Proceedings of the National Academy of Sciences of the United States of America, 2011, 108(3): 937-943.

[24] Vrubel H, Hu X L. Molybdenum boride and carbide catalyze hydrogen evolution in both acidic and basic solutions[J]. Angewandte Chemie International Edition, 2012, 51(51): 12703-12706.

[25] Liao L, Wang S N, Xiao J J, et al. A nanoporous molybdenum carbide nanowire as an electrocatalyst for hydrogen evolution reaction[J]. Energy &Environmental Science 2014, 7(1): 387-392.

[26] Ge C J, Jiang P, Cui W, et al. Shape-controllable synthesis of Mo2C nanostructures as hydrogen evolution reaction electrocatalysts with high activity[J]. Electrochimica Acta, 2014, 134(10): 182-186.

[27] Wu H B, Xia B Y, Yu L, et al. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production[J]. Nature Communications, 2015, 6: 6512.

[28] Tang C Y, Sun A K, Xu Y S, et al. High specific surface area Mo2C nanoparticles as an efficient electrocatalyst for hydrogen evolution[J]. Journal of Power Sources, 2015, 296(20): 18-22.

[29] Chen W F, Wang C H, Sasaki K, et al. Highly active and durable nanostructured molybdenum carbide electrocatalysts for hydrogen production[J]. Energy & Environmental Science, 2013, 6(3): 943-951.

[30] Zhang K, Zhao Y, Fu D Y, et al. Molybdenum carbide nanocrystal embedded N-doped carbon nanotubes as electrocatalysts for hydrogen generation[J]. Journal of Materials Chemistry A, 2015, 3(11): 5783-5788.

[31] He C Y, Tao J Z. Synthesis of nanostructured clean surface molybdenum carbides on graphene sheets as efficient and stable hydrogen evolution reaction catalysts[J]. Chemical Communications, 2015, 51(39): 8323-8325.

[32] Wan C, Regmi Y N, Leonard B M. Multiple phases of molybdenum carbide as electrocatalysts for the hydrogen evolution reaction[J]. Angewandte Chemie International Edition, 2014, 53(25): 6407-6410.

[33] Pan L F, Li Y H, Yang S, et al. Molybdenum carbide stabilized on graphene with high electrocatalytic activity for hydrogen evolution reaction[J]. Chemical Communications, 2014, 50(86): 13135-13137.

[34] Youn D H, Han S, Kim J Y, et al. Highly active and stable hydrogen evolution electrocatalysts based on molybdenum compounds on carbon nanotube-graphene hybrid support[J]. ACS Nano, 2014, 8(5): 5164-5173.

[35] Chen W F, Iyer S, Iyer S, et al. Biomass-derived electrocatalytic composites for hydrogen evolution[J]. Energy & Environmental Science, 2013, 6(6): 1818-1826.

[36] Cui W, Cheng N Y, Liu Q, et al. Mo2C nanoparticles decorated graphitic carbon sheets: Biopolymer-derived solid-state synthesis and application as an efficient electrocatalyst for hydrogen Generation[J]. ACS Catalysis, 2014, 4(8): 2658-2661.

[37] Fan M H, Chen H, Wu Y Y, et al. Growth of molybdenum carbide micro-islands on carbon cloth toward binder-free cathodes for efficient hydrogen evolution reaction[J]. Journal of Materials Chemistry A, 2015, 3(31): 16320-16326.

[38] Ma L, Ting L R L, Molinari V, et al. Efficient hydrogen evolution reaction catalyzed by molybdenum carbide and molybdenum nitride nanocatalysts synthesized via the urea glass route[J]. Journal of Materials Chemistry A, 2015, 3(16): 8361-8368.

[39]Wan C, Leonard B M. Iron-doped molybdenum carbide catalyst with high activity and stability for the hydrogen evolution reaction[J]. Chemistry of Materials, 2015, 27(12): 4281-4288.

[40]Xiao P, Ge X M, Wang H B, et al. Novel molybdenum carbide-tungsten carbide composite nanowires and their electrochemical activation for efficient and stable hydrogen evolution[J]. Advanced Functional Materials, 2015, 25(10): 1520-1526.

[41] Prins R, Bussell M E. Metal phosphides: Preparation, characterization and catalytic reactivity[J]. Catalysis Letters, 2012, 142(12): 1413-1436.

[42] Chen X B, Wang D Z, Wang Z P, et al. Molybdenum phosphide: A new highly efficient catalyst for the electrochemical hydrogen evolution reaction[J]. Chemical Communions, 2014, 50(79): 11683-11685.

[43] Xiao P, Sk M A, Thia L, et al. Molybdenum phosphide as an efficient electrocatalyst for the hydrogen evolution reaction[J]. Energy& Environmental Science, 2014, 7(8): 2624-2629.

[44] Xing Z, Liu Q, Asiri A M, et al. Closely interconnected network of molybdenum phosphide nanoparticles: A highly efficient electrocatalyst for generating hydrogen from water[J]. Advanced Materials, 2014, 26(32): 5702-5707.

[45] Cui W, Liu Q, Xing Z C, et al. MoP nanosheets supported on biomass-derived carbon flake: One-step facile preparation and application as a novel high-active electrocatalyst toward hydrogen evolution reaction[J]. Applied Catalysis B: Environmental, 2015, 164: 144-150.

[46] Kibsgaard J, Jaramillo T F. Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction[J]. Angewandte Chemie International Edition, 2014, 53(52): 14433-14437.

[47] McEnaney J M, Crompton J C, Callejas J F, et al. Amorphous molybdenum phosphide nanoparticles for electrocatalytic hydrogen evolution[J]. Chemistry of Materials, 2014, 26(16): 4826-4831.

[48] Ham D J, Lee J S. Transition metal carbides and nitrides as electrode materials for low temperature fuel cells[J]. Energies, 2009, 2(4): 873-899.

[49] Xie J F, Li S, Zhang X D, et al. Atomically-thin molybdenum nitride nanosheets with exposed active surface sites for efficient hydrogen evolution[J]. Chemical Science, 2014, 5: 4615-4620.

[50] Chen W F, Sasaki K, Ma C, et al. Hydrogen-evolution catalysts based on non-noble metal nickel-molybdenum nitride nanosheets[J]. Angewandte Chemie International Edition, 2012, 51(25): 6131-6135.

[51] Cao B F, Veith G M, Neuefeind J C, et al. Mixed close-packed cobalt molybdenum nitrides as non-noble metal electrocatalysts for the hydrogen evolution reaction[J]. Journal of the American Chemical Society, 2013, 135(51): 19186-19192.

[52] Zhao Y, Kamiya K, Hashimoto K, et al. In situ CO2-emission assisted synthesis of molybdenum carbonitride nanomaterial as hydrogen evolution electrocatalyst[J]. Journal of the American Chemical Society, 2015, 137(1): 110-113.

[53] Li Y G, Wang H L, Xie L M, et al. MoS2 nanoparticles grown on graphene: An advanced catalyst for the hydrogen evolution reaction[J]. Journal of the American Chemical Society, 2011, 133(19): 7296-7299.

[54] Nikam R D, Lu A Y, Sonawane P A, et al. Three-dimensional heterostructures of MoS2 nanosheets on conducting MoO2 as an efficient electrocatalyst to enhance hydrogen evolution reaction[J]. ACS Applied Materials &Interfaces, 2015, 7(41): 23328-23335.

[55] Kibsgaard J, Chen Z B, Reinecke B N, et al. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis[J]. Nature Materials, 2012, 11(11): 963-969.

[56] Guo Y X, Zhang X Y, Zhang X P, et al. Defect- and S-rich ultrathin MoS2 nanosheet embedded N-doped carbon nanofibers for efficient hydrogen evolution[J]. Journal of Materials Chemistry A, 2015, 3(31): 15927-15934.

[57] Shi S P, Gao D Q, Xia B R, et al. Enhanced hydrogen evolution catalysis in MoS2 nanosheets by incorporation of a metal phase[J]. Journal of Materials Chemistry A, 2015, 3(48): 24414-24421.

[58] Deng Z H, Li L, Ding W, et al. Synthesized ultrathin MoS2 nanosheets perpendicular to graphene for catalysis of hydrogen evolution reaction[J]. Chemical Communications, 2015, 51(10): 1893-1896.

[59] 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.

[60] Wang T Y, Zhuo J Q, Du K Z, et al. Electrochemically fabricated polypyrrole and MoSx copolymer films as a highly active hydrogen evolution electrocatalyst[J]. Advanced Materials, 2014, 26(22): 3761-3766.

[61] Nikam R D, Lu A Y, Sonawane P A, et al. Three-dimensional heterostructures of MoS2 nanosheets on conducting MoO2 as an efficient electrocatalyst to enhance hydrogen evolution reaction[J]. ACS Applied Materials &Interfaces, 2015, 7(41): 23328-23335.

[62] Yang L J, Zhou W J, Hou D M, et al. Porous metallic MoO2-supported MoS2 nanosheets for enhanced electrocatalytic activity in the hydrogen evolution reaction[J]. Nanoscale, 2015, 7(12): 5203-5208.

[63] Smith A J, Chang Y H, Raidongia K, et al. Molybdenum sulfide supported on crumpled graphene balls for electrocatalytic hydrogen production[J]. Advanced Energy Materials, 2014, 4(14): 1400398.

[64] Tan Y W, Liu P, Chen L Y, et al. Monolayer MoS2 films supported by 3D nanoporous metals for high-efficiency electrocatalytic hydrogen production[J]. Advanced Materials, 2014, 26(47): 8023-8028.

[65] Kumar T N, Chandrasekaran N, Phani K L. Structural and electronic modification of MoS2 nanosheets using S-doped carbon for efficient electrocatalysis of the hydrogen evolution reaction[J]. Chemical Communications, 2015, 51(24): 5052-5055.

[66] Ren X P, Ma Q, Fan H B, et al. A Se-doped MoS2 nanosheet for improved hydrogen evolution reaction[J]. Chemical Communications, 2015, 51(88): 15997-16000.

[67] Miao J M, Xiao F X, Yang H B, et al. Hierarchical Ni-Mo-S nanosheets on carbon fiber cloth: A flexible electrode for efficient hydrogen generation in neutral electrolyte[J]. Science Advances, 2015, 1(7): e1500259.

[68] Gao M R, Chan M K Y, Sun Y G. Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production[J]. Nature Communications, 2015, 6:74693.

[69] Lukowski M A, Daniel A S, Meng F, et al. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets[J]. Journal of the American Chemical Society, 2013, 135(28): 10274-10277.

[70] Seo B, Jung G Y, Sa Y J, et al. Monolayer-precision synthesis of molybdenum sulfide nanoparticles and their nanoscale size effects in the hydrogen evolution reaction[J]. ACS Nano, 2015, 9(4): 3728-3739.

Download

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.