Galvanic Exchange as a Novel Method for Carbon Nitride Supported CoAg Catalyst Synthesis for Oxygen Reduction and Carbon Dioxide Conversion

Abstract

A bimetallic alloy of CoAg nanoparticles (NPs) on a carbon nitride (CN) surface was synthesized using a galvanic exchange process for the oxygen reduction reaction (ORR) and carbon dioxide electrocatalytic conversion. The reduction potential of cobalt is ([Co2+(aq) + 2e− → Co(s)], −0.28 eV) is smaller than that of Ag ([Ag+(aq) + e− → Ag(s)], 0.80 eV), which makes Co(0) to be easily replaceable by Ag+ ions. Initially, Co NPs (nanoparticles) were synthesized on a CN surface via adsorbing the Co2+ precursor on the surface of CN and subsequently reducing them with NaBH4 to obtain Co/CN NP. The Co NPs on the surface of CN were then subjected to galvanic exchange, where the sacrificial Co atoms were replaced by Ag atoms. As the process takes place on a solid surface, only the partial replacement of Co by Ag was possible generating CoAg/CN NPs. Synthesized CoAg/CN bimetallic alloy were characterized using different techniques such as powder x-ray diffraction (PXRD), x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and electron diffraction spectroscopy (EDS) to confirm the product. Both the catalysts, Co/CN and CoAg/CN, were evaluated for oxygen reduction reaction in 1M KOH solution and carbon dioxide conversion in 0.5 M KHCO3. In the case of ORR, the CoAg/CN was found to be an efficient electrocatalyst with the onset potential of 0.93 V, which is comparable to commercially available Pt/C having Eonset at 0.91 V. In the electrocatalytic conversion of CO2, the CoAg/CN showed better performance than Co/CN. The cathodic current decreased dramatically below −0.9V versus Ag/AgCl indicating the high conversion of CO2.