A fundamental understanding of the origin of oxygen evolution reaction (OER) activity of transition-metal-based electrocatalysts, especially for single precious metal atoms supported on layered double hydroxides (LDHs), is highly required for the design of efficient electrocatalysts toward further energy conversion technologies. Here, we aim toward single-atom Au supported on NiFe LDH (Au/NiFe LDH) to clarify the activity origin of LDHs system and a 6-fold OER activity enhancement by 0.4 wt % Au decoration. Combining with theoretical calculations, the active behavior of NiFe LDH results from the in situ generated NiFe oxyhydroxide from LDH during the OER process. With the presence ofAu, Au/NiFe LDH possesses an overpotential of 0.21 V in contrast to the calculated result (0.18 V). We ascribe the excellent OER activity ofAu/NiFe LDH to the charge redistribution of active Fe as well as its surrounding atoms causing by the neighboring Au on NiFe oxyhydroxide stabilized by interfacial CO and HO interfacing with LDH.
In-situ X-ray absorption spectroscopy (XAS) at the oxygen K-edge was used to investigate the role of oxygen during the oxygen evolution reaction (OER) in an electrodeposited Ni-Fe(OxHy) electrocatalyst in alkaline pH. We show the rise of a pre-peak feature at 529 eV in the O K-edge spectra, correlated to the appearance of a shoulder at the Ni L3-edge and formation of oxidized Ni3+/4+-O. Then, for the first time, we track the spectral changes in a dynamic fashion in both the soft and hard X-ray regimes during cyclic voltammetry (in situ CV-XAS) to obtain a fine-tuned resolution of the potential-related changes. The pre-peak feature at the O K-edge likely signifies formation of an electron deficient oxygen site. The electrophilic oxygen species appears and disappears reversibly in correlation with the Ni2+ ↔ Ni3+/4+ process, and persists during OER catalysis as long the metal is oxidized. Our study provides new insight into OER electrocatalysis: Before onset of the O-O bond formation step, the catalytic oxyhydroxide has accumulated electron deficiencies by both, oxidation of transition metal ions and formation of partially oxidized oxygen sites.
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