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Title: Light‐driven Transformation of Carbon Monoxide into Hydrocarbons using CdS@ZnS : VFe Protein Biohybrids

Journal Article · · ChemSusChem
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]
  1. Department of Chemical and Biological Engineering University of Colorado Boulder Boulder CO 80303 USA
  2. Department of Molecular Biology and Biochemistry University of California, Irvine Irvine CA 92697-3900 USA
  3. Department of Molecular Biology and Biochemistry University of California, Irvine Irvine CA 92697-3900 USA, Department of Chemistry University of California Irvine USA
  4. Sachi Bio Louisville CO 80027 USA, Antimicrobial Regeneration Consortium Labs Louisville CO 80027 USA
  5. Department of Chemical and Biological Engineering University of Colorado Boulder Boulder CO 80303 USA, Sachi Bio Louisville CO 80027 USA, Antimicrobial Regeneration Consortium Labs Louisville CO 80027 USA
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Abstract Enzymatic Fisher‐Tropsch (FT) process catalyzed by vanadium (V)‐nitrogenase can convert carbon monoxide (CO) to longer‐chain hydrocarbons (>C2) under ambient conditions, although this process requires high‐cost reducing agent(s) and/or the ATP‐dependent reductase as electron and energy sources. Using visible light‐activated CdS@ZnS (CZS) core‐shell quantum dots (QDs) as alternative reducing equivalent for the catalytic component (VFe protein) of V‐nitrogenase, we first report a CZS : VFe biohybrid system that enables effective photo‐enzymatic C−C coupling reactions, hydrogenating CO into hydrocarbon fuels (up to C4) that can be hardly achieved with conventional inorganic photocatalysts. Surface ligand engineering optimizes molecular and opto‐electronic coupling between QDs and the VFe protein, realizing high efficiency (internal quantum yield >56 %), ATP‐independent, photon‐to‐fuel production, achieving an electron turnover number of >900, that is 72 % compared to the natural ATP‐coupled transformation of CO into hydrocarbons by V‐nitrogenase. The selectivity of products can be controlled by irradiation conditions, with higher photon flux favoring (longer‐chain) hydrocarbon generation. The CZS : VFe biohybrids not only can find applications in industrial CO removal for high‐value‐added chemical production by using the cheap, renewable solar energy, but also will inspire related research interests in understanding the molecular and electronic processes in photo‐biocatalytic systems.

Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0020361; SC0014470
OSTI ID:
1994003
Journal Information:
ChemSusChem, Journal Name: ChemSusChem Vol. 16 Journal Issue: 20; ISSN 1864-5631
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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