Multiscale Engineering and Multiphysics Control of Molecular-Based Crystalline Materials in Electrocatalytic Reactions

ConspectusElectrocatalytic technology is the core driving force for the utilization of renewable energy, which can lead to efficient chemical transformations under mild conditions. However, electrocatalytic reactions, including anodic oxidation reactions (such as oxygen evolution reaction, OER) and cathodic reduction reactions (such as CO2 reduction reaction, CO2RR), still face many challenges, such as a high catalytic energy barrier, a multistep complex reaction mechanism, and slow kinetics, which make it difficult to rationally design and synthesize highly selective catalysts. Although traditional nanocatalysts are widely used, the establishment of precise structure–activity relationships (SARs) and the regulation of product selectivity are seriously restricted due to the unclear active sites. Therefore, it is of great significance to design a catalyst model with accurate atomic structure information. Molecular-based crystalline materials (MCMs), represented by supramolecular assemblies, coordination clusters, metal–organic frameworks (MOFs), and covalent organic frameworks (COFs), provide an ideal platform for the establishment of precise SARs by virtue of their highly ordered crystal structures and designability at the molecular level.This Account systematically summarizes our recent progress in the multiscale structural regulation strategies and performance exploration of MCMs. We highlight the regulation engineering from the microscopic scale (precise control of metal centers, coordination environments, and organic ligands) to the macroscale (optimizing crystal morphology and exposing specific crystal facets) and the combination of multiphysics coupling of external fields, such as light and heat, aiming to enhance the activity and stability of MCMs in electrocatalytic oxidation/reduction reactions and integrated full reactions. With the help of in situ characterization techniques and theoretical computational validation, we can reveal the intrinsic SARs in the catalytic process. Notably, by precisely controlling the spatial arrangement, distance, and symmetry of active sites, we successfully achieved the directional evolution of electrocatalytic products from simple C1 molecules (e.g., CO, CH4) to high-value C2 molecules (e.g., C2H4, C2H5OH). Additionally, this Account further discusses the simultaneous driving of anode and cathode reactions by a single bifunctional catalyst to maximize energy and resource utilization efficiency. We hope this work can provide a solid theoretical foundation and practical guidance for the synthesis of high-performance catalysts and the development of an energy-efficient transformation.