An enhanced photo(electro)catalytic CO₂ reduction onto advanced BiOX (X = Cl, Br, I) semiconductors and the BiOI-PdCu...

The photoelectrocatalytic reduction of CO₂ (CO₂RR) onto bismuth oxyhalides (BiOX, X = Cl, Br, I) was studied through physicochemical and photoelectrochemical measurements. The successful synthesis of the BiOX compounds was carried out through a solvothermal methodology and confirmed by XRD measurements. The morphology was analyzed by SEM; meanwhile, area and pore size were determined through BET area measurements. BiOI and BiOCl present a lower particle size (3.15 and 2.71 μm, respectively); however, the sponge-like morphology presented by BiOI results in an increase in the BET area, which can enhance the catalytic activity of this semiconductor. In addition, DRS measurements allowed us to determine bandgap values of 1.9, 2.4, and 3.6 eV for BiOI, BiOBr, and BiOCl, respectively. Such results predict better visible light harvesting for BiOI. Photoelectrochemical measurements indicated that BiOX shows p-type semiconductor behavior, being the holes the majority charge carriers, making BiOI the most active material to carry out photoelectrocatalytic CO₂RR. In the second stage, three different composites, BiOI-Pd, BiOI-Cu, and BiOI-PdCu, (BiOI-M; M = Pd, Cu, PdCu), were fabricated to study the influence of active metal nanoparticles (NP's) in the BiOI CO₂RR activity. XRD measurements confirmed the interaction between BiOI and the metallic NP's, the three composites overpassed by 20% the BET area of pristine BiOI. Photoelectrochemical measurements indicate that all BiOI-metal composites are suitable materials to perform CO₂ reduction in neutral media efficiently; however, the BiOI-PdCu composites surpassed the faradaic current of BiOI-Pd and BiOI-Cu at 0.85 V vs. RHE (3.15, 2.06 and 2.15 mA cm^-2, respectively). BiOI-PdCu presented photoactivity to carry out the CO₂ reduction evolving formic acid and acetic acid as the main products under visible-light irradiation.