Proceedings of MATSUS Spring 2024 Conference (MATSUS24)
Publication date: 18th December 2023
The photoelectrochemical (PEC) conversion of CO2 to obtain high-value chemicals is a promising strategy to mitigate CO2 emissions as well as produce fuels for energy storage from sunlight harvesting. Although significant progress has been achieved in developing oxides semiconductors to promote CO2 reduction reaction (CO2RR), the performance and long-term stability of these materials remain insufficient for commercial application.1 The little-studied p-type semiconductor Cu2WO4 has shown interesting properties to be used as a photocathode, such as a narrow band gap (1.98 eV) and conduction band with energy enough to promote CO2 conversion under irradiation. In this work, the ternary oxide Cu2WO4 was used as a photoactive material for photoassisted CO2 reduction reaction (CO2RR).2 The Cu2WO4 was synthesized by arc-melting method from the precursor’s mixture of copper oxide and tungstate oxide (2.3 Cu: 1 W atom molar ratio). After powdering the obtained sample, the X-ray diffraction (XRD) structural analysis revealed that the crystalline reddish particulate was a Cu2WO4 material and by-products or residues of precursor oxides were not observed in the XRD spectra of the sample. Moreover, electrodes prepared with Cu2WO4 sample exhibited a positive photopotential (+ 60 mV) and a cathodic photocurrent under irradiation, which was intensified in a CO2-saturated aqueous solution (35 µAcm-2 at 0.25 V vs RHE), demonstrating the photoactivity of this semiconductor for CO2RR. Gas diffusion electrodes containing Cu2WO4 (GDE/Cu2WO4) were characterized by XRD, SEM and EDS analyses and used as photocathodes to promote photoassisted CO2 reduction into ethanol. We also investigated the photo(corrosion) mechanism of copper(I) tungstate during the photoelectrochemical CO2 reduction reaction. In these studies, in situ Raman spectroscopy measurements and X-ray Diffraction (XRD) analyses of Cu2WO4 photoelectrode showed Cu2O as a second crystalline phase formed on Cu2WO4 surface during the PEC CO2 reduction, these results were corroborated with ICP-OES and XPS analyses. Therefore, this work provided important insights related to the performance and degradation reaction of Cu2WO4 photoelectrode during the CO2RR.
The authors gratefully acknowledge support from Unicamp, Imperial College London, CINE, FAPESP (Process 2021/05853-8 and 2023/02684-6), CNPEM, CNPq and CAPES.
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