Optimizing the reaction pathway of methane photo-oxidation over single copper sites.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39433749.
- Also identified by DOI 10.1038/s41467-024-53483-z and PMC identifier 11494074.
- Licence recorded as CC BY-NC-ND.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
Direct photocatalytic conversion of methane to value-added C<sub>1</sub> oxygenate with O<sub>2</sub> is of great interest but presents a significant challenge in achieving highly selective product formation. Herein, a general strategy for the construction of copper single-atom catalysts with a well-defined coordination microenvironment is developed on the basis of metal-organic framework for selective photo-oxidation of CH<sub>4</sub> to HCHO. We propose the directional activation of O<sub>2</sub> on the mono-copper site breaks the original equilibrium and tilts the balance of radical formation almost completely toward •OOH. The synchronously generated •OOH and •CH<sub>3</sub> radicals rapidly combine to form HCHO while inhibiting competing reactions, thus resulting in ultra-highly selective HCHO production (nearly 100%) with a time yield of 2.75 mmol g<sub>cat</sub><sup>-1</sup> h<sup>-1</sup>. This work highlights the potential of rationally designing reaction sites to manipulate reaction pathways and achieve selective CH<sub>4</sub> photo-oxidation, and could guide the further design of high-performance single-atom catalysts to meet future demand.