Interface Molecular Functionalization of Cu₂O for Synchronous Electrocatalytic Generation of Formate

Abstract

The electrocatalytic generation of valuable fuels and chemicals from carbon dioxide (CO2) and others with the assistance of clean solar energy is a highly promising way to realize the carbon-neutral cycle, which invokes the systematic development of advanced electrocatalysts for efficient and selective redox reactions of feedstocks. Herein, we demonstrate the interface modification of cuprous oxide with polyvinylpyrrolidone (PVP) to improve the electrocatalytic efficiency for the synchronous formate generation. Density functional theory calculations reveal that the interfacial properties can be effectively regulated by the PVP functionalization for the favorable formation of intermediates to improve the selectivity of formate generation. Importantly, the advanced electrocatalyts enable an efficient coupling of CO2 reduction with methanol oxidation in an electrochemical cell powered with a solar cell. The work provides a predictive link between the electrocatalytic redox reactions by applying the interfacial regulation strategies of electrocatalysts.

Tailoring Interfacial Physicochemical Properties in Cu2O-TiO2@rGO Heterojunction: Insights from EXAFS and Electron Trap Distribution Analysis

“…The X-ray absorption near edge structure (XANES) spectra of the photocatalysts were acquired to investigate their in-depth electronic states. For all samples displayed in Figure a, the Cu + peak at 8982 eV agrees very closely with the reference Cu 2 O . The magnified XANES spectra on low energy regions are given in Figure S2.…”

“…For all samples displayed in Figure 2a, the Cu + peak at 8982 eV agrees very closely with the reference Cu 2 O. 34 The magnified XANES spectra on low energy regions are given in Figure S2. The linear combination fitting results for the quantitative compositions of Cu species are displayed in Figure 2b.…”

Facet Dopant Regulation of Cu2O Boosts Electrocatalytic CO2 Reduction to Formate

“…Previously, Cu‐based electrocatalysts have been extensively studied in CO 2 RR because of their ability in converting CO 2 to CO, HCOO − , hydrocarbons, and alcohols by multiple electron‐proton pairs transfer reactions. [ 4 ] However, Cu‐based electrocatalysts have moderate binding energy to the reaction intermediates, so that they have a broad range of CO 2 RR products and poor energy efficiency [ 5 ] Alloying, [ 6 ] surface functionalization, [ 7 ] defect engineering, [ 8 ] oxidation state regulation, [ 9 ] and facet engineering [ 10 ] of Cu‐based electrocatalysts have been applied to tune the selectivity and electrolytic efficiency of CO 2 RR. Among these tactics, adjusting exposed facets of nano‐electrocatalysts can rationally change specific atom arrangements, reaction intermediate affinity, and surface energy, thereby effectively influencing CO 2 RR pathways and product distribution.…”

Review and Perspective on Transition Metal Electrocatalysts Toward Carbon-Neutral Energy

“…Copper-based catalysts are widely known for producing C 2+ value-added fuels and chemical. This is due to the negative binding energy between the catalyst active site and CO* intermediate as opposed to their positive binding energy toward H. − For this reason, CO* remains adsorbed on the surface while undergoing continuous protonation reactions. Albeit, this multitude of H + /e – transfer steps require a high overpotential to overcome the energy barrier of the intermediate/product formation, which is a major limitation for these catalysts. − Recent research efforts have focused on tuning the selectivity of the Cu catalyst toward C 2+ products, either through morphological, crystal plane, size, or electronic structure modifications.…”