Facet Dopant Regulation of Cu₂O Boosts Electrocatalytic CO₂ Reduction to Formate

Abstract

Electrochemical carbon dioxide reduction reaction (CO 2 RR) using clean electric energy provides a sustainable route to generate highly-valuable chemicals and fuels, which is beneficial for realizing the carbon-neutral cycle. Up to now, achieving a narrow product distribution and highly targeted product selectivity over Cu-based electrocatalysts is still a big challenge. Herein, sulfur modification on different crystal planes of cuprous oxide (Cu 2 O) is demonstrated, results in an improvement for formate generation to different degrees. Experimental results and density functional theory (DFT) calculations reveal that sulfur species modified on the surface of Cu 2 O (100) facet effectively lower the formation energy of key intermediate *OCOH for formate generation compared with Cu 2 O (111) facet. As a consequence, the modification of p-Block elements over Cu-based electrocatalysts is an effective strategy to optimize the adsorption energy of key intermediate during CO 2 RR, leading to a highly selective product.

Atomically Dispersed W1–O3 Bonded on Pd Metallene for Cascade NO Electroreduction to NH3

“…Generally, the NH 3 yield rate of the NORR operated in a H-type cell is greatly restricted by the low current density due to the poor NO solubility and diffusion in the electrolyte . To address this issue, the gas diffusion electrode assembled in a flow cell is utilized to boost the NO diffusion capability (Figure e). − As expected, the current density of W 1 Pd in the flow cell shows a substantial enhancement over that in the H-type cell (Figure S21). Consequently, the NH 3 yield rate of W 1 Pd in the flow cell is largely increased to 758.5 μmol h –1 cm –2 (−0.4 V), which is 2.5 times higher than that in the H-type cell (Figure f).…”

Direct coupling of two inert CO2 molecules to form a C–C bond on the Cu0 atomic interfaces of the nitrogen-doped graphene-supported Cu4 cluster

“…The CO 2 molecule could be reduced to *OCHO, *COOH, *CO, *CHO, *CH, and *CH 2 , and others in the series of electrochemical elementary steps, which would become the potential coupling species for the formation of the C-C bond in CO 2 RR. 49,79,80 These species may occupy the active sites of the catalyst and suppress the direct coupling of two CO 2 molecules over the surface of the Cu 4 /N 3 GN catalyst. Owing to the low surface concentrations of *CHO, *CH, *CH 2 , and other multiple reduced species of CO 2 molecule over the catalytic surface, the reaction pathway for the coupling of these species to form the C-C bond is not important when compared with the high concentration species *CO 2 , *OCHO, *COOH, and *CO.…”

A review on electrocatalytic CO2 conversion via C–C and C–N coupling

“…It is urgently necessary to convert CO 2 and these nitrogen‐containing species (such as NO 3 − , NO 2 − , NO, N 2 O, and N 2 ) 1–3 to alleviate the artificially imbalanced carbon and nitrogen cycles. Using renewable electrical energy, the electrocatalytic process can produce desired products by controlling the catalysts, applied voltage, and reaction medium 4–6 . CO 2 can be electrocatalytically reduced into carbon monoxide (CO), formic acid, and other C 2+ products, such as ethanol (C 2 H 6 O), ethylene (C 2 H 4 ), or propanol (C 3 H 8 O) through C–C coupling 7–12 .…”

“…Using renewable electrical energy, the electrocatalytic process can produce desired products by controlling the catalysts, applied voltage, and reaction medium. [4][5][6] CO 2 can be electrocatalytically reduced into carbon monoxide (CO), formic acid, and other C 2+ products, such as ethanol (C 2 H 6 O), ethylene (C 2 H 4 ), or propanol (C 3 H 8 O) through C-C coupling. [7][8][9][10][11][12] Moreover, the integration of nitrogen-containing reactants into the CO 2 reduction process can further produce more valuable chemicals through C-N coupling.…”