Confined bismuth single atoms and nanoparticles dual-sites constructed via reverse etching for CO2 photoreduction to CH4

Synchronizing the directional photogenerated transfer of electrons and regulating the CO2 photocatalytic reduction process are key to achieving the efficient and highly selective photocatalytic reduction of CO2. The design of highly-dispersed active sites and the efficient collaboration of multiple sites are of great importance in attaining the above target. Herein, a reverse etching route was first proposed to confine Bi single atoms and nanoparticles as dual-sites for assisting CO2 photoreduction on TiO2, avoiding the mutual masking of the active sites. The Synergism of the dual-sites achieves the hydrodeoxygenation of * COOH and ushers the directional conversion of CO2 to CH4. Highly dispersed single Bi atoms could induce the transfer of photogenerated electrons, enhance CO2 absorption, and further provide active sites for reducing CO2 to *COOH intermediates. Besides, appropriate Bi nanoparticles could promote the separation and transfer of photogenerated and inhibit the formation of hydroxyl groups; more importantly, they could promote the release of protons, which would further accelerate the conversion of *COOH to CH4. After being integrated, the optimized dual-Bi/TiO2 catalyst achieves a CH4 generation rate of 103.89 μmol·g−1·h−1 with an impressive selectivity of 96.87 % as well as remarkable durability for photocatalytic CO2 reduction. This work provides new insights into developing robust catalysts through the artful design of synergistic catalytic sites for efficient photocatalytic CO2 conversion.