Beyond immobilization: critical roles of support materials in modulating heterogeneous molecular electrocatalysis

The escalating global energy crisis and environmental challenges urgently demand innovative technologies for sustainable energy conversion. Electrochemical technology shows great potential for converting small molecules into clean fuels and valuable chemicals under mild conditions. Molecular catalysts exhibit exceptional activity and theoretical 100% atom utilization but face limitations in stability and recyclability under homogeneous conditions. Heterogenization via immobilization of molecular catalysts on solid supports is considered as a potential strategy to bridge this gap. This review systematically examines recent advances in support materials, including carbon, metals/metal compounds and non-metallic oxides, for constructing and engineering high-performance heterogeneous molecular electrocatalysts. The main interactions between supports and molecular catalysts, including π-π stacking, axial coordination and confinement, are elucidated to highlight their roles in enhancing activity, selectivity and durability. By establishing structure-activity relationships across diverse support classes, this review provides a design framework for next-generation electrocatalysts. This work bridges fundamental insights with practical strategies, advancing sustainable energy conversion technologies.