Issue 2, 2022

Dynamics and control of active sites in hierarchically nanostructured cobalt phosphide/chalcogenide-based electrocatalysts for water splitting

Abstract

The rational design of efficient electrocatalysts for industrial water splitting is essential to generate sustainable hydrogen fuel. However, a comprehensive understanding of the complex catalytic mechanisms under harsh reaction conditions remains a major challenge. We apply a self-templated strategy to introduce hierarchically nanostructured “all-surface” Fe-doped cobalt phosphide nanoboxes (Co@CoFe–P NBs) as alternative electrocatalysts for industrial-scale applications. Operando Raman spectroscopy and X-ray absorption spectroscopy (XAS) experiments were carried out to track the dynamics of their structural reconstruction and the real catalytically active intermediates during water splitting. Our operando analyses reveal that partial Fe substitution in cobalt phosphides promotes a structural reconstruction into P–Co–O–Fe–P configurations with low-valence metal centers (M0/M+) during the hydrogen evolution reaction (HER). Results from density functional theory (DFT) demonstrate that these in situ reconstructed configurations significantly enhance the HER performance by lowering the energy barrier for water dissociation and by facilitating the adsorption/desorption of HER intermediates (H*). The competitive activity in the oxygen evolution reaction (OER) arises from the transformation of the reconstructed P–Co–O–Fe–P configurations into oxygen-bridged, high-valence CoIV–O–FeIV moieties as true active intermediates. In sharp contrast, the formation of such CoIII/IV–O–FeIII/IV moieties in Co–FeOOH is hindered under the same conditions, which outlines the key advantages of phosphide-based electrocatalysts. Ex situ studies of the as-synthesized reference cobalt sulfides (Co–S), Fe doped cobalt selenides (Co@CoFe–Se), and Fe doped cobalt tellurides (Co@CoFe–Te) further corroborate the observed structural transformations. These insights are vital to systematically exploit the intrinsic catalytic mechanisms of non-oxide, low-cost, and robust overall water splitting electrocatalysts for future energy conversion and storage.

Graphical abstract: Dynamics and control of active sites in hierarchically nanostructured cobalt phosphide/chalcogenide-based electrocatalysts for water splitting

Supplementary files

Article information

Article type
Paper
Submitted
20 Jul 2021
Accepted
03 Dec 2021
First published
06 Jan 2022
This article is Open Access
Creative Commons BY-NC license

Energy Environ. Sci., 2022,15, 727-739

Dynamics and control of active sites in hierarchically nanostructured cobalt phosphide/chalcogenide-based electrocatalysts for water splitting

Y. Zhao, N. Dongfang, C. A. Triana, C. Huang, R. Erni, W. Wan, J. Li, D. Stoian, L. Pan, P. Zhang, J. Lan, M. Iannuzzi and G. R. Patzke, Energy Environ. Sci., 2022, 15, 727 DOI: 10.1039/D1EE02249K

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