泡沫镍负载NiFeMoCu析氢阴极电极材料的电化学制备研究
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摘要
以泡沫镍(NF)为基板,分别通过恒电位法(i-t)和计时电位法(CP)沉积镍铁钼铜四元合金,经去合金化处理,获得了具有高催化活性的析氢阴极电极材料NiFeMoCu/NF。电沉积过程设计了6种电解液配方进行优选,去合金化处理时采用恒电位法(i-t)分别进行了金属铜的原位溶出和独立溶出。结果表明:参照配方4的物料配比组织电解液,以计时电位法沉积四元合金,经铜的独立溶出后制得了由纳米颗粒堆积而成团簇状结构的析氢电极材料。在1mol/L KOH溶液中,催化电流密度为10mA/cm~2时,NiFeMoCu/NF电极的析氢过电位仅为65mV,其高催化活性主要归因于镍铁钼铜四元合金的金属间协同作用。
Ni-Fe-Mo-Cu quaternary alloy catalysts for hydrogen evolution reaction(HER),which was grown insitu 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 of10 mA·cm~(-2) for HER in 1 mol/L KOH.The excellent electrocatalytic activity can be ascribed to the intermetallic synergistic effect between the four metals.
Ni-Fe-Mo-Cu quaternary alloy catalysts for hydrogen evolution reaction(HER),which was grown insitu 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 of10 mA·cm~(-2) for HER in 1 mol/L KOH.The excellent electrocatalytic activity can be ascribed to the intermetallic synergistic effect between the four metals.
引文
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[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 grapheneprotected 3DNi 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.