Subsurface Oxygen Defects Electronically Interacting with Active Sites on In2O3 for Enhanced Photothermocatalytic CO2 Reduction

Oxygen defects play an important role in many catalytic reactions. Increasing surface oxygen defects can be done through reduction treatment. However, excessive reduction blocks electron channels and deactivates the catalyst surface due to electron-trapped effects by subsurface oxygen defects. How to effectively extract electrons from subsurface oxygen defects which cannot directly interact with reactants is challenging and remains elusive. Herein, we report a metallic In-embedded In2O3 nanoflake catalyst over which the turnover frequency of CO2 reduction into CO increases by a factor of 866 (7615 h-1) and 376 (2990 h-1) at same light intensity and reaction temperature, respectively, compared to In2O3. Under electron-delocalization effect of O-In-(O)Vo-In-In structural units at the interface, the electrons in the subsurface oxygen defects are extracted and gather at surface active sites. This improves the electronic coupling with CO2 and stabilizes COOH intermediate. The study opens up new insights for exquisite electronic manipulation of oxygen defects.

CO2 reduction on pure Cu produces only H2 after subsurface O is depleted: Theory and experiment

We elucidate the role of subsurface oxygen on the production of C2 products from CO2 reduction over Cu electrocatalysts using the newly developed grand canonical potential kinetics density functional theory method, which predicts that the rate of C2 production on pure Cu with no O is ∼500 times slower than H2 evolution. In contrast, starting with Cu2O, the rate of C2 production is >5,000 times faster than pure Cu(111) and comparable to H2 production. To validate these predictions experimentally, we combined time-dependent product detection with multiple characterization techniques to show that ethylene production decreases substantially with time and that a sufficiently prolonged reaction time (up to 20 h) leads only to H2 evolution with ethylene production ∼1,000 times slower, in agreement with theory. This result shows that maintaining substantial subsurface oxygen is essential for long-term C2 production with Cu catalysts.