Bimetallic Cobalt‐Based Phosphide Zeolitic Imidazolate Framework: CoPx Phase‐Dependent Electrical Conductivity and Hydrogen Atom Adsorption Energy for Efficient Overall Water Splitting

Cobalt‐based bimetallic phosphide encapsulated in carbonized zeolitic imadazolate frameworks has been successfully synthesized and showed excellent activities toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Density functional theory calculation and electrochemical measurements reveal that the electrical conductivity and electrochemical activity are closely associated with the Co2P/CoP mixed phase behaviors upon Cu metal doping. This relationship is found to be the decisive factor for enhanced electrocatalytic performance. Moreover, the precise control of Cu content in Co‐host lattice effectively alters the Gibbs free energy for H* adsorption, which is favorable for facilitating reaction kinetics. Impressively, an optimized performance has been achieved with mild Cu doping in Cu0.3Co2.7P/nitrogen‐doped carbon (NC) which exhibits an ultralow overpotential of 0.19 V at 10 mA cm–2 and satisfying stability for OER. Cu0.3Co2.7P/NC also shows excellent HER activity, affording a current density of 10 mA cm–2 at a low overpotential of 0.22 V. In addition, a homemade electrolyzer with Cu0.3Co2.7P/NC paired electrodes shows 60% larger current density than Pt/RuO2 couple at 1.74 V, along with negligible catalytic deactivation after 50 h operation. The manipulation of electronic structure by controlled incorporation of second metal sheds light on understanding and synthesizing bimetallic transition metal phosphides for electrolysis‐based energy conversion.

[1]  Chengzhou Zhu,et al.  Facilely Tuning Porous NiCo2 O4 Nanosheets with Metal Valence-State Alteration and Abundant Oxygen Vacancies as Robust Electrocatalysts Towards Water Splitting. , 2016, Chemistry.

[2]  Yujie Sun,et al.  Hierarchically Porous Urchin-Like Ni2P Superstructures Supported on Nickel Foam as Efficient Bifunctional Electrocatalysts for Overall Water Splitting , 2016 .

[3]  Chengzhou Zhu,et al.  Highly efficient nonprecious metal catalysts towards oxygen reduction reaction based on three-dimensional porous carbon nanostructures. , 2016, Chemical Society reviews.

[4]  Li Wang,et al.  Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH-Value Electrochemical and Photocatalytic Hydrogen Evolution. , 2016, Journal of the American Chemical Society.

[5]  Yong Wang,et al.  Molybdenum-Carbide-Modified Nitrogen-Doped Carbon Vesicle Encapsulating Nickel Nanoparticles: A Highly Efficient, Low-Cost Catalyst for Hydrogen Evolution Reaction. , 2015, Journal of the American Chemical Society.

[6]  S. Gul,et al.  High-Performance Overall Water Splitting Electrocatalysts Derived from Cobalt-Based Metal–Organic Frameworks , 2015 .

[7]  Shannon W. Boettcher,et al.  Oxygen Evolution Reaction Electrocatalysis on Transition Metal Oxides and (Oxy)hydroxides: Activity Trends and Design Principles , 2015 .

[8]  Tatsuya Shinagawa,et al.  Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion , 2015, Scientific Reports.

[9]  Shuhong Yu,et al.  From Bimetallic Metal‐Organic Framework to Porous Carbon: High Surface Area and Multicomponent Active Dopants for Excellent Electrocatalysis , 2015, Advanced materials.

[10]  Xiaoxin Zou,et al.  Noble metal-free hydrogen evolution catalysts for water splitting. , 2015, Chemical Society reviews.

[11]  Zhe Zhang,et al.  Defect‐Rich CoP/Nitrogen‐Doped Carbon Composites Derived from a Metal–Organic Framework: High‐Performance Electrocatalysts for the Hydrogen Evolution Reaction , 2015 .

[12]  Lain‐Jong Li,et al.  Rugae-like FeP nanocrystal assembly on a carbon cloth: an exceptionally efficient and stable cathode for hydrogen evolution. , 2015, Nanoscale.

[13]  R. E. Schaak,et al.  Nanostructured Co2P Electrocatalyst for the Hydrogen Evolution Reaction and Direct Comparison with Morphologically Equivalent CoP , 2015 .

[14]  X. Lou,et al.  Formation of nickel sulfide nanoframes from metal-organic frameworks with enhanced pseudocapacitive and electrocatalytic properties. , 2015, Angewandte Chemie.

[15]  Chengzhou Zhu,et al.  Nickel cobalt oxide hollow nanosponges as advanced electrocatalysts for the oxygen evolution reaction. , 2015, Chemical communications.

[16]  X. Lou,et al.  Designed Formation of Co₃O₄/NiCo₂O₄ Double-Shelled Nanocages with Enhanced Pseudocapacitive and Electrocatalytic Properties. , 2015, Journal of the American Chemical Society.

[17]  Luai M. Al-Hadhrami,et al.  Pumped hydro energy storage system: A technological review , 2015 .

[18]  Charles C. L. McCrory,et al.  Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. , 2015, Journal of the American Chemical Society.

[19]  X. Lou,et al.  Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production , 2015, Nature Communications.

[20]  Zhengxiao Guo,et al.  Visible-light driven heterojunction photocatalysts for water splitting – a critical review , 2015 .

[21]  Yong Wang,et al.  In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution. , 2015, Journal of the American Chemical Society.

[22]  Mietek Jaroniec,et al.  Metal-organic framework derived hybrid Co3O4-carbon porous nanowire arrays as reversible oxygen evolution electrodes. , 2014, Journal of the American Chemical Society.

[23]  Yanguang Li,et al.  Ultrathin WS2 nanoflakes as a high-performance electrocatalyst for the hydrogen evolution reaction. , 2014, Angewandte Chemie.

[24]  Fei Meng,et al.  Highly active hydrogen evolution catalysis from metallic WS2 nanosheets , 2014 .

[25]  Xiaoming Ge,et al.  Molybdenum phosphide as an efficient electrocatalyst for the hydrogen evolution reaction , 2014 .

[26]  Fang Song,et al.  Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis , 2014, Nature Communications.

[27]  Mohd Wazir Mustafa,et al.  Energy storage systems for renewable energy power sector integration and mitigation of intermittency , 2014 .

[28]  Brian M. Leonard,et al.  Multiple phases of molybdenum carbide as electrocatalysts for the hydrogen evolution reaction. , 2014, Angewandte Chemie.

[29]  P. Ajayan,et al.  Porous Spinel Zn(x)Co(3-x)O(4) hollow polyhedra templated for high-rate lithium-ion batteries. , 2014, ACS nano.

[30]  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.

[31]  K. Zhou,et al.  Zeolitic imidazolate framework 67-derived high symmetric porous Co₃O₄ hollow dodecahedra with highly enhanced lithium storage capability. , 2014, Small.

[32]  Xin Wang,et al.  Recent Development of Molybdenum Sulfides as Advanced Electrocatalysts for Hydrogen Evolution Reaction , 2014 .

[33]  Giovanna Cavazzini,et al.  A new generation of small hydro and pumped-hydro power plants: Advances and future challenges , 2014 .

[34]  Shun Mao,et al.  High-performance bi-functional electrocatalysts of 3D crumpled graphene–cobalt oxide nanohybrids for oxygen reduction and evolution reactions , 2014 .

[35]  X. Lou,et al.  Defect‐Rich MoS2 Ultrathin Nanosheets with Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen Evolution , 2013, Advanced materials.

[36]  Zhaolin Liu,et al.  Facile synthesis of low crystalline MoS2 nanosheet-coated CNTs for enhanced hydrogen evolution reaction. , 2013, Nanoscale.

[37]  D. Portehault,et al.  Nanoscaled metal borides and phosphides: recent developments and perspectives. , 2013, Chemical reviews.

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

[39]  T. Jaramillo,et al.  In situ X-ray absorption spectroscopy investigation of a bifunctional manganese oxide catalyst with high activity for electrochemical water oxidation and oxygen reduction. , 2013, Journal of the American Chemical Society.

[40]  Jakob Kibsgaard,et al.  Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. , 2012, Nature materials.

[41]  Vladimir Strezov,et al.  Assessment of utility energy storage options for increased renewable energy penetration , 2012 .

[42]  Andreas Sumper,et al.  A review of energy storage technologies for wind power applications , 2012 .

[43]  T. Jaramillo,et al.  Core-shell MoO3-MoS2 nanowires for hydrogen evolution: a functional design for electrocatalytic materials. , 2011, Nano letters.

[44]  Tom Regier,et al.  Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. , 2011, Nature materials.

[45]  Guosong Hong,et al.  MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. , 2011, Journal of the American Chemical Society.

[46]  Se-Yeun Lee,et al.  Effects of projected climate change on energy supply and demand in the Pacific Northwest and Washington State , 2010 .

[47]  Gvozden S. Tasic,et al.  Electrocatalytic activation of Ni electrode for hydrogen production by electrodeposition of Co and V species , 2009 .

[48]  A. Mar,et al.  X-ray Photoelectron and Absorption Spectroscopy of Metal-Rich Phosphides M2P and M3P (M = Cr−Ni) , 2008 .

[49]  Daniel G. Nocera,et al.  In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+ , 2008, Science.

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

[51]  Ping Liu,et al.  Catalysts for hydrogen evolution from the [NiFe] hydrogenase to the Ni2P(001) surface: the importance of ensemble effect. , 2005, Journal of the American Chemical Society.