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

Abstract

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.

Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal‐Organic Frameworks

“…Metal phosphonates have the potential to offer ultra‐stable structures owing to more charge‐assisted bonding. This has led to marked interest with no fewer than ten reviews in this subfield since 2018 [36,38–46] . The coordinative pliancy of the phosphonate functional group can enable multiple coordination scenarios with relatively small energy differences that can allow ligand packings to optimize and compromise porosity.…”

Activity Promotion of Core and Shell in Multifunctional Core–Shell Co2P@NC Electrocatalyst by Secondary Metal Doping for Water Electrolysis and Zn‐Air Batteries

“…Recently, transition-metal-phosphorousbased electrocatalysts, especially transitionmetal phosphides (TMPs), have received considerable attention owing to their huge potential in the clean energy conversion processes. [6][7][8][9] Nevertheless, their electrochemical performance still urgently needs to be further enhanced in comparison with noble-metalbased catalysts. Encapsulating TMPs into nitrogen-doped carbon materials (TMPs@NC) has been regarded as a promising strategy to enhance activity and stability, especially for HER electrocatalysis.…”

Highly Dispersed Pt Nanoparticles Embedded in N‐Doped Porous Carbon for Efficient Hydrogen Evolution

“…Alternatively, hydrogen evolution reaction (HER) reacted in the cathode reaction of water electrolysis provides a promising approach to supply hydrogen consumption because of the extensive water source and zero pollutant emission [6–9] . In this regard, a variety of electrocatalysts have been developed to catalyze HER [10–15] . Among them, Pt with excellent H adsorption feature is the most efficient electrocatalyst for HER [16] .…”

“…[6][7][8][9] In this regard, a variety of electrocatalysts have been developed to catalyze HER. [10][11][12][13][14][15] Among them, Pt with excellent H adsorption feature is the most efficient electrocatalyst for HER. [16] However, Pt's shortage and prohibitive cost, as well as its susceptibility to aggregation/dissolution/Ostwald ripening and an ensuing decline in performance, seriously restrict the large-scale application of Pt towards HER.…”