An integrated photocatalytic/enzymatic system for the reduction of CO2 to methanol in bioglycerol-water

Michele Aresta; Angela Dibenedetto; Tomasz Baran; Antonella Angelini; Przemysław Labuz; Wojciech Macyk

doi:10.3762/bjoc.10.267

An integrated photocatalytic/enzymatic system for the reduction of CO2 to methanol in bioglycerol-water

Beilstein J Org Chem. 2014 Nov 3:10:2556-65. doi: 10.3762/bjoc.10.267. eCollection 2014.

Authors

Michele Aresta¹, Angela Dibenedetto², Tomasz Baran³, Antonella Angelini², Przemysław Labuz⁴, Wojciech Macyk⁴

Affiliations

¹ Chemical and Biomolecular Engineering Department, NUS, 4 Engineering Drive 4, Singapore 117585-SG ; IC2R srl Tecnopolis, km 3 via Casamassima, 70018 Valenzano (BA), Italy.
² CIRCC, Via Celso Ulpiani 27, 70126 Bari, Italy ; Department of Chemistry, University of Bari, Via Orabona 4, 70125 Bari, Italy.
³ Department of Chemistry, University of Bari, Via Orabona 4, 70125 Bari, Italy ; Faculty of Chemistry Jagiellonian University Ingardena 3, 30-060 Kraków, Poland.
⁴ Faculty of Chemistry Jagiellonian University Ingardena 3, 30-060 Kraków, Poland.

Abstract

A hybrid enzymatic/photocatalytic approach for the conversion of CO2 into methanol is described. For the approach discussed here, the production of one mol of CH3OH from CO2 requires three enzymes and the consumption of three mol of NADH. Regeneration of the cofactor NADH from NAD(+) was achieved by using visible-light-active, heterogeneous, TiO2-based photocatalysts. The efficiency of the regeneration process is enhanced by using a Rh(III)-complex for facilitating the electron and hydride transfer from the H-donor (water or a water-glycerol solution) to NAD(+). This resulted in the production of 100 to 1000 mol of CH3OH from one mol of NADH, providing the possibility for practical application.

Keywords: CO2 chemistry; NADH regeneration; electron transfer; enzymatic CO2 reduction; photochemistry; photosensitization.