Ru-O<sub>V</sub> Site-Mediated Product Selectivity Switch for Overall Photocatalytic CO<sub>2</sub> Reduction.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39659098.
- Also identified by DOI 10.1002/adma.202411813.
- No licence information is recorded for this record.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
The photocatalytic reduction of carbon dioxide (CO<sub>2</sub>) to methane (CH<sub>4</sub>) represents a sustainable route for directly converting greenhouse gases into chemicals but poses a significant challenge in achieving high selectivity due to thermodynamic and kinetic limitations during the reaction process. This work establishes Ru-O<sub>V</sub> active sites on the surface of TiO<sub>2</sub> by anchoring coordination unsaturated Ru single-atoms, which stabilize crucial reaction intermediates and facilitate local mass transfer to achieve dual optimization of the thermodynamics and kinetics of the overall photocatalytic CO<sub>2</sub> reduction. Combining operando spectroscopy with density functional theory (DFT) calculations indicates that oxygen vacancies (O<sub>V</sub>) inhibits the desorption of *CO, whereas Ru facilitates proton extraction. This configuration not only lowers the overall activation energy barrier but has also been engineered to serve as a selectivity switch, changing the reaction route to produce CH<sub>4</sub> instead of CO. Consequently, the Ru-O<sub>V</sub>/TiO<sub>2</sub> exhibits a 195.4-fold improvement in the CH<sub>4</sub> yield compared to TiO<sub>2</sub>, accompanied by an increase in selectivity to 81%.