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A photoactive porphyrinic metal−organic framework (MOF) has been prepared by exchanging Ti into a Zr‐based MOF precursor. The resultant mixed‐metal Ti/Zr porphyrinic MOF demonstrates much‐improved efficiency for gas‐phase CO2 photoreduction into CH4 and CO under visible‐light irradiation using water vapor compared to the parent Zr‐MOF. Insightful studies have been conducted to probe the photocatalysis processes. This work provides the first example of gas‐phase CO2 photoreduction into methane without organic sacrificial agents on a MOF platform, thereby paving an avenue for developing MOF‐based photocatalysts for application in CO2 photoreduction and other types of photoreactions. [ABSTRACT FROM AUTHOR]

Described for the first time is that carbon dioxide (CO2) can be successfully inserted into aryl C−H bonds of the backbone of a metal-organic framework (MOF) to generate free carboxylate groups, which serve as Brønsted acid sites for efficiently catalyzing the methanolysis of epoxides. The work delineates the very first example of utilizing CO2 for heterogeneous C−H activation and carboxylation reactions on MOFs, and opens a new avenue for CO2 chemical transformations under mild reaction conditions. [ABSTRACT FROM AUTHOR]