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Title: CoP as an Acid-Stable Active Electrocatalyst for the Hydrogen-Evolution Reaction: Electrochemical Synthesis, Interfacial Characterization and Performance Evaluation

Abstract

Films of CoP have been electrochemically synthesized, characterized, and evaluated for performance as a catalyst for the hydrogen-evolution reaction (HER). The film was synthesized by cathodic deposition from a boric acid solution of Co 2+ and H 2PO 2 on copper substrates followed by operando remediation of exogenous contaminants. The films were characterized structurally and compositionally by scanning-electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman spectrophotometry. The catalytic activity was evaluated by cyclic voltammetry and chronopotentiometry. Surface characterization prior to electrocatalysis indicated that the film consisted of micrometer-sized spherical clusters located randomly and loosely on a slightly roughened surface. The composition of both the clusters and surface consisted of cobalt in the metallic, phosphide, and amorphous-oxide forms (CoO·Co 2O 3) and of phosphorus as phosphide and orthophosphate. The orthophosphate species, produced by air-oxidation, were eliminated upon HER electrocatalysis in sulfuric acid. The operando film purification yielded a functional electrocatalyst with a Co:P stoichiometric ratio of 1:1. After the HER, the surface was densely packed with micrometer-sized, mesa-like particles whose tops were flat and smooth. The CoP eletrodeposit exhibited an 85 mV overvoltage (η) for the HER at a current density of 10 mA cm –2 and wasmore » stable under operation in highly acidic solution, with an increase in η of 18 mV after 24 h of continuous operation. In conclusion, the comparative HER catalytic performance of CoP, film or nanoparticles, is as follows: ηPt < ηCoP film = ηCoP NP, ηNi 2P < ηCoSe 2 < ηMoS 2 < ηMoSe 2.« less

Authors:
 [1];  [1];  [1];  [2];  [1];  [3]
  1. California Institute of Technology (CalTech), Pasadena, CA (United States)
  2. California Institute of Technology (CalTech), Pasadena, CA (United States); Univ. of California, Irvine, CA (United States)
  3. California Institute of Technology (CalTech), Pasadena, CA (United States); Texas A & M Univ., College Station, TX (United States)
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1635017
Grant/Contract Number:  
SC0004993
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 118; Journal Issue: 50; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; thin films; inorganic compounds; electrical properties; evolution reactions; cobalt

Citation Formats

Saadi, Fadl H., Carim, Azhar I., Verlage, Erik, Hemminger, John C., Lewis, Nathan S., and Soriaga, Manuel P. CoP as an Acid-Stable Active Electrocatalyst for the Hydrogen-Evolution Reaction: Electrochemical Synthesis, Interfacial Characterization and Performance Evaluation. United States: N. p., 2014. Web. doi:10.1021/jp5054452.
Saadi, Fadl H., Carim, Azhar I., Verlage, Erik, Hemminger, John C., Lewis, Nathan S., & Soriaga, Manuel P. CoP as an Acid-Stable Active Electrocatalyst for the Hydrogen-Evolution Reaction: Electrochemical Synthesis, Interfacial Characterization and Performance Evaluation. United States. https://doi.org/10.1021/jp5054452
Saadi, Fadl H., Carim, Azhar I., Verlage, Erik, Hemminger, John C., Lewis, Nathan S., and Soriaga, Manuel P. Sat . "CoP as an Acid-Stable Active Electrocatalyst for the Hydrogen-Evolution Reaction: Electrochemical Synthesis, Interfacial Characterization and Performance Evaluation". United States. https://doi.org/10.1021/jp5054452. https://www.osti.gov/servlets/purl/1635017.
@article{osti_1635017,
title = {CoP as an Acid-Stable Active Electrocatalyst for the Hydrogen-Evolution Reaction: Electrochemical Synthesis, Interfacial Characterization and Performance Evaluation},
author = {Saadi, Fadl H. and Carim, Azhar I. and Verlage, Erik and Hemminger, John C. and Lewis, Nathan S. and Soriaga, Manuel P.},
abstractNote = {Films of CoP have been electrochemically synthesized, characterized, and evaluated for performance as a catalyst for the hydrogen-evolution reaction (HER). The film was synthesized by cathodic deposition from a boric acid solution of Co2+ and H2PO2– on copper substrates followed by operando remediation of exogenous contaminants. The films were characterized structurally and compositionally by scanning-electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman spectrophotometry. The catalytic activity was evaluated by cyclic voltammetry and chronopotentiometry. Surface characterization prior to electrocatalysis indicated that the film consisted of micrometer-sized spherical clusters located randomly and loosely on a slightly roughened surface. The composition of both the clusters and surface consisted of cobalt in the metallic, phosphide, and amorphous-oxide forms (CoO·Co2O3) and of phosphorus as phosphide and orthophosphate. The orthophosphate species, produced by air-oxidation, were eliminated upon HER electrocatalysis in sulfuric acid. The operando film purification yielded a functional electrocatalyst with a Co:P stoichiometric ratio of 1:1. After the HER, the surface was densely packed with micrometer-sized, mesa-like particles whose tops were flat and smooth. The CoP eletrodeposit exhibited an 85 mV overvoltage (η) for the HER at a current density of 10 mA cm–2 and was stable under operation in highly acidic solution, with an increase in η of 18 mV after 24 h of continuous operation. In conclusion, the comparative HER catalytic performance of CoP, film or nanoparticles, is as follows: ηPt < ηCoP film = ηCoP NP, ηNi2P < ηCoSe2 < ηMoS2 < ηMoSe2.},
doi = {10.1021/jp5054452},
url = {https://www.osti.gov/biblio/1635017}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 50,
volume = 118,
place = {United States},
year = {2014},
month = {9}
}

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