biostudies-literatureUnknown15(1)Feng CDirect photocatalytic conversion of methane to value-added C₁ oxygenate with O₂ 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 CH₄ to HCHO. We propose the directional activation of O₂ 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 •CH₃ radicals rapidly combine to form HCHO while inhibiting competing reactions, thus resulting in ultra-highly selectNature communications9088https://www.ebi.ac.uk/biostudies/studies/S-EPMC11494074biostudies-literatureOptimizing the reaction pathway of methane photo-oxidation over single copper sites.PMC11494074Xia LLuo JZhu YRueping MWang SRen YZhang HHu MHan YZou CZuo SFeng CfalseOptimizing the reaction pathway of methane photo-oxidation over single copper sites.Direct photocatalytic conversion of methane to value-added C₁ oxygenate with O₂ 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 CH₄ to HCHO. We propose the directional activation of O₂ 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 •CH₃ radicals rapidly combine to form HCHO while inhibiting competing reactions, thus resulting in ultra-highly select2024-01-01T00:00:00Z2024 Oct2025-04-04T14:37:10.662Z2025-04-04T14:37:10.662ZS-EPMC114940743943374910.1038/s41467-024-53483-z