A Confined CuxO@Styrene Microreactor Achieves the Conversion of CO2 to C2+ Products via Intermediate Trapping.

The electrochemical reduction of carbon dioxide to multi-carbon (C2+) products is impeded by the instability and inefficient utilization of key reaction intermediates. To address this challenge, we developed a strategy based on geometric control of spatially confined microenvironments, enabling the rational design of programmable CuxO microreactors on Cu2+(111)/Cu+(200) substrates. Two distinct catalyst architectures-small-ordered (s-CuxO@styrene) and large-ordered (c-CuxO@styrene)-were systematically engineered to modulate CO intermediate behavior, thereby directing reaction selectivity toward ethylene and ethanol production. Faradaic efficiencies for C2+ products demonstrate pronounced dependence on microstructure: increasing from negligible values in the small-ordered s-CuxO@styrene (25.6% ethylene,12.4% ethanol, 3% propylene) to 78.8% in the large-ordered c-CuxO@styrene (55% ethylene, 23% ethanol, 1% propylene). In situ infrared spectroscopy reveals that the highly ordered configuration enhances CO adsorption, promoting the accumulation of critical *OCCOH and *OC2H5 intermediates. Moreover, synergistic interactions between Cu+ and Cu0 active sites accelerate C-C coupling kinetics, favoring selective formation of C2+ species. This work establishes a geometry-driven paradigm for controlling catalytic selectivity independent of compositional tuning, offering a promising avenue for the development of adaptive catalytic systems in renewable energy conversion.