Immobilized Enzymes on Graphene as Nanobiocatalyst

ACS Appl Mater Interfaces. 2020 Jan 8;12(1):250-259. doi: 10.1021/acsami.9b17777. Epub 2019 Dec 30.


Using enzymes as bioelectrocatalysts is an important step toward the next level of biotechnology for energy production. In such biocatalysts, a sacrificial cofactor as an electron and proton source is needed. This is a great obstacle for upscaling, due to cofactor instability and product separation issues, which increase the costs. Here, we report a cofactor-free electroreduction of CO2 to a high energy density chemical (methanol) catalyzed by enzyme-graphene hybrids. The biocatalyst consists of dehydrogenases covalently bound on a well-defined carboxyl graphene derivative, serving the role of a conductive nanoplatform. This nanobiocatalyst achieves reduction of CO2 to methanol at high current densities, which remain unchanged for at least 20 h of operation, without production of other soluble byproducts. It is thus shown that critical improvements on the stability and rate of methanol production at a high Faradaic efficiency of 12% are possible, due to the effective electrochemical process from the electrode to the enzymes via the graphene platform.

Keywords: bioelectrocatalysis; carbon dioxide reduction; enzyme catalysis; enzyme immobilization; graphene; methanol.

MeSH terms

  • Biocatalysis*
  • Carbon Dioxide / chemistry*
  • Enzymes, Immobilized / chemistry*
  • Graphite / chemistry*
  • Methanol / chemical synthesis*
  • Oxidation-Reduction


  • Enzymes, Immobilized
  • Carbon Dioxide
  • Graphite
  • Methanol