Connecting Biological and Synthetic Approaches for Electrocatalytic CO2 Reduction

Electrocatalytic CO2 reduction has developed into a broad field, spanning fundamental studies of enzymatic ‘model’ catalysts to synthetic molecular catalysts and heterogeneous gas diffusion electrodes producing commercially relevant quantities of product. This diversification has resulted in apparent differences and a disconnect between seemingly related approaches when using different types of catalysts. Enzymes possess discrete and well understood active sites that can perform reactions with high selectivity and activities at their thermodynamic limit. Synthetic small molecule catalysts can be designed with desired active site composition but do not yet display enzyme‐like performance. These properties of the biological and small molecule catalysts contrast with heterogeneous materials, which can contain multiple, often poorly understood active sites with distinct reactivity and therefore introducing significant complexity in understanding their activities. As these systems are being better understood and the continuously improving performance of their heterogeneous active sites closes the gap with enzymatic activity, this performance difference between heterogeneous and enzymatic systems begins to close. This convergence removes the barriers between using different types of catalysts and future challenges can be addressed without multiple efforts as a unified picture for the biological‐synthetic catalyst spectrum emerges. Electrochemical CO2 utilization has quickly expanded and diversified into employing a wide range of catalysts and device configurations. This mini‐review seeks to highlight the significant progress and common elements in heterogeneous, small molecule and enzymatic systems to bridge the gap between these seemingly disparate approaches and to provide a more holistic and unified strategy to develop the field of electrocatalytic CO2 reduction.