Design Strategies of Transition-Metal Phosphate and Phosphonate Electrocatalysts for Energy-Related Reactions

The key challenge to developing renewable energy conversion and storage devices lies in the exploration and rational engineering of cost-effective and highly efficient electrocatalysts for various energy-related electrochemical reactions. Transition-metal phosphates and phosphonates have shown remarkable performances for these reactions based on their unique physicochemical properties. Compared with transition-metal oxides, phosphate groups in transition-metal phosphates and phosphonates show flexible coordination with diverse orientations, making them an ideal platform for designing active electrocatalysts. Although numerous efforts have been spent on the development of transition-metal phosphate and phosphonate electrocatalysts, some urgent issues, such as low intrinsic catalytic efficiency and low electronic conductivity, have to be resolved in accordance with their applications. In this Review, we focus on the design strategies of highly efficient transition-metal phosphate and phosphonate electrocatalysts, with special emphasis on the tuning of transition-metal-center coordination environment, optimization of electronic structures, increase of catalytically active site densities, and construction of heterostructures. Guided by these strategies, recently developed transition-metal phosphate and phosphonate materials have exhibited excellent activity, selectivity, and stability for various energy-related electrocatalytic reactions, showing great potential for replacing noble-metal-based catalysts in next-generation advanced energy techniques. The existing challenges and prospects regarding these materials are also presented.