Development of CuAg/Cu₂O nanoparticles on carbon nitride surface for methanol oxidation and selective conversion of...

Herein we report a catalyst consisting of CuAg/Cu₂O nanoparticles (NPs), synthesized on the two-dimensional carbon nitride (CN) surface via galvanic exchange route for electrocatalytic methanol oxidation and carbon dioxide reduction. The lower reduction potential of copper ([Cu⁺(aq) + e^- → Cu(s)], + 0.52 eV) compared to Ag ([Ag⁺(aq) + e^- → Ag(s)], +0.80 eV) makes Cu(0) easily exchangeable by Ag⁺ ions via galvanic exchange without applying any external bias. In a two-step process, the Cu NPs are synthesized first on CN surface by adsorbing Cu²⁺ precursors and reducing them by NaBH₄. Due to unstable nature of Cu²⁺ in aqueous medium some Cu₂O NPs (a mixed phase of Cu/CuO) were also formed. Thereafter in the second step, Ag⁺ precursors are brought in contact with the already synthesized Cu and Cu₂O nanoparticles (NPs). The Cu and Cu₂O NPs present on the surface of CN are partially exchanged by Ag atoms to generate bimetallic CuAg/Cu₂O NPs. Two atoms of Ag are expected to be deposited for every Cu atom replaced. As galvanic replacement occurs on the solid surface of carbon nitride, there is only a partial replacement of Cu and Cu₂O atoms. The catalysts CN/Cu/Cu₂O and CN/CuAg/Cu₂O were evaluated for their performance towards methanol oxidation and carbon dioxide reduction. CN/CuAg/Cu₂O showed twice the current density for methanol oxidation than CN/Cu/Cu₂O in a 0.5 M methanol solution. Probably the reason for high activity of Ag than Cu is related to the weak bond of oxygen on silver substrate for oxidation reactions and strong binding affinity on copper substrate. In case of carbon dioxide reduction (CO₂ reduction) the product was identified to be formate by oxidizing the product (formate) on a Pt ring electrode. The results revealed CN/CuAg/Cu₂O shows a better selectivity towards formic acid formation than CN/Cu/Cu₂O using the rotating ring disc electrode (RRDE). A probable reason may be the strain induced by alloy formation which could favor a reduced coverage of adsorbed hydrogen and a decrease in oxophilicity of the compressively strained copper.