Low-Dimensional Nanostructured Molecular Architectures for Advanced CO2 Electroreduction

Abstract Molecular catalysts have been found to be selective for the CO2 reduction reaction (CO2RR), with Faradaic efficiencies approaching 100% for two-electron products such as CO and formic acid. However, translating the intrinsic activity of well-defined molecular active sites into practical high-current-density electrolysis remains challenging due to molecular aggregation, poor electronic coupling with electrodes, and limited stability. In addition, multielectron molecular CO2RR is hampered by complex reaction pathways and insufficient adsorption of intermediates. This perspective discusses how nanostructured molecular architectures, from controlled aggregation and support interactions to reticular frameworks, fundamentally alter catalytic performance beyond what is achievable through conventional coordination chemistry alone. We highlight recent advances demonstrating that molecular dispersion, curvature-induced strain, nanoconfinement, and layered confinement can redirect reaction pathways, enabling multielectron reduction products such as methanol and ethanol. We further discuss emerging opportunities in computation-accelerated molecular discovery, strategies to address high overpotentials, and the integration of CO2 capture with electrochemical conversion. By engineering the microenvironment surrounding molecular active sites, we argue that the next generation of molecular electrocatalysts can achieve the activity, selectivity, and stability required for practical deployment.