Relation between the nature of the surface facets and the reactivity of Cu2O nanostructures anchored on TiO2NT@PDA electrodes in the photoelectrocatalytic conversion of CO2 to methanol

• Published in: Applied catalysis. B, Environmental Environmental, 2020-02, Vol.261, p.118221, Article 118221
• Main Authors: Torquato, Lilian D. Moura, Pastrian, Fabián A.C., Perini, João A. Lima, Irikura, Kallyni, de L. Batista, Ana Paula, de Oliveira-Filho, Antonio G.S., Córdoba de Torresi, Susana I., Zanoni, Maria V. Boldrin
• Format: Article
• Language: English
• Subjects: Carbon dioxide; Catalytic activity; CO2 reduction; Conversion coating; Copper oxides; Cu2O; Cubes; Electrodes; Methanol; Morphology; Nanoparticles; Nanostructure; Nanotechnology; Nanotubes; Octahedrons; Optical properties; Oxygen; Photoelectrocatalysis; Polydopamine; Titanium dioxide; Vacancies
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2019.118221

[Display omitted] •PDA was used to anchor different structures of Cu2O on TiO2 nanotubes.•PDA contributes to photosensitization and CO2 adsorption on heterojunctions.•The optical properties and performance of Cu2O structures are facet-dependent.•Cubes show superior catalytic performance in the conversion of CO2 to methanol.•Control of morphology plays a key role in the effective application of photocatalysts. This paper investigates the influence of morphology of Cu2O nanoparticles (cubes, NcCu2O; spheres, NsCu2O; octahedrons, NoCu2O), deposited on TiO2 nanotubes (TiO2NT) coated with PDA, in the photoelectrocatalytic conversion of CO2 to methanol. At low bias (+0.2 V) a production of 10.0, 6.0 and 5.4 mg L−1 of methanol was obtained for TiO2NT@PDA-NsCu2O, TiO2NT@PDA-NoCu2O, and TiO2NT@PDA-NcCu2O electrodes, with faradaic efficiencies of 27, 39, and 66%, respectively. The conversion to methanol was 357% higher with NcCu2O, compared to the TiO2NT@PDA electrode. The results indicated that both the optical properties and the photocatalytic performance of nanostructures were facet-dependent. The superior catalytic activity of NcCu2O was attributed to the higher concentration of oxygen vacancies on {100} facets, which promotes the activation of CO2 with an energy of −1.2 kcal mol−1. With a lower concentration of oxygen vacancies, CO2 molecule is only physisorbed on {111} facets with an energy of −8.8 kcal mol−1.