Next-Generation Cu-MOF-based electrocatalysts for CO2 reduction: Bridging mechanistic insights and rational design

Abstract

The electrochemical reduction of carbon dioxide (CO₂RR) represents a promising pathway toward sustainable and carbon-neutral production of fuels and chemicals. Among various electrocatalysts, copper-based metal–organic frameworks (Cu-MOFs) have emerged as a highly versatile class of materials. This review provides a comprehensive overview of Cu-MOF-based electrocatalysts, with a particular focus on controlling rate and product selectivity toward C₁ (CO, HCOOH, CH₄, CH₃OH) and C₂ (C₂H₄, C₂H₅OH) compounds. We critically examine how operando/DFT informed factors such as metal-ligand coordination, framework topology, and electronic structure influence key mechanistic steps of CO₂RR. Persistent challenges such as low intrinsic electrical conductivity, structural instability, and insufficient selectivity toward multicarbon products are thoroughly examined. This review is distinctive in connecting fundamental mechanistic pathways of CO₂RR with material design, highlighting how π-conjugated linkers, heteroatom doping, in situ reconstruction and derivatives, as well as hydrophobic surface engineering can be harnessed to optimize activity, selectivity and stability. Particular attention is given to operando and in situ characterization techniques. Finally, we propose a future roadmap that integrates band structure engineering, development of bimetallic and multi-functional active sites, and implementation of standardized testing protocols. By bridging mechanistic understanding with rational material design, this review aims to accelerate the development of high-performance, durable, and scalable Cu-MOF-based electrocatalysts for efficient CO₂ reduction.