Synergistic Nanotubular Copper-Doped Nickel Catalysts for Hydrogen Evolution Reactions.

Developing highly active electrocatalysts with low cost and high efficiency for hydrogen evolution reactions (HERs) is of great significance for industrial water electrolysis. Herein, a 3D hierarchically structured nanotubular copper-doped nickel catalyst on nickel foam (NF) for HER is reported, denoted as Ni(Cu), via facile electrodeposition and selective electrochemical dealloying. The as-prepared Ni(Cu)/NF electrode holds superlarge electrochemical active surface area and exhibits Pt-like electrocatalytic activity for HER, displaying an overpotential of merely 27 mV to achieve a current density of 10 mA cm-2 and an extremely small Tafel slope of 33.3 mV dec-1 in 1 m KOH solution. The Ni(Cu)/NF electrode also shows excellent durability and robustness in both continuous and intermittent bulk water electrolysis. Density functional theory calculations suggest that Cu substitution and the formation of NiO on the surface leads to more optimal free energy for hydrogen adsorption. The lattice distortion of Ni caused by Cu substitution, the increased interfacial activity induced by surface oxidation of nanoporous Ni, and numerous active sites at Ni atom offered by the 3D hierarchical porous structure, all contribute to the dramatically enhanced catalytic performance. Benefiting from the facile, scalable preparation method, this highly efficient and robust Ni(Cu)/NF electrocatalyst holds great promise for industrial water-alkali electrolysis.

[1]  Y. Tong,et al.  Efficient Hydrogen Evolution on Cu Nanodots-Decorated Ni3S2 Nanotubes by Optimizing Atomic Hydrogen Adsorption and Desorption. , 2018, Journal of the American Chemical Society.

[2]  Lei Zhang,et al.  Highly Efficient and Stable Water‐Oxidation Electrocatalysis with a Very Low Overpotential using FeNiP Substitutional‐Solid‐Solution Nanoplate Arrays , 2017, Advanced materials.

[3]  Xiaomin Zhang,et al.  Mo doped Ni2P nanowire arrays: an efficient electrocatalyst for the hydrogen evolution reaction with enhanced activity at all pH values. , 2017, Nanoscale.

[4]  Xiaozhou Liao,et al.  Hydrogen evolution reaction activity of nickel phosphide is highly sensitive to electrolyte pH , 2017 .

[5]  Shuangming Chen,et al.  Nickel Diselenide Ultrathin Nanowires Decorated with Amorphous Nickel Oxide Nanoparticles for Enhanced Water Splitting Electrocatalysis. , 2017, Small.

[6]  P. Menezes,et al.  From a Molecular 2Fe-2Se Precursor to a Highly Efficient Iron Diselenide Electrocatalyst for Overall Water Splitting. , 2017, Angewandte Chemie.

[7]  Xiaodong Zhuang,et al.  Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics , 2017, Nature Communications.

[8]  Shengli Zhai,et al.  A hierarchically porous nickel-copper phosphide nano-foam for efficient electrochemical splitting of water. , 2017, Nanoscale.

[9]  Yibing Li,et al.  Enhancing Water Oxidation Catalysis on a Synergistic Phosphorylated NiFe Hydroxide by Adjusting Catalyst Wettability , 2017 .

[10]  Boštjan Genorio,et al.  Design principles for hydrogen evolution reaction catalyst materials , 2016 .

[11]  Xiaobo Chen,et al.  FeNi3/NiFeOx Nanohybrids as Highly Efficient Bifunctional Electrocatalysts for Overall Water Splitting , 2016 .

[12]  Tianxi Liu,et al.  Molybdenum Carbide Anchored on Graphene Nanoribbons as Highly Efficient All-pH Hydrogen Evolution Reaction Electrocatalyst , 2016 .

[13]  P. Dong,et al.  Electrochemical fabrication of porous Ni-Cu alloy nanosheets with high catalytic activity for hydrogen evolution , 2016 .

[14]  Abdullah M. Asiri,et al.  Ternary FexCo1-xP Nanowire Array as a Robust Hydrogen Evolution Reaction Electrocatalyst with Pt-like Activity: Experimental and Theoretical Insight. , 2016, Nano letters.

[15]  B. Zhang,et al.  Iron–Nickel Nitride Nanostructures in Situ Grown on Surface-Redox-Etching Nickel Foam: Efficient and Ultrasustainable Electrocatalysts for Overall Water Splitting , 2016 .

[16]  Jinhui Hao,et al.  Superhydrophilic and Superaerophobic Copper Phosphide Microsheets for Efficient Electrocatalytic Hydrogen and Oxygen Evolution , 2016 .

[17]  R. Schmid,et al.  Pentlandite rocks as sustainable and stable efficient electrocatalysts for hydrogen generation , 2016, Nature Communications.

[18]  Yan Lin,et al.  Metal Doping Effect of the M-Co2P/Nitrogen-Doped Carbon Nanotubes (M = Fe, Ni, Cu) Hydrogen Evolution Hybrid Catalysts. , 2016, ACS applied materials & interfaces.

[19]  Zhiyi Lu,et al.  Binary nickel–iron nitride nanoarrays as bifunctional electrocatalysts for overall water splitting , 2016 .

[20]  Yi Cui,et al.  Porous MoO2 Nanosheets as Non‐noble Bifunctional Electrocatalysts for Overall Water Splitting , 2016, Advanced materials.

[21]  Yifu Yu,et al.  Anchoring CoO Domains on CoSe2 Nanobelts as Bifunctional Electrocatalysts for Overall Water Splitting in Neutral Media , 2016, Advanced science.

[22]  Z. Dai,et al.  Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution , 2016, Nature Communications.

[23]  C. Liu,et al.  Characteristics of a sintered porous Ni–Cu alloy cathode for hydrogen production in a potassium hydroxide solution , 2016 .

[24]  Yang Tian,et al.  Ternary NiFeMn layered double hydroxides as highly-efficient oxygen evolution catalysts. , 2016, Chemical communications.

[25]  Hung-Chih Chang,et al.  Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide. , 2015, Nature materials.

[26]  Xin-bo Zhang,et al.  C and N Hybrid Coordination Derived Co-C-N Complex as a Highly Efficient Electrocatalyst for Hydrogen Evolution Reaction. , 2015, Journal of the American Chemical Society.

[27]  Gengfeng Zheng,et al.  Nanoparticle Superlattices as Efficient Bifunctional Electrocatalysts for Water Splitting. , 2015, Journal of the American Chemical Society.

[28]  Tianxi Liu,et al.  In-Situ Growth of Few-Layered MoS2 Nanosheets on Highly Porous Carbon Aerogel as Advanced Electrocatalysts for Hydrogen Evolution Reaction , 2015 .

[29]  Dezhi Wang,et al.  Sulfur-Decorated Molybdenum Carbide Catalysts for Enhanced Hydrogen Evolution , 2015 .

[30]  K. Ng,et al.  Electrodeposition of ultrathin nickel–cobalt double hydroxide nanosheets on nickel foam as high-performance supercapacitor electrodes , 2015 .

[31]  Xunyu Lu,et al.  Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities , 2015, Nature Communications.

[32]  Bryan T. Yonemoto,et al.  Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution , 2015, Nature Communications.

[33]  N. Yao,et al.  Nanocrystalline Ni5P4: A hydrogen evolution electrocatalyst of exceptional efficiency in both alkaline and acidic media , 2015 .

[34]  Ib Chorkendorff,et al.  Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation. , 2015, The journal of physical chemistry letters.

[35]  Yi Xie,et al.  Atomically-thin two-dimensional sheets for understanding active sites in catalysis. , 2015, Chemical Society reviews.

[36]  M. Mecklenburg,et al.  Two-dimensional metal-organic surfaces for efficient hydrogen evolution from water. , 2015, Journal of the American Chemical Society.

[37]  Weifeng Zhang,et al.  A highly efficient flexible dye-sensitized solar cell based on nickel sulfide/platinum/titanium counter electrode , 2015, Nanoscale Research Letters.

[38]  J. Zhang,et al.  Electrodeposition of magnetic, superhydrophobic, non-stick, two-phase Cu-Ni foam films and their enhanced performance for hydrogen evolution reaction in alkaline water media. , 2014, Nanoscale.

[39]  Abdullah M. Asiri,et al.  Self-supported Cu3P nanowire arrays as an integrated high-performance three-dimensional cathode for generating hydrogen from water. , 2014, Angewandte Chemie.

[40]  Yongfeng Hu,et al.  Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis , 2014, Nature Communications.

[41]  S. Ding,et al.  Hierarchical NiCo2O4 Nanosheets@halloysite Nanotubes with Ultrahigh Capacitance and Long Cycle Stability As Electrochemical Pseudocapacitor Materials , 2014 .

[42]  J. S. Lee,et al.  Highly active and stable hydrogen evolution electrocatalysts based on molybdenum compounds on carbon nanotube-graphene hybrid support. , 2014, ACS nano.

[43]  E. Nelsen,et al.  Hydrogen evolution reaction measurements of dealloyed porous NiCu , 2013, Nanoscale Research Letters.

[44]  S. Nam,et al.  Effect of morphology of electrodeposited Ni catalysts on the behavior of bubbles generated during the oxygen evolution reaction in alkaline water electrolysis. , 2013, Chemical communications.

[45]  James R. McKone,et al.  Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction. , 2013, Journal of the American Chemical Society.

[46]  Yexiang Tong,et al.  Amorphous nickel hydroxide nanospheres with ultrahigh capacitance and energy density as electrochemical pseudocapacitor materials , 2013, Nature Communications.

[47]  Lain-Jong Li,et al.  Highly Efficient Electrocatalytic Hydrogen Production by MoSx Grown on Graphene‐Protected 3D Ni Foams , 2013, Advanced materials.

[48]  J. Xu,et al.  Fabrication of three-dimensional nanoporous nickel films with tunable nanoporosity and their excellent electrocatalytic activities for hydrogen evolution reaction , 2013 .

[49]  G. F. Ortiz,et al.  Improved Energy Storage Solution Based on Hybrid Oxide Materials , 2013 .

[50]  Jiaoyang Li,et al.  Ultrathin Mesoporous NiCo2O4 Nanosheets Supported on Ni Foam as Advanced Electrodes for Supercapacitors , 2012 .

[51]  J. Tu,et al.  Three-dimensional porous nano-Ni supported silicon composite film for high-performance lithium-ion batteries , 2012 .

[52]  G. Shi,et al.  Graphene Hydrogels Deposited in Nickel Foams for High‐Rate Electrochemical Capacitors , 2012, Advanced materials.

[53]  Akihiko Hirata,et al.  Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors. , 2011, Nature nanotechnology.

[54]  Thomas Bligaard,et al.  Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations , 2010 .

[55]  A. Inoue,et al.  Nanoporous Metals by Dealloying Multicomponent Metallic Glasses , 2008 .

[56]  Jeng‐Kuei Chang,et al.  Formation of Nanoporous Nickel by Selective Anodic Etching of the Nobler Copper Component from Electrodeposited Nickel−Copper Alloys , 2008 .

[57]  X. Xia,et al.  Superhydrophobicity of 3D Porous Copper Films Prepared Using the Hydrogen Bubble Dynamic Template , 2007 .

[58]  Thomas F. Jaramillo,et al.  Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts , 2007, Science.

[59]  C. Chien,et al.  Fabrication of Nanoporous Nickel by Electrochemical Dealloying , 2004 .

[60]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[61]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[62]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[63]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[64]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[65]  M. Morinaga,et al.  Hydrogen overpotential for transition metals and alloys, and its interpretation using an electronic model , 1993 .

[66]  Zhancheng Guo,et al.  The intensification technologies to water electrolysis for hydrogen production - A review , 2014 .

[67]  Haitao Hu,et al.  High photocatalytic activity and stability for decomposition of gaseous acetaldehyde on TiO2/Al2O3 composite films coated on foam nickel substrates by sol-gel processes , 2008 .