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Title: Lattice Matched Carbide–Phosphide Composites with Superior Electrocatalytic Activity and Stability

Journal Article · · Chemistry of Materials
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4];  [5];  [6]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Tennessee, Knoxville, TN (United States). Center for Renewable Carbon
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Education
  3. Stanford Univ., CA (United States). Dept. of Chemical Engineering
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  5. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
  6. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Education

Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. Here, to identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide–phosphide composite prevents catalyst dissolution in acid electrolyte. Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Lastly, our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Nuclear Energy (NE)
Grant/Contract Number:
AC05-00OR22725; NE0000693
OSTI ID:
1410911
Journal Information:
Chemistry of Materials, Vol. 29, Issue 21; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

References (56)

Earth-Abundant Heterogeneous Water Oxidation Catalysts journal October 2016
Advancing the Electrochemistry of the Hydrogen-Evolution Reaction through Combining Experiment and Theory journal November 2014
Noble metal-free hydrogen evolution catalysts for water splitting journal January 2015
Earth-abundant inorganic electrocatalysts and their nanostructures for energy conversion applications journal January 2014
Electrocatalysis developments for hydrogen evolution reaction in alkaline solutions – A Review journal January 2015
New generation, metal-free electrocatalysts for fuel cells, solar cells and water splitting journal January 2011
Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices journal March 2015
Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials journal October 2014
Highly active and durable nanostructured molybdenum carbide electrocatalysts for hydrogen production journal January 2013
Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production journal March 2015
Transition Metal Carbides and Nitrides in Energy Storage and Conversion journal February 2016
Molybdenum carbide catalysts I. Synthesis of unsupported powders journal July 1987
Nanocrystalline Mo 2 C as a Bifunctional Water Splitting Electrocatalyst journal October 2015
A Review of Phosphide-Based Materials for Electrocatalytic Hydrogen Evolution journal October 2015
Earth-Rich Transition Metal Phosphide for Energy Conversion and Storage journal May 2016
Synthesis, Characterization, and Properties of Metal Phosphide Catalysts for the Hydrogen-Evolution Reaction journal August 2016
A robust hydrogen evolution catalyst based on crystalline nickel phosphide nanoflakes on three-dimensional graphene/nickel foam: high performance for electrocatalytic hydrogen production from pH 0–14 journal January 2015
Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction journal June 2013
Three-dimensional interconnected network of nanoporous CoP nanowires as an efficient hydrogen evolution cathode journal January 2014
Mo 2 C as Non-Noble Metal Co-Catalyst in Mo 2 C/CdS Composite for Enhanced Photocatalytic H 2 Evolution under Visible Light Irradiation journal March 2016
Mo2N: An efficient non-noble metal cocatalyst on CdS for enhanced photocatalytic H2 evolution under visible light irradiation journal December 2016
A novel ultraefficient non-noble metal composite cocatalyst Mo2N/Mo2C/graphene for enhanced photocatalytic H2 evolution journal July 2017
Semiconductor–Electrocatalyst Interfaces: Theory, Experiment, and Applications in Photoelectrochemical Water Splitting journal April 2016
Particle suspension reactors and materials for solar-driven water splitting journal January 2015
Modeling, simulation, and design criteria for photoelectrochemical water-splitting systems journal January 2012
An analysis of the optimal band gaps of light absorbers in integrated tandem photoelectrochemical water-splitting systems journal January 2013
Heterogeneous photocatalyst materials for water splitting journal January 2009
Electrocatalytic Activity and Stability Enhancement through Preferential Deposition of Phosphide on Carbide journal February 2017
Scalable and Tunable Carbide–Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass journal August 2017
Nickel Phosphide Nanoparticles with Hollow, Solid, and Amorphous Structures journal October 2009
A Nonaqueous Approach to the Preparation of Iron Phosphide Nanowires journal February 2010
Synthesis of Single-Crystalline CoP Nanowires by a One-Pot Metal−Organic Route journal November 2005
General Synthesis Method for Bimetallic Carbides of Group VIIIA First Row Transition Metals with Molybdenum and Tungsten journal April 2014
Nanostructured Co 2 P Electrocatalyst for the Hydrogen Evolution Reaction and Direct Comparison with Morphologically Equivalent CoP journal May 2015
XRD and TEM study of high pressure treated single-walled carbon nanotubes and C60-peapods journal January 2005
Self-Supported Nanoporous Cobalt Phosphide Nanowire Arrays: An Efficient 3D Hydrogen-Evolving Cathode over the Wide Range of pH 0–14 journal May 2014
Self-Supported FeP Nanorod Arrays: A Cost-Effective 3D Hydrogen Evolution Cathode with High Catalytic Activity journal October 2014
One-Step Synthesis of Self-Supported Nickel Phosphide Nanosheet Array Cathodes for Efficient Electrocatalytic Hydrogen Generation journal June 2015
Iron-Doped Molybdenum Carbide Catalyst with High Activity and Stability for the Hydrogen Evolution Reaction journal June 2015
Cobalt-Doping in Molybdenum-Carbide Nanowires Toward Efficient Electrocatalytic Hydrogen Evolution journal May 2016
Ni-Decorated Molybdenum Carbide Hollow Structure Derived from Carbon-Coated Metal–Organic Framework for Electrocatalytic Hydrogen Evolution Reaction journal August 2016
Auger parameters and relaxation energies of phosphorus in solid compounds journal July 1991
X-ray photoelectron spectra and bonding in transition-metal phosphides journal June 1985
On chemical shifts of ESCA and Auger lines in cobalt oxides journal January 1977
X-ray diffraction and X-ray photoelectron spectroscopy studies of Ni–P deposited onto carbon fiber surfaces: impact properties of a carbon-fiber-reinforced matrix journal July 2003
Effect of Phosphorus and Carbon Incorporation in Amorphous Cobalt Films Prepared by Chemical Vapor Deposition journal January 2010
Phosphorus-Mo 2 C@carbon nanowires toward efficient electrochemical hydrogen evolution: composition, structural and electronic regulation journal January 2017
Amorphous Molybdenum Phosphide Nanoparticles for Electrocatalytic Hydrogen Evolution journal August 2014
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction journal October 2013
Benchmarking nanoparticulate metal oxide electrocatalysts for the alkaline water oxidation reaction journal January 2016
Synthesis of α-MoC 1− x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation journal June 2016
Molybdenum Phosphosulfide: An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction journal October 2014
Nanocrystalline Ni 5 P 4 : a hydrogen evolution electrocatalyst of exceptional efficiency in both alkaline and acidic media journal January 2015
Active Edge Sites Engineering in Nickel Cobalt Selenide Solid Solutions for Highly Efficient Hydrogen Evolution journal January 2017
Sulfur-Decorated Molybdenum Carbide Catalysts for Enhanced Hydrogen Evolution journal October 2015
Large-Scale Synthesis of Carbon-Shell-Coated FeP Nanoparticles for Robust Hydrogen Evolution Reaction Electrocatalyst journal May 2017

Cited By (5)

Bi-Metal Phosphide NiCoP: An Enhanced Catalyst for the Reduction of 4-Nitrophenol journal January 2019
Heterostructures for Electrochemical Hydrogen Evolution Reaction: A Review journal August 2018
Structural Design and Electronic Modulation of Transition-Metal-Carbide Electrocatalysts toward Efficient Hydrogen Evolution journal August 2018
Noble‐Metal‐Free Colloidal‐Copper Based Low Overpotential Water Oxidation Electrocatalyst journal July 2019
An Intriguing Pea-Like Nanostructure of Cobalt Phosphide on Molybdenum Carbide Incorporated Nitrogen-Doped Carbon Nanosheets for Efficient Electrochemical Water Splitting journal October 2018