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

磷化物 分解水 X射线吸收光谱法 析氧 材料科学 硫系化合物 价(化学) 化学工程 催化作用 化学 电化学 无机化学 过渡金属 吸收光谱法 物理化学 光催化 生物化学 物理 有机化学 电极 量子力学 工程类 冶金
作者
Yonggui Zhao,Nanchen Dongfang,Carlos A. Triana,Chong Huang,Rolf Erni,Wenchao Wan,Jingguo Li,Dragos Stoian,Long Pan,Ping Zhang,Jinggang Lan,Marcella Iannuzzi,Greta R. Patzke
出处
期刊:Energy and Environmental Science [The Royal Society of Chemistry]
卷期号:15 (2): 727-739 被引量:101
标识
DOI:10.1039/d1ee02249k
摘要

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.
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