Photoelectrochemical reduction of CO2 using a TiO2 photoanode and a gas diffusion electrode modified with a metal phthalocyanine catalyst

The mass transport limitations encountered in classical H-cells for electrochemical CO2 reduction reaction (CO2RR) have spurred research in gas diffusion electrode (GDE) systems. However, current reports on CO2RR required large biases (anode potential vs. cathode potential > -2.0 V) for high current efficiencies. In this work, we combined a TiO2 photoanode and a GDE modified with a Co, Ni or Sn metal phthalocyanine (MPc) catalyst to reduce the external bias requirement for CO2RR. We found the Faradaic efficiencies and the selectivity of the photoelectrolysis products were influenced by (i) the metal cation (Ni, Co or Sn) coordinated to the phthalocyanine, (ii) the electrolyte temperature and concentration and (iii) the magnitude of the applied bias. In addition, analyzes of the voltage distributions between the TiO2 photoanode and the MPc-GDE revealed the current efficiency of the TiO2/MPc-GDE cell was limited predominantly by a high ohmic polarization loss at the TiO2 photoanode due to an excessive thickness of the TiO2 layer. The cathodic process at the MPc-GDE was governed by the activation energy of the electrode. The thickness of the TiO2 photoanode was subsequently optimized for higher current efficiency. The highest Faradaic efficiency for PEC CO2RR was obtained when a NiPc catalyst was utilized as the CO2RR catalyst and the optimum cell conditions were as follows: (i) a GDE electrolyte temperature of <11 degrees C, (ii) a GDE electrolyte concentration of >1 M aq. Na2SO4 electrolyte solution and (iii) a TiO2 oxidation time of 3 h. Using these optimized cell conditions and under UV illumination, the as-prepared TiO2/NiPc-GDE cell shows a notably high CO2RR Faradaic efficiency and selectivity for CO (at 98%) and at a lowest reported cell bias of 0.8 V (anode potential vs cathode potential). This work provides an improved understanding of the cell designs of a vapor-fed CO2RR reactor based on a TiO2/MPc-GDE photoelectrochemical system. (C) 2020 Elsevier Ltd. All rights reserved.