Reversible Structural Evolution of NiCoOxHy during the Oxygen Evolution Reaction and Identification of the Catalytically Active Phase

Zhu Chen, Li Cai, Xiaofang Yang, Coleman Kronawitter, Liejin Guo, Shaohua Shen, Bruce E. Koel

Research output: Contribution to journalArticle

49 Scopus citations

Abstract

Operando Raman spectroscopy and electrochemical techniques were used during the oxygen evolution reaction to identify the composition and local structure of electrodeposited CoOxHy and NiCoOxHy catalyst films. Before evaluation, the electrodeposited samples were subjected to a variety of thermal and electrochemical conditioning procedures, which generated unique initial catalyst structures and crystallinities. During oxygen evolution, Ni-modified CoOxHy films having lower initial crystallinity underwent substantial structural evolution that began with an irreversible transformation of a spinel local structure to an amorphous CoO structure at low anodic potentials (0.2 V vs Ag/AgCl). Increasing anodic polarization to greater than 0.3 V vs Ag/AgCl facilitated additional structural conversion from the amorphous CoO structure to a complex phase best described as an amalgamation of NiOOH and layered CoO2 motifs (NiOOH-h-CoO2) under elevated oxygen evolution rates. The formation of this NiOOH-h-CoO2 active structure was correlated with improved OER activity, which at 0.35 V overpotential is 100% greater than that of the catalyst where Ni was coordinated in a spinel structure. Independent of the initial cobalt oxide structure, the same NiOOH-h-CoO2 structure was formed during oxygen evolution, which suggests the active phase identified herein could be the universally active structure for NiCoOxHy materials.

Original languageEnglish (US)
Pages (from-to)1238-1247
Number of pages10
JournalACS Catalysis
Volume8
Issue number2
DOIs
StatePublished - Feb 2 2018

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • Ni incorporation
  • amorphous cobalt oxide
  • cobalt oxyhydroxide
  • layered delafossite
  • operando Raman spectroscopy
  • oxygen evolution reaction
  • reversible structural evolution
  • spinel structure

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