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[Display omitted] • In-doped amino-functionalized UiO-66 Zr-MOFs are synthesized by one-pot reaction. • Amino groups reduce band gap by lifting valence band maximum. • In doping facilities LMCT process by inducing oxygen vacancies. • aU(Zr/In) exhibits the excellent photoreduction activity of CO 2 to CO. Metal organic frameworks (MOFs) with high porosity and highly tunable physical/chemical properties can serve as heterogeneous catalysts for CO 2 photoreduction, but the application is hindered by the large band gap (E g) and insufficient ligand-to-metal charge transfer (LMCT). In this study, a simple one-pot solvothermal strategy is proposed to prepare an amino-functionalized MOF (aU(Zr/In)) featuring an amino-functionalizing ligand linker and In-doped Zr-oxo clusters, which enables efficient CO 2 reduction driven with visible light. The amino functionalization leads to a significant reduction of E g as well as a charge redistribution of the framework, allowing the absorption of visible light and the efficient separation of photogenerated carriers. Furthermore, the incorporation of In not only promotes the LMCT process by creating oxygen vacancies in Zr-oxo clusters, but also greatly lowers the energy barrier of the intermediates for CO 2 -to-CO conversion. With the synergistic effects of the amino groups and the In dopants, the optimized aU(Zr/In) exhibits a CO production rate of 37.58 ± 1.06 μmol g-1 h−1, outperforming the isostructural University of Oslo-66- and Material of Institute Lavoisier-125-based photocatalysts. Our work demonstrates the potential of modifying MOFs with ligands and heteroatom dopants in metal-oxo clusters for solar energy conversion. [ABSTRACT FROM AUTHOR]

An efficient S-scheme photocatalyst based on 3D flower-like Fe-doped In 2 S 3 /Fe 3 S 4 hetero-microspheres assembled from interconnected nanosheets was synthesized via a facile one-pot solvothermal reaction, which exhibits the enhanced interfacial electric field and boosted visible-light-driven CO 2 reduction. [Display omitted] S-scheme heterojunctions hold great potential for CO 2 photoreduction into solar fuels, but their activities are severely limited by the low efficiency of interfacial charge transfer. In this work, a facile one-pot solvothermal reaction has been developed to dope Fe into flower-like In 2 S 3 /Fe 3 S 4 hetero-microspheres (Fe-In 2 S 3 /Fe 3 S 4 HMSs), which are demonstrated as an efficient S-scheme photocatalyst for visible-light-driven CO 2 photoreduction. The doping of Fe not only reduces the bandgap of In 2 S 3 and thus extends the optical response to the visible-light region, but also increases the densities of donors and sulfur vacancies, which leads to an elevated Fermi level (E f). The difference of E f between In 2 S 3 and Fe 3 S 4 is enlarged and their band bending at the interface is therefore enhanced, which results in promoted carriers transfer in the S-scheme pathway due to the reinforced interfacial electric field. Moreover, Fe-doped In 2 S 3 reduces the formation energy of the *CO intermediate, which thermodynamically favors the CO evolution at the surface. As a result, the Fe-In 2 S 3 /Fe 3 S 4 HMSs exhibit a significantly boosted CO 2 photoreduction activity in comparison with bare In 2 S 3 and Fe-In 2 S 3 samples. This work demonstrates the great potential of heteroatom-engineered S-scheme photocatalysts for CO 2 photoreduction. [ABSTRACT FROM AUTHOR]