Perovskite Photocatalytic CO2 Reduction or Photoredox Organic Transformation?. Issue 39 (23rd August 2022)

• Record Type: Journal Article
• Authors: San Martin, Jovan; Dang, Nhu; Raulerson, Emily; Beard, Matthew C.; Hartenberger, Joseph; Yan, Yong
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 39(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-23
• Subjects: CO Surrogate -- CO2 Reduction -- Perovskite -- Photocatalytic Organic Reactions -- Photoredox; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202205572
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Metal‐halide perovskites have been explored as photocatalysts for CO2 reduction. We report that perovskite photocatalytic CO2 reduction in organic solvents is likely problematic. Instead, the detected products (i.e., CO) likely result from a photoredox organic transformation involving the solvent. Our observations have been validated using isotopic labeling experiments, band energy analysis, and new control experiments. We designed a typical perovskite photocatalytic setup in organic solvents that led to CO production of up to ≈1000 μmol g −1 h −1 . CO2 reduction in organic solvents must be studied with extra care because photoredox organic transformations can produce orders of magnitude higher rate of CO or CH4 than is typical for CO2 reduction routes. Though CO2 reduction is not likely to occur, in situ CO generation is extremely fast. Hence a suitable system can be established for challenging organic reactions that use CO as a feedstock but exploit the solvent as a CO surrogate. Abstract : Halide perovskite photocatalytic CO2 reduction in organic solvent is likely problematic. The observed CO product clearly results from photocatalytic organic transformation involving solvents (i.e., ethyl acetate or chloroform). Perovskite‐photocatalyzed generation of CO from solvent at a fast rate may create synthetic opportunities for useful organic syntheses using organic solvent as the CO surrogate.