Phase-selective synthesis of self-supported RuP films for efficient hydrogen evolution electrocatalysis in alkaline media.

Large-scale hydrogen production through alkaline water electrolysis requires highly active and less expensive materials to replace platinum as a catalyst for the hydrogen evolution reaction (HER). Ruthenium, as the cheapest platinum-group element, has recently been demonstrated to exhibit excellent activity toward the HER. However, achieving better HER activity of ruthenium-based materials by selecting a more active phase is still unexplored. Herein, we report the fabrication of self-supported RuP and RuP2 catalyst films on carbon cloth (RuP/CC and RuP2/CC) via a facile, potentially scalable, and phase-controllable synthetic method. RuP/CC displays superior catalytic activity with a low overpotential of 13 mV at 10 mA cm-1, outperforming RuP2/CC (33 mV at 10 mA cm-1) and most non-Pt HER catalysts. Moreover, good electrochemical stability and faradaic efficiency of nearly 100% are also demonstrated for RuP/CC. Density functional theory calculations reveal that RuP with a higher charge density at the Ru site is more favorable for the chemisorption of hydrogen, thereby exhibiting better HER activity than RuP2.

[1]  Y. Jiao,et al.  The Hydrogen Evolution Reaction in Alkaline Solution: From Theory, Single Crystal Models, to Practical Electrocatalysts. , 2018, Angewandte Chemie.

[2]  Y. Tong,et al.  Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts. , 2018, Journal of the American Chemical Society.

[3]  Abdullah M. Asiri,et al.  Co(OH)2 Nanoparticle‐Encapsulating Conductive Nanowires Array: Room‐Temperature Electrochemical Preparation for High‐Performance Water Oxidation Electrocatalysis , 2018, Advanced materials.

[4]  Haijun Wu,et al.  Metal-organic framework derived hollow CoS2 nanotube arrays: an efficient bifunctional electrocatalyst for overall water splitting. , 2017, Nanoscale horizons.

[5]  Q. Zhang,et al.  3D Self‐Supported Fe‐Doped Ni2P Nanosheet Arrays as Bifunctional Catalysts for Overall Water Splitting , 2017 .

[6]  Ibrahim Saana Amiinu,et al.  RuP2 -Based Catalysts with Platinum-like Activity and Higher Durability for the Hydrogen Evolution Reaction at All pH Values. , 2017, Angewandte Chemie.

[7]  Abdullah M. Asiri,et al.  Enhanced Electrocatalysis for Energy‐Efficient Hydrogen Production over CoP Catalyst with Nonelectroactive Zn as a Promoter , 2017 .

[8]  Lei Zhang,et al.  Engineering Pt/Pd Interfacial Electronic Structures for Highly Efficient Hydrogen Evolution and Alcohol Oxidation. , 2017, ACS applied materials & interfaces.

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

[10]  Min Han,et al.  Component-Controlled Synthesis of Necklace-Like Hollow NiXRuy Nanoalloys as Electrocatalysts for Hydrogen Evolution Reaction. , 2017, ACS applied materials & interfaces.

[11]  S. Luo,et al.  Fe2P/reduced graphene oxide/Fe2P sandwich-structured nanowall arrays: a high-performance non-noble-metal electrocatalyst for hydrogen evolution , 2017 .

[12]  B. Fokwa,et al.  Boron-Dependency of Molybdenum Boride Electrocatalysts for the Hydrogen Evolution Reaction. , 2017, Angewandte Chemie.

[13]  Y. Jiao,et al.  Polydopamine‐Inspired, Dual Heteroatom‐Doped Carbon Nanotubes for Highly Efficient Overall Water Splitting , 2017 .

[14]  J. Baek,et al.  An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction. , 2017, Nature nanotechnology.

[15]  Qiuju Zhang,et al.  Cobalt-Borate Nanoarray: An Efficient and Durable Electrocatalyst for Water Oxidation under Benign Conditions. , 2017, ACS applied materials & interfaces.

[16]  Qianwang Chen,et al.  Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media , 2017, Nature Communications.

[17]  Yadong Li,et al.  Cage-Confinement Pyrolysis Route to Ultrasmall Tungsten Carbide Nanoparticles for Efficient Electrocatalytic Hydrogen Evolution. , 2017, Journal of the American Chemical Society.

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

[19]  Qianwang Chen,et al.  Pt-like electrocatalytic behavior of Ru–MoO2 nanocomposites for the hydrogen evolution reaction , 2017 .

[20]  M. Jaroniec,et al.  High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst. , 2016, Journal of the American Chemical Society.

[21]  Xiao Shang,et al.  Novel CoP Hollow Prisms as Bifunctional Electrocatalysts for Hydrogen Evolution Reaction in Acid media and Overall Water-splitting in Basic media , 2016 .

[22]  Jamesh MOHAMMED IBRAHIM Recent progress on earth abundant hydrogen evolution reaction and oxygen evolution reaction bifunctional electrocatalyst for overall water splitting in alkaline media , 2016 .

[23]  S. Kundu,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 , 2016 .

[24]  Xiaoxin Li,et al.  In situ fabrication of Ni-Co (oxy)hydroxide nanowire-supported nanoflake arrays and their application in supercapacitors. , 2016, Nanoscale.

[25]  Q. Tang,et al.  Robust and stable ruthenium alloy electrocatalysts for hydrogen evolution by seawater splitting , 2016 .

[26]  B. K. Gupta,et al.  Highly stable hollow bifunctional cobalt sulfides for flexible supercapacitors and hydrogen evolution , 2016 .

[27]  Tian-Yi Ma,et al.  Self-supported electrocatalysts for advanced energy conversion processes , 2016 .

[28]  Q. Xie,et al.  Co-, N-, and S-Tridoped Carbon Derived from Nitrogen- and Sulfur-Enriched Polymer and Cobalt Salt for Hydrogen Evolution Reaction. , 2016, ACS applied materials & interfaces.

[29]  Bin Zhang,et al.  Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction. , 2016, Chemical Society reviews.

[30]  Jinhua Ye,et al.  Active Sites Implanted Carbon Cages in Core-Shell Architecture: Highly Active and Durable Electrocatalyst for Hydrogen Evolution Reaction. , 2016, ACS nano.

[31]  Jun Jiang,et al.  Trimetallic TriStar Nanostructures: Tuning Electronic and Surface Structures for Enhanced Electrocatalytic Hydrogen Evolution , 2016, Advanced materials.

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

[33]  D. Morgan Resolving ruthenium: XPS studies of common ruthenium materials , 2015 .

[34]  A. Schechter,et al.  Ruthenium Phosphide Synthesis and Electroactivity toward Oxygen Reduction in Acid Solutions , 2015 .

[35]  Zonghua Pu,et al.  Ferric phosphide nanoparticles film supported on titanium plate: A high-performance hydrogen evolution cathode in both acidic and neutral solutions , 2015 .

[36]  Xiujun Fan,et al.  WC Nanocrystals Grown on Vertically Aligned Carbon Nanotubes: An Efficient and Stable Electrocatalyst for Hydrogen Evolution Reaction. , 2015, ACS nano.

[37]  Zidong Wei,et al.  In situ growth of ruthenium oxide-nickel oxide nanorod arrays on nickel foam as a binder-free integrated cathode for hydrogen evolution , 2015 .

[38]  Song Jin,et al.  High-performance electrocatalysis using metallic cobalt pyrite (CoS₂) micro- and nanostructures. , 2014, Journal of the American Chemical Society.

[39]  Abdullah M. Asiri,et al.  Self-supported nanoporous cobalt phosphide nanowire arrays: an efficient 3D hydrogen-evolving cathode over the wide range of pH 0-14. , 2014, Journal of the American Chemical Society.

[40]  X. Lou,et al.  Two-dimensional nanosheets for photoelectrochemical water splitting: Possibilities and opportunities , 2013 .

[41]  Jingguang G. Chen,et al.  Correlating the hydrogen evolution reaction activity in alkaline electrolytes with the hydrogen binding energy on monometallic surfaces , 2013 .

[42]  H. Gray,et al.  Hydrogen evolution catalyzed by cobaloximes. , 2009, Accounts of chemical research.

[43]  R. F. Jardim,et al.  Preparation of recoverable Ru catalysts for liquid-phase oxidation and hydrogenation reactions , 2009 .

[44]  Harry B Gray,et al.  Powering the planet with solar fuel. , 2009, Nature chemistry.

[45]  R. C. Forrey,et al.  Influence of CO Poisoning on Hydrogen Chemisorption onto a Pt6 Cluster , 2008 .

[46]  Hansong Cheng,et al.  Density Functional Study of Sequential H2 Dissociative Chemisorption on a Pt6 Cluster , 2007 .

[47]  Raymond J. Kopp,et al.  Energy Resources and Global Development , 2003, Science.

[48]  S. Rundqvist,et al.  Phosphides of the B31 (MnP) Structure Type. , 1961 .

[49]  Abdullah M. Asiri,et al.  Recent Progress in Cobalt‐Based Heterogeneous Catalysts for Electrochemical Water Splitting , 2016, Advanced materials.

[50]  A. Kjekshus,et al.  Compounds with the Marcasite Type Crystal Structure. XII. Structural Data for RuP2, RuAs2, RuSb2, OsP2, OsAs2, and OsSb2. , 1977 .