Novel functionalized copper nanowires for electrocatalytic production of renewable feedstocks

This thesis explores the synthesis, characterization, and electrocatalytic applications of copper nanocrystals, with a particular focus on their role in the electrochemical reduction of CO2 into value-added products. Within a collaborative framework with Basell Poliolefine Italia S.r.l., the project addresses the urgent need for sustainable production of light hydrocarbons and olefins, key building blocks for the polymer industry, traditionally derived from fossil resources. In this context, nanostructured copper emerges as a natural candidate to drive CO2 electroreduction toward green ethylene and other monomers. A systematic Design of Experiments was employed to optimize the synthesis of copper nanowires (CuNWs), revealing how experimental parameters govern their morphology and physicochemical properties. Surface studies combining spectroscopic and electrochemical techniques showed that CuNWs possess stepped motifs rather than atomically flat facets. A comparative investigation between CuNWs (1D) and copper nanoplates (CuNPls, 2D) provided fundamental insights into their electrocatalytic behavior toward hydrogen evolution, CO2 reduction, and catalyst degradation. Building on this knowledge, strategies were developed to tailor CuNWs for selective CO2 conversion. Surface functionalization enabled the production of methanol at low overpotentials, while coupling CuNWs with in-situ formed organic shells successfully suppressed the competing hydrogen evolution reaction, achieving ethylene selectivity close to state-of-the-art benchmarks. Furthermore, a research stay at ICN2 (Barcelona) allowed the implementation of advanced techniques such as underpotential deposition and operando Raman spectroscopy to probe surface restructuring in polycrystalline copper. Finally, this work demonstrates the central role of copper nanocrystals in electrocatalysis, highlighting how their morphology and surface chemistry can be rationally engineered to steer CO2 reduction toward desired products. The findings underscore the power of complementary characterization methods and metal–organic coupling strategies, paving the way for the design of next-generation catalysts for sustainable carbon valorization.