Enantioselective Synthesis of Amino Acids by Photocatalytic Reduction of CO2 on Chiral Mesostructured ZnS

26 December 2023, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Reduction and fixation of CO2 in natural systems via solar energy generates diverse products, ranging from small molecules to biomolecules. To date, only a few multicarbon species have been obtained by artificial CO2 photoreduction1-5, especially abiotic photosynthesis of biomolecules with various functional groups, which has long been a fundamental yet challenging issue. Herein, we report the photocatalytic synthesis of amino acids from CO2 and NH3 on a chiral mesostructured ZnS (CMZ) nanosphere, which is constructed by arrays of chiral nanorods. Serine (Ser) is the main component of various amino acids, with an enantiomeric excess (ee) greater than 96% and a total yield of over 30 μmol gcat-1. The Ser formation pathway could be accessed through *OCCO intermediates due to C-C coupling, as demonstrated by experimental data. Chiral-induced spin polarization of CMZ has been speculated to facilitate the separation of photogenerated carriers and the production of stable triplet OCCO. Different activation energies of reduction reactions driven by the spin-polarized electrons in CMZ lead to the formation of enantiomeric amino acids. Our findings will inspire new perspectives in catalytic theory and the formation of chiral biomolecules in artificial synthesis and nature.

Keywords

photocatalytic CO2 reduction
amino acids
chirality
photocatalysis
ZnS
enantioselective synthesis

Supplementary materials

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Supplementary Information
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Supplementary Figures, Tables and Notes for detailed experiments condition, material characterizations, control experiments and DFT calculations
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