4.8 Article

Fast and Selective Photoreduction of CO2 to CO Catalyzed by a Complex of Carbon Monoxide Dehydrogenase, TiO2, and Ag Nanoclusters

Journal

ACS CATALYSIS
Volume 8, Issue 4, Pages 2789-2795

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b04308

Keywords

carbon monoxide dehydrogenase; silver nanoclusters; artificial photosynthesis; CO2 photoreduction; photocatalytic enzyme assembly

Funding

  1. Royal Society
  2. UK Biotechnology and Biological Sciences Research Council (BBSRC) [BB/M005720/1]
  3. Newton fund [DHR00490]
  4. NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R37GM039451] Funding Source: NIH RePORTER
  5. BBSRC [BB/M005720/1] Funding Source: UKRI
  6. Biotechnology and Biological Sciences Research Council [BB/M005720/1] Funding Source: researchfish

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Selective, visible-light-driven conversion of CO2 to CO with a turnover frequency of 20 s(-1) under visible light irradiation at 25 degrees C is catalyzed by an aqueous colloidal system comprising a pseudoternary complex formed among carbon monoxide dehydrogenase (CODH), silver nanoclusters stabilized by polymethacrylic acid (AgNCs-PMAA), and TiO2 nanoparticles. The photocatalytic assembly, which is stable over several hours and for at least 250000 turnovers of the enzyme's active site, was investigated by separate electrochemical (dark) and fluorescence measurements to establish specific connectivities among the components. The data show (a) that a coating of AgNCs-PMAA on TiO2 greatly enhances its ability as an electrode for CODH-based electrocatalysis of CO2 reduction and (b) that the individual Ag nanoclusters interact directly and dynamically with the enzyme surface, most likely at exposed cysteine thiols. The results lead to a model for photocatalysis in which the AgNCs act as photosensitizers, CODH captures the excited electrons for catalysis, and TiO2 mediates hole transfer from the AgNC valence band to sacrificial electron donors. The results greatly increase the benchmark for reversible CO2 reduction under ambient conditions and demonstrate that, with such efficient catalysts, the limiting factor is the supply of photogenerated electrons.

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