In situ formation of a 3D core/shell structured Ni3N@Ni–Bi nanosheet array: an efficient non-noble-metal bifunctional electrocatalyst toward full water splitting under near-neutral conditions

It is of great importance but still remains a key challenge to develop non-noble-metal bifunctional catalysts for efficient full water splitting under mild pH conditions. In this communication, we report the in situ electrochemical development of an ultrathin Ni–Bi layer on a metallic Ni3N nanosheet array supported on a Ti mesh (Ni3N@Ni–Bi NS/Ti) as a durable 3D core/shell structured nanoarray electrocatalyst for water oxidation at near-neutral pH. The Ni3N@Ni–Bi NS/Ti demands overpotentials of 405 and 382 mV to deliver a geometrical catalytic current density of 10 mA cm−2 in 0.1 and 0.5 M K–Bi (pH: 9.2), respectively, superior in activity to Ni3N NS/Ti and most reported non-precious metal catalysts under benign conditions. It also performs efficiently for the hydrogen evolution reaction requiring an overpotential of 265 mV for 10 mA cm−2 and its two-electrode electrolyser affords 10 mA cm−2 at a cell voltage of 1.95 V in 0.5 M K–Bi at 25 °C.

[1]  Xuping Sun,et al.  Core–Shell‐Structured NiS2@Ni‐Bi Nanoarray for Efficient Water Oxidation at Near‐Neutral pH , 2017 .

[2]  De-jun Wang,et al.  Efficient electrocatalysis of overall water splitting by ultrasmall NixCo3−xS4 coupled Ni3S2 nanosheet arrays , 2017 .

[3]  Abdullah M. Asiri,et al.  Interconnected Network of Core-Shell CoP@CoBiPi for Efficient Water Oxidation Electrocatalysis under Near Neutral Conditions. , 2017, ChemSusChem.

[4]  Abdullah M. Asiri,et al.  In situ surface derivation of an Fe–Co–Bi layer on an Fe-doped Co3O4 nanoarray for efficient water oxidation electrocatalysis under near-neutral conditions , 2017 .

[5]  Xuping Sun,et al.  In situ electrochemical surface derivation of cobalt phosphate from a Co(CO3)0.5(OH)·0.11H2O nanoarray for efficient water oxidation in neutral aqueous solution. , 2017, Nanoscale.

[6]  Abdullah M. Asiri,et al.  Cu(OH)2 @CoCO3 (OH)2 ·nH2 O Core-Shell Heterostructure Nanowire Array: An Efficient 3D Anodic Catalyst for Oxygen Evolution and Methanol Electrooxidation. , 2017, Small.

[7]  De-jun Wang,et al.  In situ electrochemical formation of NiSe/NiOx core/shell nano-electrocatalysts for superior oxygen evolution activity , 2016 .

[8]  Harry B Gray,et al.  Earth-Abundant Heterogeneous Water Oxidation Catalysts. , 2016, Chemical reviews.

[9]  Guodong Li,et al.  Overall Water Splitting Catalyzed Efficiently by an Ultrathin Nanosheet‐Built, Hollow Ni3S2‐Based Electrocatalyst , 2016 .

[10]  Shuai Wang,et al.  Ultra-small Fe2N nanocrystals embedded into mesoporous nitrogen-doped graphitic carbon spheres as a highly active, stable, and methanol-tolerant electrocatalyst for the oxygen reduction reaction , 2016 .

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

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

[13]  M. Antonietti,et al.  The Synthesis of Nanostructured Ni5P4 Films and their Use as a Non‐Noble Bifunctional Electrocatalyst for Full Water Splitting , 2015 .

[14]  Hui Li,et al.  High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting. , 2015, Journal of the American Chemical Society.

[15]  N. Kosugi,et al.  Direct Observation of Active Nickel Oxide Cluster in Nickel–Borate Electrocatalyst for Water Oxidation by In Situ O K-Edge X-ray Absorption Spectroscopy , 2015 .

[16]  Weiguo Song,et al.  A novel Ni3N/graphene nanocomposite as supercapacitor electrode material with high capacitance and energy density , 2015 .

[17]  Wei Xing,et al.  NiSe Nanowire Film Supported on Nickel Foam: An Efficient and Stable 3D Bifunctional Electrode for Full Water Splitting. , 2015, Angewandte Chemie.

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

[19]  Xiaojun Wu,et al.  Metallic nickel nitride nanosheets realizing enhanced electrochemical water oxidation. , 2015, Journal of the American Chemical Society.

[20]  Jens K Nørskov,et al.  Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. , 2015, Journal of the American Chemical Society.

[21]  Ping Jiang,et al.  A cost-effective 3D hydrogen evolution cathode with high catalytic activity: FeP nanowire array as the active phase. , 2014, Angewandte Chemie.

[22]  Mohammad Khaja Nazeeruddin,et al.  Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts , 2014, Science.

[23]  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.

[24]  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.

[25]  D. Nocera,et al.  Proton-electron transport and transfer in electrocatalytic films. Application to a cobalt-based O2-evolution catalyst. , 2013, Journal of the American Chemical Society.

[26]  Daniel G. Nocera,et al.  Mechanistic studies of the oxygen evolution reaction mediated by a nickel-borate thin film electrocatalyst. , 2013, Journal of the American Chemical Society.

[27]  Vittal K. Yachandra,et al.  Structure-activity correlations in a nickel-borate oxygen evolution catalyst. , 2012, Journal of the American Chemical Society.

[28]  Y. Shao-horn,et al.  Synthesis and Activities of Rutile IrO2 and RuO2 Nanoparticles for Oxygen Evolution in Acid and Alkaline Solutions. , 2012, The journal of physical chemistry letters.

[29]  J. Goodenough,et al.  A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles , 2011, Science.

[30]  Marc T. M. Koper,et al.  Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis , 2011 .

[31]  James R. McKone,et al.  Solar water splitting cells. , 2010, Chemical reviews.

[32]  Qiushi Yin,et al.  A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals , 2010, Science.

[33]  J. Nørskov,et al.  Electrolysis of water on oxide surfaces , 2007 .

[34]  T. Korányi Phosphorus promotion of Ni (Co)-containing Mo-free catalysts in thiophene hydrodesulfurization , 2003 .

[35]  M. Dresselhaus,et al.  Alternative energy technologies , 2001, Nature.

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