Corresponding Author

Wei ZHANG(zw@snnu.edu.cn);
Rui CAO(ruicao@ruc.edu.cn)


Electrocatalytic water splitting is considered as a promising technology for renewable energy. The development of efficient, stable, cost-effective, and bifunctional catalysts for both water reduction and oxidation has continued to face significant challenges. Herein, we report a robust and highly active nickel selenide (NiSe) spheres grown on carbon cloth (CC) by electrodeposition from a nickel selenite complex which is a single source containing both Ni and Se. A combination of two chemicals containing, separately, Ni and Se is used in traditional preparations of metal selenides, causing possible problems in the uniformity of the products. The as-prepared NiSe-EA/CC electrode exhibited electrocatalytic activities toward both water reduction and oxidation, with overpotentials of 154 mV at 10 mA·cm-2 and 250 mV at 20 mA·cm-2, respectively. A water electrolysis cell could realize a current density of 10 mA·cm-2 at a cell voltage of 1.53 V with excellent stability, when using NiSe-EA/CC electrode as both the anode and the cathode.

Graphical Abstract


electrocatalysis, nickel selenide, water splitting, hydrogen evolution reaction, oxygen evolution reaction

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[1] Qi J, Zhang W, Cao R. Solar-to-hydrogen energy conversion based on water splitting[J]. Advanced Energy Materials, 2018, 8(5): 1701620.
[2] Zhang X Q, Cheng X B, Zhang Q. Nanostructured energy materials for electrochemical energy conversion and storage: A review[J]. Journal of Energy Chemistry, 2016, 25(6): 967-984.
[3] Dou S, Tao L, Wang R L, et al. Plasma-assisted synthesis and surface modification of electrode materials for renewable energy[J]. Advanced Materials, 2018, 30(21): 1705850.
[4] Duan X C, Xu J T, Ma J M, et al. Atomically thin transition-metal dichalcogenides for electrocatalysis and energy storage[J]. Small Methods, 2017, 1(11): 1700156.
[5] Qi J, Zhang W, Cao R. Porous materials as highly efficient electrocatalysts for the oxygen evolution reaction[J]. ChemCatChem, 2018, 10(6): 1206-1220.
[6] Zhu W X, Yue X Y, Zhang W T, et al. Nickel sulfide microsphere film on Ni foam as an efficient bifunctional electrocatalyst for overall water splitting[J]. Chemical Communications, 2016, 52(7): 1486-1489.
[7] Li X, Zhang L, Huang M R, et al. Cobalt and nickel selenide nanowalls anchored on graphene as bifunctional electrocatalysts for overall water splitting[J]. Journal of Materials Chemistry A, 2016, 4(38): 14789-14795.
[8] Hou C C, Cao S, Fu W F, et al. Ultrafine CoP nanoparticles supported on carbon nanotubes as highly active electrocatalyst for both oxygen and hydrogen evolution in basic media[J]. ACS Applied Materials & Interfaces, 2015, 7(51): 28412-28419.
[9] Liu H F, Gao X Q, Yao X L, et al. Manganese(II) phosphate nanosheet assembly with native out-of-plane Mn centres for electrocatalytic water oxidation[J]. Chemical Science, 2018,10(1): 191-197.
[10] Wan S, Qi J, Zhang W, et al. Hierarchical Co(OH)F superstructure built by low-dimensional substructures for electrocatalytic water oxidation[J]. Advanced Materials, 2017, 29(28): 1700286.
[11] Tian J Q, Liu Q, Asiri A M, et al. Self-supported nanoporous cobalt phosphide nanowire arrays: An efficient 3D hydrogen-evolving cathode over the wide range of pH 0-14[J]. Journal of the American Chemical Society, 2014, 136(21): 7587-7590.
[12] Zhou W J, Wu X J, Cao X H, et al. Ni3S2 nanorods/Ni foam composite electrode with low overpotential for electrocatalytic oxygen evolution[J]. Energy & Environmental Science, 2013, 6(10): 2921-2924.
[13] Zhang M T, Chen Z, Kang P, et al. Electrocatalytic water oxidation with a copper(II) polypeptide complex[J]. Journal of the American Chemical Society, 2013, 135(6): 2048-2051.
[14] Wu Y Z, Chen M X, Han Y Z, et al. Fast and simple preparation of iron-based thin films as highly efficient water-oxidation catalysts in neutral aqueous solution[J]. Angewandte Chemie International Edition, 2015, 54(16): 4870-4875.
[15] Chen M X, Qi J, Zhang W, et al. Electrosynthesis of NiPx nanospheres for electrocatalytic hydrogen evolution from a neutral aqueous solution[J]. Chemical Communications, 2017, 53(40): 5507-5510.
[16] Gao Z, Qi J, Chen M X, et al. An electrodeposited NiSe for electrocatalytic hydrogen and oxygen evolution reactions in alkaline solution[J]. Electrochimica Acta, 2017, 224: 412-418.
[17] Hernandez-Pagan E A, Vargas-Barbosa N M, Wang T H, et al. Resistance and polarization losses in aqueous buffer-membrane electrolytes for water-splitting photoelectrochemical cells[J]. Energy & Environmental Science, 2012, 5(6): 7582-7589.
[18] McCrory C C L, Jung S, Ferrer I M, et al. Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices[J]. Journal of the American Chemical Society, 2015, 137(13): 4347-4357.
[19] Bau J A, Luber E J, Buriak J M. Oxygen evolution catalyzed by nickel-iron oxide nanocrystals with a nonequilibrium phase[J]. ACS Applied Materials & Interfaces, 2015, 7(35): 19755-19763.
[20] Gao Y G, Li H B, Yang G W. Amorphous nickel hydroxide nanosheets with ultrahigh activity and super-long-term cycle stability as advanced water oxidation catalysts[J]. Crystal Growth & Design, 2015, 15(9): 4475-4483.
[21] Tang D, Liu J, Wu X Y, et al. Carbon quantum dot/NiFe layered double-hydroxide composite as a highly efficient electrocatalyst for water oxidation[J]. ACS Applied Materials & Interfaces, 2014, 6(10): 7918-7925.
[22] Wang T x, Li X, Jiang Y M, et al. Reduced graphene oxide-polyimide/carbon nanotube film decorated with NiSe nanoparticles for electrocatalytic hydrogen evolution reactions[J]. Electrochimica Acta, 2017, 243: 291-298.
[23] Li Y X, Yan D F, Zou Y Q, et al. Rapidly engineering the electronic properties and morphological structure of NiSe nanowires for the oxygen evolution reaction[J]. Journal of Materials Chemistry A, 2017, 5(48): 25494-25500.
[24] Wang F M, Li Y C, Shifa TA, et al. Selenium-enriched nickel selenide nanosheets as a robust electrocatalyst for hydrogen generation[J]. Angewandte Chemie International Edition, 2016, 55(24): 6919-6924.
[25] Zhao Q, Zhong D Z, Liu L, et al. Facile fabrication of robust 3D Fe-NiSe nanowires supported on nickel foam as a highly efficient, durable oxygen evolution catalyst[J]. Journal of Materials Chemistry A, 2017, 5(28): 14639-14645.
[26] Zhang W, Qi J, Liu K Q, et al. A nickel-based integrated electrode from an autologous growth strategy for highly efficient water oxidation[J]. Advanced Energy Materials, 2016, 6(12): 1502489.
[27] Akbar K, Jeon J H, Kim M, et al. Bifunctional electrodeposited 3D NiCoSe2/nickle foam electrocatalysts for its applications in enhanced oxygen evolution reaction and for hydrazine oxidation[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(6): 7735-7742.
[28] Swesi A T, Masud J, Nath M. Nickel selenide as a high-efficiency catalyst for oxygen evolution reaction[J]. Energy & Environmental Science, 2016, 9(5): 1771-1782.
[29] Liu F Y, Wang B, Lai Y Q, et al. Electrodeposition of cobalt selenide thin films[J]. Journal of the Electrochemical Society, 2010, 157(10): D523-D527.
[30] Xiao P, Chen W, Wang X. A review of phosphide-based materials for electrocatalytic hydrogen evolution[J]. Advanced Energy Materials, 2015, 5(24): 1500985.
[31] Liu Z J, Zhao Z H, Wang Y Y, et al. In situ exfoliated, edge-rich, oxygen-functionalized graphene from carbon fibers for oxygen electrocatalysis[J]. Advanced Materials, 2017, 29(18): 1606207.
[32] Mi L W, Sun H, Ding Q, et al. 3D hierarchically patterned tubular NiSe with nano-/microstructures for Li ion battery design[J]. Dalton Transactions, 2012, 41(40): 12595-12600.
[33] Kukunuri S, Krishnan M R, Sampath S. The effect of structural dimensionality on the electrocatalytic properties of the nickel selenide phase[J]. Physical Chemistry Chemical Physics, 2015, 17(36): 23448-23459.
[34] Biesinger M C, Payne B P, Lau L W M, et al. X-ray photoelectron spectroscopic chemical state quantification of mixed nickel metal, oxide and hydroxide systems[J]. Surface and Interface Analysis, 2009, 41(4): 324-332.
[35] Tang C, Cheng N Y, Pu Z H, et al. NiSe nanowire film supported on nickel foam: An efficient and stable 3D bifunctional electrode for full water splitting[J]. Angewandte Chemie International Edition, 2015, 54(32): 9351-9355.
[36] Frost RL, Keeffe E C. Raman spectroscopic study of the selenite mineral: Ahifeldite, NiSeO3·2H2O[J]. Journal of Raman Spectroscopy, 2009, 40(5): 509-512.
[37] Zhou X M, Gao P, Sun S C, et al. Amorphous, crystalline and crystalline/amorphous selenium nanowires and their different (de)lithiation mechanisms[J]. Chemistry of Materials, 2015, 27(19): 6730-6736.
[38] Qi J, Zhang W, Cao R. Aligned cobalt-based Co@CoOx nanostructures for efficient electrocatalytic water oxidation[J]. Chemical Communications, 2017, 53(66): 9277-
[39] Song D Y, Wang H Q, Wang X Q, et al. NiSe2 nanoparticles embedded in carbon nanowires as highly efficient and stable electrocatalyst for hydrogen evolution reaction[J]. Electrochimica Acta, 2017, 254: 230-237.
[40] Louie M W, Bell A T. An investigation of thin-film Ni-Fe oxide catalysts for the electrochemical evolution of oxygen[J]. Journal of the American Chemical Society, 2013, 135(33): 12329-12337.



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