In response to the escalating global energy demand, photoelectrocatalytic (PEC) water splitting has emerged as a promising renewable energy strategy for hydrogen production, superseding conventional heterogeneous catalysis due to its superior cleanliness, efficiency, and environmental compatibility. Heterometallic metal-organic frameworks (MOFs) offer distinct potential in PEC applications owing to their tunable electronic structures, abundant active sites, and efficient charge separation capabilities. This review systematically examines recent advancements in the development of heterometallic MOFs employed as photoanodes in PEC water splitting. It explores the various synthesis methods for metallic MOF photoanodes, elucidates the strategies for enhancing their performance through heterometal incorporation, and discusses prospective research directions. The insights provide herein furnish essential theoretical foundations and guidance for the rational design and fabrication of high-performance photoanodes.

Contents

1 Introduction

2 Preparation of Heterometallic MOF Photoanodes

2.1 Dip-coating method

2.2 In-situ growth method

2.3 Stepwise synthesis method

2.4 Electrodeposition method

3 Strategies for Enhancing PEC Water Splitting Performance via Introduction of Heterometals into MOFs

3.1 Optimization of band structure

3.2 Promotion of photogenerated charge separation and transfer

3.3 Construction of heterometallic center synergistic catalytic system

4 Conclusion and outlook