Improving CO₂-to-C₂₊ Product Electroreduction Efficiency via Atomic Lanthanide Dopant-Induced Tensile-Strained CuO_x Catalysts

Abstract

Cu is a promising electrocatalyst in CO 2 reduction reaction (CO 2 RR) to high-value C 2+ products. However, as important C−C coupling active sites, the Cu + species is usually unstable under reduction conditions. How atomic dopants affect the performance of Cu-based catalysts is interesting to be studied. Herein, we first calculated the difference between the thermodynamic limiting potentials of CO 2 RR and the hydrogen evolution reaction, as well as the *CO binding energy over Cu 2 O doped with different metals, and the results indicated that doping atomic Gd into Cu 2 O could improve the performance of the catalyst effectively. On the basis of the theoretical study, we designed Gd 1 / CuO x catalysts. The distinctive electronic structure and large ion radii of Gd not only keep the Cu + species stable during the reaction but also induce tensile strain in Gd 1 /CuO x , resulting in excellent performance of the catalysts for electroreduction of CO 2 to C 2+ products. The Faradic efficiency of C 2+ products could reach 81.4% with a C 2+ product partial current density of 444.3 mA cm −2 at −0.8 V vs a reversible hydrogen electrode. Detailed experimental and theoretical studies revealed that Gd doping enhanced CO 2 activation on the catalyst, stabilized the key intermediate O*CCO, and reduced the energy barrier of the C−C coupling reaction.

Oxygen defect engineering on low-crystalline iron(iii) oxyhydroxide as a highly efficient electrocatalyst for water oxidation

“…2h) without any identifiable diffraction points, further revealing the characteristics of long-range disorder but short-term order. 36 The lattice fringe width of V O -FeOOH was measured to be 0.26 nm from Fig. 1i.…”

Highly Efficient Electroreduction of CO2 to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

“…This phenomenon can be attributed to excessive reaction potential overlapping with the formate potential window, making C−C coupling difficult. 5,47 Interestingly, as the Sn content continued to increase, formate became the dominant product. This phenomenon is likely due to the excess Sn content leading to the generation of di-tin or multi-tin sites, which favors formate product (Figures S18 and S19).…”

Enhanced electron penetration triggering interfacial charge redistribution in N-doped graphene-wrapped NiGd nanoparticles for coupling methanol electroreforming to H2 production

“…2d), the binding energies of 143.0 and 148.5 eV are observed for Gd 4d 5/2 and Gd 4d 3/2 . 40,48 The high-resolution XPS peaks of N 1s in NiGd@N–C can be deconvoluted into four peaks centered at 398.7 eV (pyridinic N), 399.6 eV (pyrrolic N) and 400.5 eV (graphitic N), and N + –O species (402–405 eV) (Fig. 2e).…”

“…More recently, modification of TM-based electrocatalysts with rare earth (RE) elements is of particular interest because of the special specific 4f orbital occupancy and lower electronegativity of RE metals than TMs. 38–41 Theoretically, when modifying TM-based materials with RE elements, TM atoms will accept electrons from RE metal atoms and change their surrounding electronic environment due to the electronegativity difference between RE metal and TM elements. Accordingly, the incorporation of RE elements into TM@C-typed catalysts may engineer the local electron structures of TM 3d orbitals, thereby regulating the electron penetration effect and realizing enhanced electrocatalytic performance.…”