Corresponding Author

Jun-jie GE(gejj@ciac.ac.cn);
Chang-peng LIU(liuchp@ciac.ac.cn);
Wei XING(xingwei@ciac.ac.cn)


Hydrogen energy technology with hydrogen as an energy carrier is gaining more and more attention due to its cleanliness and high energy density. Hydrogen fuel cell vehicles have been listed as one of the ultimate energy technologies in the 21st century. Among them, sustainable hydrogen production technology is a necessary prerequisite for the future development of hydrogen energy economy. Electrolyzed water technology driven by renewable resources represents an important way to support the sustainable development of hydrogen energy economy. The development and utilization of high activity, low cost hydrogen evolution catalysts is a key factor in improving the efficiency and reducing the cost of water electrolysis technology. This paper mainly introduces the recent research progress of hydrogen evolution catalysts including low platinum catalysts and non-platinum transition metal catalysts such as metal sulfides metal phosphides, metal selenides, etc; catalytic properties, synthesis methods, and structure-catalytic properties. Finally, the advantages and challenges of water electrolysis low platinum and non-platinum transition metal catalysts in the future development are prospected.

Graphical Abstract


low Pt, non-Pt, hydrogen evolution catalysts, water electrolysis

Publication Date


Online Available Date


Revised Date


Received Date



[1] Ma Y Y(马元元), Guo Z W(郭昭薇), Wang Y G(王永刚), et al. The new application of battery-electrode reaction: decoupled hydrogen production in water electrolysis[J]. Journal of Electrochemistry(电化学),2018,24(5):444-454.

[2] Seh Z W, Kibsgaard J, Dickens C F, et al. Combining theory and experiment in electrocatalysis: Insights into materials design[J]. Science, 2017, 355(6321): eaad4998.

[3] Wang M Y, Wang Z, Gong X Z, et al. The intensification technologies to water electrolysis for hydrogen production - A review[J]. Renewable & Sustainable Energy Reviews, 2014, 29: 573-588.

[4] Zou X X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting[J]. Chemical Society Reviews, 2015, 44 (15): 5148-5180.

[5] Trancik J E. Back the renewables boom[J]. Nature, 2014, 507(7492): 300-302.

[6] Zhang L L(张玲玲), Dong S J(董绍俊). Developments of photo-assisted fuel cells[J]. Journal of Electrochemistry(电化学), 2016, 22(3): 219-230.

[7] Mallouk T E. Water electrolysis divide and conquer[J]. Nature Chemistry, 2013, 5(5): 362-363.

[8] Thomas C E. Fuel cell and battery electric vehicles compared[J]. International Journal of Hydrogen Energy, 2009, 34 (15): 6005-6020.

[9] Kreuter W, Hofmann H. Electrolysis: The important energy transformer in a world of sustainable energy[J]. International Journal of Hydrogen Energy, 1998, 23(8): 661-666.

[10] Leroy R L. Industrial water electrolysis-present and future[J]. International Journal of Hydrogen Energy, 1983, 8(6): 401-417.

[11] Jiao Y, Zheng Y, Jaroniec M T, et al. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions[J]. Chemical Society Reviews, 2015, 44(8): 2060-2086.

[12] Voiry D, Yang J, Chhowalla M. Recent strategies for improving the catalytic activity of 2D TMD nanosheets toward the hydrogen evolution reaction[J]. Advanced Materials, 2016, 28(29): 6197-6206.

[13] Zeng K, Zhang D K. Recent progress in alkaline water electrolysis for hydrogen production and applications[J]. Progress in Energy and Combustion Science, 2010, 36(3): 307-326.

[14] Cook T R, Dogutan D K, Reece S Y, et al. Solar energy supply and storage for the legacy and non legacy worlds[J]. Chemical Reviews, 2010, 110(11): 6474-6502.

[15] 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.

[16] Shinde S S, Sami A, Lee J H. Electrocatalytic hydrogen evolution using graphitic carbon nitride coupled with nanoporous graphene co-doped by S and Se[J]. Journal of Materials Chemistry A, 2015, 3(24): 12810-12819.

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

[18] Vrubel H, Moehl T, Graetzel M, et al. Revealing and accelerating slow electron transport in amorphous molybdenum sulphide particles for hydrogen evolution reaction[J]. Chemical Communications, 2013, 49(79): 8985-8987.

[19] Yan H J, Jiao Y Q, Wu A P, et al. Cluster-like molybdenum phosphide anchored on reduced graphene oxide for efficient hydrogen evolution over a broad pH range[J]. Chemical Communications, 2016, 52(61): 9530-9533.

[20] Quaino P, Juarez F, Santos E, et al. Volcano plots in hydrogen electrocatalysis-uses and abuses[J]. Beilstein Journal of Nanotechnology, 2014, 5: 846-854.

[21] Chang J F, Xiao Y, Luo Z Y, et al. Recent progress of non-noble metal catalysts in water electrolysis for hydrogen production[J]. Acta Physico-Chimica Sinica, 2016, 32(7): 1556-1592.

[22] Antolini E. Catalysts for direct ethanol fuel cells[J]. Journal of Power Sources, 2007, 170(1): 1-12.

[23] Li K, Li Y, Wang Y M, et al. Enhanced electrocatalytic performance for the hydrogen evolution reaction through surface enrichment of platinum nanoclusters alloying with ruthenium in situ embedded in carbon[J]. Energy & Environmental Science, 2018, 11(5): 1232-1239.

[24] Wang J, Chen J W, Chen J D, et al. Designed synthesis of size-controlled Pt-Cu alloy nanoparticles encapsulated in carbon nanofibers and their high efficient electrocatalytic activity toward hydrogen evolution reaction[J]. Advanced Materials Interfaces, 2017, 4(12): 1700005.

[25] Tiwari J N, Sultan S, Myung C W, et al. Multicomponent electrocatalyst with ultralow Pt loading and high hydrogen evolution activity[J]. Nature Energy, 2018, 3(9): 773-782.

[26] Kim J, Kim H E, Lee H. Single-atom catalysts of precious metals for electrochemical reactions[J]. ChemSusChem, 2018, 11(1): 104-113.

[27] Cheng N C, Stambula S, Wang D, et al. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction[J]. Nature Communications, 2016, 7: 13638.

[28] Jiang B B, Liao F, Sun Y Y, et al. Pt nanocrystals on nitrogen-doped graphene for the hydrogen evolution reaction using Si nanowires as a sacrificial template[J]. Nano-scale, 2017, 9(28): 10138-10144.

[29] Huang R J, Sun Z T, Chen S, et al. Pt-Cu hierarchical quasi great dodecahedrons with abundant twinning defects for hydrogen evolution[J]. Chemical Communications, 2017, 53(51): DOI: 10.1039/c7cc03643d.

[30] Wu Z X(吴则星), Wang J(王杰), Guo J P(郭军坡), et al. Recent progresses in molybdenum-based electrocatalysts for the hydrogen reaction[J]. Journal of Electrochemistry(电化学), 2016, 22(2): 194-204.

[31] Luo Z Y, Ouyang Y X, Zhang H, et al. Chemically activating MoS2 via spontaneous atomic palladium interfacial doping towards efficient hydrogen evolution[J]. Nature Communications, 2018, 9: 2120.

[32] Xie J F, Zhang H, Li S, et al. Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution[J]. Advanced Materials, 2013, 25(40): 5807-5813.

[33] Yang Q B, He Y, Zou C J, et al. Composite electrocatalyst MoxW1-xS2 nanosheets on carbon fiber paper for highly efficient hydrogen evolution reaction[J]. Journal of Solid State Electrochemistry, 2018, 22(10): 2969-2976.

[34] Oyama S T, Gott T, Zhao H, et al. Transition metal phosphide hydroprocessing catalysts: A review[J]. Catalysis Today, 2009, 143 (1/2): 94-107.

[35] Liu P, Rodriguez J A. Catalysts for hydrogen evolution from the NiFe hydrogenase to the Ni2P(001) surface: The importance of ensemble effect[J]. Journal of the American Chemical Society, 2005, 127(42): 14871-14878.

[36] Pan Y, Liu Y, Zhao J, et al. Monodispersed nickel phosphide nanocrystals with different phases: Synthesis, characterization and electrocatalytic properties for hydrogen evolution[J]. Journal of Materials Chemistry A, 2015, 3(4): 1656-1665.

[37] Popczun E J, McKone J R, Read C G, et al. Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction[J]. Journal of the American Chemical Society, 2013, 135(25): 9267-9270.

[38] Chang J F, Li S T, Li G Q, et al. Monocrystalline Ni12P5 hollow spheres with ultrahigh specific surface areas as advanced electrocatalysts for the hydrogen evolution reaction[J]. Journal of Materials Chemistry A, 2016, 4(25): 9755-9759.

[39] Chang J F, Li K, Wu Zv J, et al. Sulfur-doped nickel phosphide nanoplates arrays: a monolithic electrocatalyst for efficient hydrogen evolution reactions[J]. ACS Applied Materials & Interfaces, 2018, 10(31): 26303-26311.

[40] Popczun E J, Read C G, Roske C W, et al. Highly active electrocatalysis of the hydrogen evolution reaction by cobalt phosphide nanoparticles**[J]. Angewandte Chemie-International Edition, 2014, 53(21): 5427-5430.

[41] Chang J F, Ouyang Y X, Ge J J, et al. Cobalt phosphosulfide in the tetragonal phase: a highly active and durable catalyst for the hydrogen evolution reaction[J]. Journal of Materials Chemistry A, 2018, 6(26): 12353-12360.

[42] Zhao W T, Lu X Q, Selvaraj M, et al. MXP(M=Co/Ni)@carbon core-shell nanoparticles embedded in 3D cross-linked graphene aerogel derived from seaweed biomass for hydrogen evolution reaction[J]. Nanoscale, 2018, 10(20): 9698-9706.

[43] Anantharaj S, Ede S R, Sakthikumar K, et al. Recent trends and perspectives in electrochemical water splitting with an emphasis on sulfide, selenide, and phosphide catalysts of Fe, Co, and Ni: A review[J]. ACS Catalysis, 2016, 6(12): 8069-8097.

[44] Zhou X L, Jiang J, Ding T, et al. Fast colloidal synthesis of scalable Mo-rich hierarchical ultrathin MoSe2-x nano-sheets for high-performance hydrogen evolution[J]. Nano-scale, 2014, 6(19): 11046-11051.

[45] Liu B, Zhao Y F, Peng H Q, et al. Nickel-cobalt diselenide 3D mesoporous nanosheet networks supported on Ni foam: an all-pH highly efficient integrated electrocatalyst for hydrogen evolution[J]. Advanced Materials, 2017, 29(19): 1606521.

[46] Fang L, Li W X, Guan Y X, et al. Tuning unique peapod-like Co(SxSe1-x)(2) nanoparticles for efficient overall water splitting[J]. Advanced Functional Materials, 2017, 27(24): 1701008.

[47] Deng S J, Zhong Y, Zeng Y X, et al. Directional construction of vertical nitrogen-doped 1T-2H MoSe2/grapheene shell/core nanoflake arrays for efficient hydrogen evolution reaction[J]. Advanced Materials, 2017, 29(21): 1700748.



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.