Constructing dual-functional porphyrin-based thorium metal-organic framework toward photocatalytic uranium(Ⅵ)reduction integrated with organic oxidation

摘要

The rational fabrication of photocatalysts with dual functions upon visible light, such as photocatalytic radioactive U(Ⅵ)reduction and value-added organic oxidation, is highly desirable but remains huge challenge. Here, we couple the photocatalytic U(Ⅵ) reduction with the oxidative organic synthesis to one system using novel extended π-conjugated framework(Cu@ThTCPP) without the expense of sacrificial reagents. Noticeably, the as-prepared Cu@Th-TCPP linked by tetratopic tetrakis(4-carboxyphenyl)porphyrin(TCPP) ligand and unique Th(μ-O)(HCOO)(HO)secondary building unit(SBU) exhibits significantly enhanced activity when the photocatalytic U(Ⅵ) reduction and thioanisole oxidation were integrated to one system.Further experimental characterizations demonstrate that the highly conjugated framework of Cu@Th-TCPP is good for the charge transfer and separation, while incorporating Cusite further accelerates the charge-carrier dynamics, thus giving rise to the dual-functional property. Apparently, this strategy conforms to atomic economy, opens a new horizon to address radioactive environmental pollution in natural water systems and soils, and simultaneously produces valuable chemicals.