Quasi-graphitic carbon shell-induced Cu confinement promotes electrocatalytic CO2 reduction toward C2+ products

Abstract

For steady electroconversion to value-added chemical products with high efficiency, electrocatalyst reconstruction during electrochemical reactions is a critical issue in catalyst design strategies. Here, we report a reconstruction-immunized catalyst system in which Cu nanoparticles are protected by a quasi-graphitic C shell. This C shell epitaxially grew on Cu with quasi-graphitic bonding via a gas–solid reaction governed by the CO (g) - CO2 (g) - C (s) equilibrium. The quasi-graphitic C shell-coated Cu was stable during the CO2 reduction reaction and provided a platform for rational material design. C2+ product selectivity could be additionally improved by doping p-block elements. These elements modulated the electronic structure of the Cu surface and its binding properties, which can affect the intermediate binding and CO dimerization barrier. B-modified Cu attained a 68.1% Faradaic efficiency for C2H4 at −0.55 V (vs RHE) and a C2H4 cathodic power conversion efficiency of 44.0%. In the case of N-modified Cu, an improved C2+ selectivity of 82.3% at a partial current density of 329.2 mA/cm2 was acquired. Quasi-graphitic C shells, which enable surface stabilization and inner element doping, can realize stable CO2-to-C2H4 conversion over 180 h and allow practical application of electrocatalysts for renewable energy conversion.

Boosting CO2 electroreduction towards C2+ products via CO* intermediate manipulation on copper-based catalysts

“…111 This prediction was verified by doping anions in copper catalysts. [112][113][114] Sargent's group successfully synthesized B-doped Cu during the preparation stage using NaBH 4 as the reactant. The doping of B effectively improved the selectivity of C 2 .…”

Three-dimensional porphyrinic covalent organic frameworks for highly efficient electroreduction of carbon dioxide

“…5–11 Compared with other products, the two-electron involved product CO that has been widely used to produce synthetic liquid fuels by the Fischer–Tropsch process may be more easily produced via the CO 2 RR. 12–15 However, the sluggish kinetics of the CO 2 RR and the associated hydrogen evolution reaction (HER) usually lead to low current density and selectivity, 16,17 which makes it difficult to meet the requirement of commercial applications. 18 Now, although noble metal-based ( e.g.…”

Infrared analysis of catalytic CO2 reduction in hydrogenated germanium

“…2 Recently, considerable effort has been devoted to the development of heterogeneous catalysts based on earth-abundant materials. [2][3][4][5] The group IV element germanium is such an (relatively) earth-abundant material. The elemental abundance of Ge is E1.8 ppm in the earth's crust, 6 which makes it more abundant than known conventional catalyst materials (Au, Pt, and Pd) and noble metal complex-based molecular catalysts (Ru, Ir, and Re), although not as abundant as elements used for novel metal complexes (Co, Ni, Fe, Mn, and Cu).…”