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Title: Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b07606· OSTI ID:1398516
 [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [5]; ORCiD logo [3];  [5]; ORCiD logo [6]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Engineering and Applied Sciences, Joint Center for Artificial Photosynthesis
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
  3. California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division
  5. California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis
  6. California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis; California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering; California Inst. of Technology (CalTech), Pasadena, CA (United States). Kavli Nanoscience Inst.; California Inst. of Technology (CalTech), Pasadena, CA (United States). Beckman Inst.

Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogen-evolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η of -η < 100 mV at a current density of -10 mA cm-2 in 0.500 M H2SO4 (aq). To obtain a chemical description of the material as-prepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H2SO4 (aq). Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Lastly, operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH)
Grant/Contract Number:
AC02-05CH11231; SC0004993; AC02-76SF00515
OSTI ID:
1398516
Journal Information:
Journal of the American Chemical Society, Vol. 139, Issue 37; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 115 works
Citation information provided by
Web of Science

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Niobium disulphide (NbS 2 )-based (heterogeneous) electrocatalysts for an efficient hydrogen evolution reaction journal January 2019
Sulphur edge and vacancy assisted nitrogen–phosphorus co-doped exfoliated tungsten disulfide: a superior electrocatalyst for hydrogen evolution reaction journal January 2018
Highly Efficient and Durable Electrocatalyst Based on Nanowires of Cobalt Sulfide for Overall Water Splitting journal September 2018
A Janus Nickel Cobalt Phosphide Catalyst for High‐Efficiency Neutral‐pH Water Splitting journal November 2018
A non-precious metal hydrogen catalyst in a commercial polymer electrolyte membrane electrolyser journal October 2019
Potential-driven surface active structure rearrangement over FeP@NC towards efficient electrocatalytic hydrogen evolution journal January 2019
S-Edge-rich Mo x S y arrays vertically grown on carbon aerogels as superior bifunctional HER/OER electrocatalysts journal January 2019
Chemical Doped Ternary and Quaternary Transition‐Metal‐Based Electrocatalysts for Hydrogen Evolution Reaction journal September 2019
In Situ/Operando Characterization Techniques to Probe the Electrochemical Reactions for Energy Conversion journal April 2018
A Janus Nickel Cobalt Phosphide Catalyst for High‐Efficiency Neutral‐pH Water Splitting journal November 2018
Recent progress in transition metal phosphides with enhanced electrocatalysis for hydrogen evolution journal January 2018
Multifunctional Transition Metal‐Based Phosphides in Energy‐Related Electrocatalysis journal September 2019
Stability of CoP x Electrocatalysts in Continuous and Interrupted Acidic Electrolysis of Water journal February 2018
Tailoring the composition of a one-step electrodeposited Co,Ni/Co,Ni(OH) 2 composite coating for a highly active hydrogen evolution electrode journal January 2020
Simple vapor–solid-reaction route for porous Cu 2 O nanorods with good HER catalytic activity journal January 2019
Single platinum atoms embedded in nanoporous cobalt selenide as electrocatalyst for accelerating hydrogen evolution reaction journal April 2019
Niobium disulphide (NbS$_2$)-based (heterogeneous) electrocatalysts for an efficient hydrogen evolution reaction text January 2020
Operando X-Ray Spectroscopic Techniques: A Focus on Hydrogen and Oxygen Evolution Reactions journal January 2020