Engineering Mo vacancies in hybrid zeolitic imidazolate frameworks to downshift the d-band center and promote CO desorption for efficient CO2 electroreduction.

The electrocatalytic carbon dioxide reduction reaction (CO2RR) is a highly promising strategy toward carbon neutrality. However, for its practical implementation, it is imperative to develop novel electrocatalysts that are structurally simple, cost-effective, and capable of delivering high current densities. Metal-organic frameworks (MOFs) are promising platforms due to their structural diversity and tunable functionality, but their practical catalytic performance is often hampered by low electrochemical activity and an insufficient number of intrinsic active sites. To address these challenges, this study employed a post-synthetic strategy by controlling the exposure of specific crystal facets to create a high concentration of molybdenum vacancies in hybrid zeolitic imidazolate frameworks (HZIF-Mo). The resulting defective MOF catalyst exhibits exceptional activity and selectivity in the CO2RR, achieving a maximum CO Faradaic efficiency of 86.5% in a flow cell and maintaining above 80% even at high current densities up to 500 mA cm-2. In situ infrared spectroscopy and Density Functional Theory (DFT) calculations revealed that the introduced Mo vacancies downshift the d-band center of metal nodes, weaken the adsorption of *CO and enhance the stabilization of the *COOH intermediate, thereby significantly improving CO selectivity. This work thus establishes a viable synthetic paradigm for high-performance defective MOF electrocatalysts and provides fundamental atomic-level insight into the vacancy-enhanced CO2RR mechanism.