Abstract: Ni-Fe-Mo-Cu quaternary alloy catalysts for hydrogen evolution reaction (HER),which was grown in-situ on nickel foam (NF) substrate by potentiostatic method and chronopotentiometry,respectively,followed by electrochemical dealloying.Six formulas for optimization of electrolyte composition were designed.The in-situ and independent potentiostatic dissolution of Cu in Ni-Fe-Mo-Cu quaternary alloy were respectively achieved during the dealloying process.Results showed that the optimal electrolyte composition was formula 4,NiFeMoCu/NF with cluster structure piled by nanoparticles,prepared by chronopotentiometry followed by the independent selective dissolution of Cu from the deposits.The as-obtained cathode required an overpotential of merely 65 mV to driver a current density of 10mA·cm-2 for HER in 1mol/L KOH.The excellent electrocatalytic activity can be ascribed to the intermetallic synergistic effect between the four metals.
孙强强. 泡沫镍负载NiFeMoCu析氢阴极电极材料的电化学制备研究[J]. 化工新型材料, 2019, 47(7): 163-168.
Sun Qiangqiang. Electrochemical preparation of Ni-Fe-Mo-Cu on nickel foam cathode for high-efficiency HER. New Chemical Materials, 2019, 47(7): 163-168.
Li J S,Wang Y,Liu C H,et al.Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution[J].Nature Communications,2016,7:11204.
[2]
Lu Q,Hutchings G S,Yu W,et al.Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution[J].Nature Communications,2015,6:6567.
[3]
Anastasopoulos A,Blake J,Hayden B E.Non-noble intertransition binary metal alloy electrocatalyst for hydrogen oxidation and hydrogen evolution[J].Journal of Physical Chemistry C,2011,115(39):19226-19230.
[4]
Saha S,Vaidya S,Ramanujachary K V,et al.Ternary alloy nanocatalysts for hydrogen evolution reaction[J].Bull Mater Sci,2016,39(2):433-436.
[5]
Zhang X,Xu H M,Li X X,et al.Facile synthesis of nickel-iron/nanocarbon hybrids as advanced electrocatalysts for efficient water splitting[J].ACS Catalysis,2016,6:580-588.
[6]
Angelo A,Lasia A C D.Surface effects in the hydrogen evolution reaction on Ni-Zn alloy electrodes in alkaline solutions[J].Journal of The Electrochemical Society,1995,142:3313-3319.
[7]
Koboski K R,Nelsen E F,Hampton J R.Hydrogen evolution reaction measurements of dealloyed porous NiCu[J].Nanoscale Research Letters,2013,8(1):528.
[8]
Shetty S,Sadiq M M J,Bhat D K,et al.Electrodeposition and characterization of Ni-Mo alloy as an electrocatalyst for alkaline water electrolysis[J].Journal of the Electrochemical Society,2017,796:57-65.
[9]
Masataka H,Mamoru M.Preparation of nanoporous Ni and Ni-Cu by dealloying of rolled Ni-Mn and Ni-Cu-Mn alloys[J].Journal of Alloys and Compounds,2009,485(1-2):583-587.
[10]
Xia M,Lei T,Lv N,et al.Synthesis and electrocatalytic hydrogen evolution performance of Ni-Mo-Cu alloy coating electrode[J].International Journal of Hydrogen Energy,2014,39(10):4794-4802.
[11]
Pashova V,Mirkova L,Monev M.Electrocatalytic materials of Ni-Co-Re electrodeposited alloy for alkaline water electrolysis[J].ECS Transactions,2010,25(35):395-401.
[12]
Allam M,Benaicha M,Dakhouche A.Electrodeposition and characterization of NiMoW alloy as electrode material for hydrogen evolution in alkaline water electrolysis[J].International Journal of Hydrogen Energy,2018,43(6):3394-3405.
[13]
Ezaki H,Morinaga M,Watanabe S.Hydrogen overpotential for transition metals and alloys,and its interpretation using an electronic model[J].Electrochimica Acta,1993,38(4):557-564.
[14]
Yin Z W,Chen F Y.Electrochemically fabricated hierarchical porous Ni(OH)2/NiCu electrodes for hydrogen evolution reaction[J].Electrochimica Acta,2014,117:84-91.
[15]
Goranova D,Avdeev G,Rashkov R.Electrodeposition and characterization of Ni-Cu alloys[J].Surface and Coatings Technology,2014,240:204-210.
[16]
Xiao C L,Li Y B,Lu X Y,et al.Bifunctional porous NiFe/NiCo2O4/Ni foam electrodes with triple hierarchy and double synergies for efficient whole cell water splitting[J].Advanced Functional Materials,2016,26(20):3515-3523.
[17]
Chang Y H,Lin C T,Chen T Y,et al.Highly efficient electrocatalytic hydrogen production by MoSx grown on graphene-protected 3D Ni foams[J].Advanced Materials,2013,25(5):756-760.
[18]
Chen J,Sheng K X,Luo P H,et al.Graphene hydrogels deposited in nickel foams for high-rate electrochemical capacitors[J].Advanced Materials,2012,24(33):4569-4573.
[19]
Haciismailoglu M,Alper M.Effect of electrolyte pH and Cu concentration on microstructure of electrodeposited Ni-Cu alloy films[J].Surface & Coatings Technology,2011,206(6):1430-1438.
[20]
Crnkovic F C,Machado S A S,Avaca L A.Electrochemical and morphological studies of electrodeposited Ni-Fe-Mo-Zn alloys tailored for water electrolysis[J].International Journal of Hydrogen Energy,2004,29(3):249-254.
[21]
Konkena B,Puring K J,Sinev I,et al.Pentlandite rocks as sustainable and stable efficient electrocatalysts for hydrogen generation[J].Nature Communications,2016,7:12269.
[22]
Brewer L,Wengert P R.Transition metal alloys of extraordinary stability:an example of generalized Lewis acid-base interactions in metallic systems[J].Metallurgical Transactions,1973,4(1):83-104.
[23]
Sun L,Chien C L,Searson P C.Fabrication of nanoporous nickel by electrochemical dealloying[J].Chemistry of Materials,2004,16(16):3125-3129.
[24]
Chang J K,Hsu S H,Sun I W,et al.Formation of nanoporous nickel by selective anodic etching of the nobler copper component from electrodeposited nickel-copper alloys[J].The Journal of Physical Chemistry C,2008,112(5):1371-1376.