Nonmetallic Heteroatom Engineering in Copper-Based Electrocatalysts: Advances in CO2 Reduction

With the escalating challenges of global warming and the energy crisis, electrocatalytic CO2 reduction reaction (CO2RR) has emerged as a promising strategy to mitigate atmospheric CO2 concentrations while converting it into high-value-added chemicals. Among various CO2RR catalysts, copper-based materials exhibit unique capabilities for C-C coupling, yet their practical application remains constrained by several limitations: Low selectivity for C2+ products (typically <60%); Catalyst instability due to dynamic reconfiguration of active sites under high overpotentials; poor energy efficiency caused by competing hydrogen evolution reactions (HERs), etc. Recent studies demonstrate that nonmetallic heteroatom doping or functionalized ligand incorporation can effectively modulate the electronic structure and surface microenvironment of Cu-based catalysts, thereby enhancing CO2RR performance. In this review, we comprehensively summarize recent advances in such strategies. We first systematically elucidate the unique advantages of copper-based catalysts as benchmark materials for multi-carbon (C2+) product synthesis, along with the current challenges they face. Subsequently, we highlight recent advances in modulating copper-based catalysts through the incorporation of diverse nonmetallic heteroatoms (e.g., N, S, B, P, halogens) or the introduction of functionalized ligands, with a particular focus on mechanistic insights and characterization methods aimed at enhancing C-C coupling efficiency and improving C2+ product selectivity. Finally, we present perspectives on the remaining opportunities and challenges in this research field.