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Title: Hydrogen on Cobalt Phosphide

Abstract

Cobalt phosphide is one of the most promising earth-abundant replacements for noble metal catalysts and electrocatalysts for energy-related and other reactions. Many of these reactions, starting with the simplest, the hydrogen evolution reaction (HER), involve the catalyst binding hydrogen atoms (protons and electrons). Theoretical studies have computed the preferred sites and energetics of bound hydrogen on phosphide surfaces. However, direct experimental studies of hydrogen on transition metal phosphides surfaces are scarce, especially at the solid/solution interfaces. Herein, we describe measurements of hydrogen stoichiometry and thermochemistry for hydrogen bound to cobalt phosphide. We studied both mesoscale cobalt phosphide particles, exhibiting phosphide surfaces after an acidic pretreatment, and colloidal cobalt phosphide nanoparticles. Treatment with H2 introduced large amounts of reactive hydrogen to cobalt phosphide, on the order of one H per Co or P surface atom. This stoichiometry was determined by titration of the bound hydrogen using alkyne hydrogenation and H-atom transfer reactions with phenoxy radicals. There are also substantial amounts of reactive hydrogen-atoms present on the as-prepared materials, before hydrogen treatment. Cobalt phosphide was found to be reactive with hydrogen atom transfer reagents, accepting hydrogen from molecules with low X–H bond dissociation free energies (BDFEs) and donating hydrogen to good H-atommore » acceptor reagents. Based on this reactivity we estimate that there is a distribution of possible binding energies for hydrogen on cobalt phosphide, between ~53 kcal/mol and ~63 kcal/mol. Operando X-ray absorption spectroscopy gave first indications about the structure of hydrogenated CoP, showing a slight lattice expansion under H2-flow and indicating that the addition of hydrogen does not significantly change the effective nuclear charge of the cobalt. These results provide a new picture of catalytically active cobalt phosphide, with a substantial amount of reactive hydrogen atoms. This revised view of cobalt phosphide is of fundamental relevance for its catalytic and electrocatalytic properties, and the approach developed here provides a road map to examine hydrogen on other materials.« less

Authors:
 [1];  [1];  [2];  [2];  [2];  [1];  [1]
  1. Yale University
  2. University of Washington
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1735735
Report Number(s):
PNNL-SA-144922
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 38
Country of Publication:
United States
Language:
English

Citation Formats

Delley, Murielle F., Wu, Zishan, Mundy, M E., Ung, David, Cossairt, Brandi M., Wang, Hailiang, and Mayer, James M. Hydrogen on Cobalt Phosphide. United States: N. p., 2019. Web. doi:10.1021/jacs.9b07986.
Delley, Murielle F., Wu, Zishan, Mundy, M E., Ung, David, Cossairt, Brandi M., Wang, Hailiang, & Mayer, James M. Hydrogen on Cobalt Phosphide. United States. https://doi.org/10.1021/jacs.9b07986
Delley, Murielle F., Wu, Zishan, Mundy, M E., Ung, David, Cossairt, Brandi M., Wang, Hailiang, and Mayer, James M. 2019. "Hydrogen on Cobalt Phosphide". United States. https://doi.org/10.1021/jacs.9b07986.
@article{osti_1735735,
title = {Hydrogen on Cobalt Phosphide},
author = {Delley, Murielle F. and Wu, Zishan and Mundy, M E. and Ung, David and Cossairt, Brandi M. and Wang, Hailiang and Mayer, James M.},
abstractNote = {Cobalt phosphide is one of the most promising earth-abundant replacements for noble metal catalysts and electrocatalysts for energy-related and other reactions. Many of these reactions, starting with the simplest, the hydrogen evolution reaction (HER), involve the catalyst binding hydrogen atoms (protons and electrons). Theoretical studies have computed the preferred sites and energetics of bound hydrogen on phosphide surfaces. However, direct experimental studies of hydrogen on transition metal phosphides surfaces are scarce, especially at the solid/solution interfaces. Herein, we describe measurements of hydrogen stoichiometry and thermochemistry for hydrogen bound to cobalt phosphide. We studied both mesoscale cobalt phosphide particles, exhibiting phosphide surfaces after an acidic pretreatment, and colloidal cobalt phosphide nanoparticles. Treatment with H2 introduced large amounts of reactive hydrogen to cobalt phosphide, on the order of one H per Co or P surface atom. This stoichiometry was determined by titration of the bound hydrogen using alkyne hydrogenation and H-atom transfer reactions with phenoxy radicals. There are also substantial amounts of reactive hydrogen-atoms present on the as-prepared materials, before hydrogen treatment. Cobalt phosphide was found to be reactive with hydrogen atom transfer reagents, accepting hydrogen from molecules with low X–H bond dissociation free energies (BDFEs) and donating hydrogen to good H-atom acceptor reagents. Based on this reactivity we estimate that there is a distribution of possible binding energies for hydrogen on cobalt phosphide, between ~53 kcal/mol and ~63 kcal/mol. Operando X-ray absorption spectroscopy gave first indications about the structure of hydrogenated CoP, showing a slight lattice expansion under H2-flow and indicating that the addition of hydrogen does not significantly change the effective nuclear charge of the cobalt. These results provide a new picture of catalytically active cobalt phosphide, with a substantial amount of reactive hydrogen atoms. This revised view of cobalt phosphide is of fundamental relevance for its catalytic and electrocatalytic properties, and the approach developed here provides a road map to examine hydrogen on other materials.},
doi = {10.1021/jacs.9b07986},
url = {https://www.osti.gov/biblio/1735735}, journal = {Journal of the American Chemical Society},
number = 38,
volume = 141,
place = {United States},
year = {Wed Sep 25 00:00:00 EDT 2019},
month = {Wed Sep 25 00:00:00 EDT 2019}
}

Works referenced in this record:

Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction
journal, January 2016


Synthesis, Characterization, and Properties of Metal Phosphide Catalysts for the Hydrogen-Evolution Reaction
journal, August 2016


Developments of Metal Phosphides as Efficient OER Precatalysts
journal, December 2016


Transition metal phosphide hydroprocessing catalysts: A review
journal, May 2009


Surface Chemistry in Cobalt Phosphide-Stabilized Lithium–Sulfur Batteries
journal, January 2018


Template-assisted synthesis of CoP nanotubes to efficiently catalyze hydrogen-evolving reaction
journal, January 2014


The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen
journal, January 1958


Mechanismus der Elektrolytischen Wasserstoffabscheidung und Adsorptionsenergie von Atomarem Wasserstoff
journal, January 1958


Work function, electronegativity, and electrochemical behaviour of metals
journal, September 1972


Designing an improved transition metal phosphide catalyst for hydrogen evolution using experimental and theoretical trends
journal, January 2015


Volcano plots in hydrogen electrocatalysis – uses and abuses
journal, January 2014


A Critical Review on Hydrogen Evolution Electrocatalysis: Re-exploring the Volcano-relationship
journal, October 2016


Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction
journal, September 2017


Electrodeposited Cobalt-Phosphorous-Derived Films as Competent Bifunctional Catalysts for Overall Water Splitting
journal, April 2015


Carbon Nanotubes Decorated with CoP Nanocrystals: A Highly Active Non-Noble-Metal Nanohybrid Electrocatalyst for Hydrogen Evolution
journal, May 2014


Elucidating Surface Restructuring-Induced Catalytic Reactivity of Cobalt Phosphide Nanoparticles under Electrochemical Conditions
journal, January 2018


Strong Metal–Phosphide Interactions in Core–Shell Geometry for Enhanced Electrocatalysis
journal, February 2017


Aminophosphines as Versatile Precursors for the Synthesis of Metal Phosphide Nanocrystals
journal, July 2018


Highly branched cobalt phosphide nanostructures for hydrogen-evolution electrocatalysis
journal, January 2015


Highly Active Electrocatalysis of the Hydrogen Evolution Reaction by Cobalt Phosphide Nanoparticles
journal, April 2014


Trioctylphosphine  A General Phosphorus Source for the Low-Temperature Conversion of Metals into Metal Phosphides
journal, August 2007


25th Anniversary Article: Exploring Nanoscaled Matter from Speciation to Phase Diagrams: Metal Phosphide Nanoparticles as a Case of Study
journal, December 2013


Phase-Programmed Nanofabrication: Effect of Organophosphite Precursor Reactivity on the Evolution of Nickel and Nickel Phosphide Nanocrystals
journal, November 2015


Recent developments in synthetic approaches to transition metal phosphide nanoparticles for magnetic and catalytic applications
journal, July 2008


Control of Phase in Phosphide Nanoparticles Produced by Metal Nanoparticle Transformation: Fe 2 P and FeP
journal, August 2009


Effect of Synthetic Levers on Nickel Phosphide Nanoparticle Formation: Ni 5 P 4 and NiP 2
journal, August 2015


Simultaneous Control of Composition, Size, and Morphology in Discrete Ni2–xCoxP Nanoparticles
journal, June 2015


Single-Crystal and Electronic Structure of a 1.3 nm Indium Phosphide Nanocluster
journal, January 2016


Conversion Reactions of Atomically Precise Semiconductor Clusters
journal, October 2018


Quantifying Ligand Exchange on InP Using an Atomically Precise Cluster Platform
journal, February 2019


Exceptionally Mild Reactive Stripping of Native Ligands from Nanocrystal Surfaces by Using Meerwein’s Salt
journal, December 2011


Effect of Ligand Coverage on Hydrogen Evolution Catalyzed by Colloidal WSe 2
journal, March 2017


Improved HER Catalysis through Facile, Aqueous Electrochemical Activation of Nanoscale WSe 2
journal, March 2018


Effect of Surface Ligands on CoP for the Hydrogen Evolution Reaction
journal, March 2019


CoP for hydrogen evolution: implications from hydrogen adsorption
journal, January 2016


Enhancing electrocatalysis for hydrogen production over CoP catalyst by strain: a density functional theory study
journal, January 2019


Activity and stability of cobalt phosphides for hydrogen evolution upon water splitting
journal, November 2016


Synthesis of Oxide-Free InP Quantum Dots: Surface Control and H 2 -Assisted Growth
journal, November 2017


Surface mode absorption and infrared optical properties of gallium phosphide nanoparticles
journal, April 2008


Elucidating the Surface Chemistry of Zinc Phosphide Nanoparticles Through Ligand Exchange
journal, July 2014


Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010


Solubility of hydrogen in 10 organic solvents at 298.15, 323.15, and 373.15 K
journal, July 1985


Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts
journal, April 2018


Examination of the Bonding in Binary Transition-Metal Monophosphides MP (M = Cr, Mn, Fe, Co) by X-Ray Photoelectron Spectroscopy
journal, November 2005


342. Thermal decomposition of hydrazobenzene, studied by the use of nitrogen isotopes
journal, January 1953


NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist
journal, May 2010


Auger parameters and relaxation energies of phosphorus in solid compounds
journal, July 1991


Phosphorus 2p electron binding energies. Correlation with extended Hueckel charges
journal, March 1970


The structural evolution and diffusion during the chemical transformation from cobalt to cobalt phosphide nanoparticles
journal, April 2011


The Structures of Co2P, Ru2P, and Related Phases.
journal, January 1960


Structural characterization of amorphous electrodeposited cobalt‐phosphorus alloys
journal, April 1979


Porous Organic Polymer-Driven Evolution of High-Performance Cobalt Phosphide Hybrid Nanosheets as Vanillin Hydrodeoxygenation Catalyst
journal, June 2019


Bond-length variation in In x Ga 1 x A s / I n P strained epitaxial layers
journal, June 1998


Core–Shell Structure of Palladium Hydride Nanoparticles Revealed by Combined X-ray Absorption Spectroscopy and X-ray Diffraction
journal, July 2017


In-situ x-ray absorption spectroscopy studies of hydride and carbide formation in supported palladium catalysts
journal, October 1993


X-ray-absorption study of the interaction of hydrogen with clusters of supported palladium
journal, May 1989


Cation Effects on the Reduction of Colloidal ZnO Nanocrystals
journal, June 2018


Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation
journal, January 2018


Quinone 1 e and 2 e /2 H + Reduction Potentials: Identification and Analysis of Deviations from Systematic Scaling Relationships
journal, November 2016


619. The polarographic reduction of pyridine, quinoline, and phenazine
journal, January 1952


Ethylene Hydrogenation on Ni(111) by Bulk Hydrogen
journal, June 1994


Finite size effects on supported Pd nanoparticles: Interaction of hydrogen with CO and C2H4
journal, August 2005


The Roles of Subsurface Carbon and Hydrogen in Palladium-Catalyzed Alkyne Hydrogenation
journal, April 2008


Reactivity of Hydrogen on and in Nanostructured Molybdenum Nitride: Crotonaldehyde Hydrogenation
journal, August 2016


Nickel phosphide nanocatalysts for the chemoselective hydrogenation of alkynes
journal, February 2012


Evidence for complexes of hydrogen with deep-level defects in bulk III-V materials
journal, April 1987


Hydrogen Passivation in Semiconductors
journal, October 1992


The Mechanism of Hydrogen Gas Evolution on GaAs Cathodes Elucidated by In Situ Infrared Spectroscopy
journal, April 1999


Hydrogen-impurity complexes in III–V semiconductors
journal, November 2004


Combined Computational and Experimental Study of Substituent Effects on the Thermodynamics of H 2 , CO, Arene, and Alkane Addition to Iridium
journal, September 2002


PNP-Pincer Complexes of Osmium: Comparison with Isoelectronic (PCP)Ir and (PNP)Ir + Units
journal, January 2018


Hydrogen in Semiconductors
journal, August 2006


Hydrogen in oxides
journal, January 2004


Titanium and Zinc Oxide Nanoparticles Are Proton-Coupled Electron Transfer Agents
journal, June 2012


The nature of active sites of Ni2P electrocatalyst for hydrogen evolution reaction
journal, June 2015