As one important electrode reaction in electrocatalytic and photoelectrochemical cells for renewable energy circulation, oxygen catalysis has attracted considerable research in developing efficient and cost-effective catalysts. Due to the inevitable formation of oxygenic intermediates on surface sites during the complex reaction steps, the surface structure dynamically evolves toward reaction-preferred active species. To date, transition metal compounds, here defined as TM-Xides, where "X" refers to typical nonmetal elements from group IIIA to VIA, including hydroxide as well, are reported as high-performance oxygen evolution reaction (OER) electrocatalysts. However, more studies observe at least exterior oxidation or amorphization of materials. Thus, whether the TM-Xides can be defined as OER catalysts deserves further discussion. This Review pays attention to recent progress on the surface reconstruction of TM-Xide OER electrocatalysts with an emphasis on the identification of the true active species for OER, and aims at disseminating the real contributors of OER performance, especially under long-duration electrocatalysis.

Recent Progress on Surface Reconstruction of Earth-Abundant Electrocatalysts for Water Oxidation

Electrocatalytic water splitting (EWS) is a promising route to produce hydrogen in a sustainable and environment-benign manner. To realize the large-scale hydrogen production, it is paramount to develop desirable electrocatalysts with engineered structure, high catalytic activity, facile accessibility, low cost, and good durability. Of late, boride-based materials, especially transition-metal borides (TMBs), are emerging as promising candidates for the EWS process. However, so far, little attempt has been made to provide a comprehensive summary on these findings. Herein, this review provides the up-to-date status on upgrading the catalytic performance of TMB-based nanomaterials by regulating the internal and external characteristics. The conventional synthetic techniques are first presented for the preparation of TMB-based catalysts. Afterwards, the advanced strategies are summarized to enhance the catalytic performance of TMBs, including morphology control, component regulation, phase engineering, surface oxidation and hybridization. Then, the design principles of TMB-based electrocatalysts for high-performance EWS are outlined. Lastly, the current challenges and future directions in the development of TMB-based materials are proposed. This review article is expected to envisage insights into the TMBs-based water splitting and to provide strategies for design of the next-generation TMB-based electrocatalysts.

https://link.springer.com/content/pdf/10.1007/s12274-020-2618-y.pdf

Boride-based electrocatalysts: Emerging candidates for water splitting

Amorphous Nickel–Iron Borophosphate for a Robust and Efficient Oxygen Evolution Reaction

https://onlinelibrary.wiley.com/doi/pdf/10.1002/cey2.79

Design and operando/in situ characterization of precious-metal-free electrocatalysts for alkaline water splitting

Designing cost-effective oxygen evolution reaction (OER) electrocatalysts is essential for sustainable water splitting. Recently, amorphous transition metal borides (TMBs) as OER pre-catalysts have acquired growing attention due to their favorable characteristics such as high conductivity, compositional and structural flexibility. Nevertheless, rational design of boride-based OER pre-catalysts remains an ongoing challenge. Herein, an efficient pre-catalyst derived from FeB with accelerated surface reconstruction and regulated intrinsic activity of evolved FeOOH is obtained by W and P co-doping. The obtained catalyst demonstrates an excellent OER activity with a low overpotential of 209 mV at a current density of 10 mA cm−2, and good stability in alkaline electrolyte, which surpasses most of boride-based OER catalysts. Specifically, the anion etching facilitates the surface reconstruction and accelerates the mass/charge transfer. Density functional theory calculations suggest W doping can enhance intrinsic catalytic activity via optimizing the adsorption free energy of reaction intermediates and improving the conductivity. Additionally, the hierarchical structure and amorphous feature also benefit the OER process. This study provides a fundamental insight into the correlation between surface structure and catalytic activity, and a powerful strategy to construct efficient OER pre-catalysts.

Tuning electronic property and surface reconstruction of amorphous iron borides via W-P co-doping for highly efficient oxygen evolution

Phosphate‐Based Electrocatalysts for Water Splitting: Recent Progress

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Phosphate‐Based Electrocatalysts for Water Splitting: Recent Progress