Abundant (110) Facets on PdCu₃ Alloy Promote Electrochemical Conversion of CO₂ to CO

Abstract

Electrochemical conversion of CO2 to high-value chemical fuels offers a promising strategy for managing the global carbon balance but faces huge challenges due to the lack of effective electrocatalysts. Here, we reported PdCu3 alloy nanoparticles with abundant exposed (110) facets supported on N-doped three-dimensional interconnected carbon frameworks (PdCu3/NC) as an efficient and durable electrocatalyst for electrochemical CO2 reduction to CO. The catalyst exhibits extremely high intrinsic CO2 reduction selectivity for CO production with a Faraday efficiency of nearly 100% at a mild potential of −0.5 V. Moreover, a rechargeable high-performance Zn–CO2 battery with PdCu3/NC as a cathode is developed to deliver a record-high energy efficiency of 99.2% at 0.5 mA cm–2 and rechargeable stability of up to 133 h. Theoretical calculations elucidate that the exposed (110) facet over PdCu3/NC is the active center for CO2 activation and rapid formation of the key *COOH intermediate.

Value‐Added Aqueous Metal‐Redox Bicatalyst Batteries

“…The introduction of a secondary metal into noble metal-based materials to construct a bimetallic alloy can not only reduced the usage of noble metals, but also form a bimetallic effect to enhance the electrocatalytic performance. [39a, [77][78] For example, N-doped 3D interconnected carbon framework-supported PdCu 3 alloy nanoparticles (PdCu 3 /NC) were reported as an efficient and stable electrocatalyst for CO 2 RR to produce CO in an aqueous Zn-CO 2 battery. [77] According to the theoretical calculations, the active site for CO 2 activation and prompt creation of the pivotal *COOH intermediate is the exposed (110) facet on PdCu 3 /NC (Figure 7a).…”

“…[39a, [77][78] For example, N-doped 3D interconnected carbon framework-supported PdCu 3 alloy nanoparticles (PdCu 3 /NC) were reported as an efficient and stable electrocatalyst for CO 2 RR to produce CO in an aqueous Zn-CO 2 battery. [77] According to the theoretical calculations, the active site for CO 2 activation and prompt creation of the pivotal *COOH intermediate is the exposed (110) facet on PdCu 3 /NC (Figure 7a). The PDS has the lowest Gibbs free energy barrier on PdCu 3 -Pd (110), indicating the thermodynamic optimization through constructing PdCu 3 alloy.…”

“…Reproduced with permission. [ 77 ] Copyright 2022, American Chemical Society. b) The possible reaction pathways available, c) calculated free energy diagrams, d) Bader charge analyses of the optimized adsorption structure of *COOH and e) surface strains of s‐PdNi nanoparticles prepared at 1000 and 800°C as simulated by MD for CO 2 electro‐reduction to CO on s‐PdNi‐2.3% (111) surfaces.…”

“…Figure 7. a) The optimized atomic configurations of PdCu 3 -Pd(110) and PdCu 3 -Cu(110) with the adsorption of *CO 2 , *COOH and *CO, and the corresponding Gibbs free energies of these reaction intermediates over Cu(110), Pd(110), PdCu 3 -Cu(110), and PdCu 3 Pd(110). Reproduced with permission [77]. Copyright 2022, American Chemical Society.…”

Nickel-nitrogen-carbon (Ni-N-C) electrocatalysts toward CO2 electroreduction: Advances, optimizations, challenges and prospects

“…FE representing the percentage of the electric quantity consumed to generate the target product in the total electric quantity, reflects the selectivity of catalyst to generate a certain product. The FE value of product can be calculated by the formula [47,48] The closer to 100% FE is, the higher the catalyst selectivity will be. (3) Current density.…”