“Two Ships in a Bottle” Design for Zn–Ag–O Catalyst Enabling Selective and Long-Lasting CO₂ Electroreduction

Abstract

Electrochemical CO 2 reduction (CO 2 RR) using renewable energy sources represents a sustainable means of producing carbon-neutral fuels. Unfortunately, low energy efficiency, poor product selectivity, and rapid deactivation are among the most intractable challenges of CO 2 RR electrocatalysts. Here, we strategically propose a "two ships in a bottle" design for ternary Zn−Ag−O catalysts, where ZnO and Ag phases are twinned to constitute an individual ultrafine nanoparticle impregnated inside nanopores of an ultrahigh-surface-area carbon matrix. Bimetallic electron configurations are modulated by constructing a Zn−Ag−O interface, where the electron density reconfiguration arising from electron delocalization enhances the stabilization of the *COOH intermediate favorable for CO production, while promoting CO selectivity and suppressing HCOOH generation by altering the rate-limiting step toward a high thermodynamic barrier for forming HCOO*. Moreover, the pore-constriction mechanism restricts the bimetallic particles to nanosized dimensions with abundant Zn−Ag−O heterointerfaces and exposed active sites, meanwhile prohibiting detachment and agglomeration of nanoparticles during CO 2 RR for enhanced stability. The designed catalysts realize 60.9% energy efficiency and 94.1 ± 4.0% Faradaic efficiency toward CO, together with a remarkable stability over 6 days. Beyond providing a high-performance CO 2 RR electrocatalyst, this work presents a promising catalyst-design strategy for efficient energy conversion.

In Operando Identification of In Situ Formed Metalloid Zincδ+ Active Sites for Highly Efficient Electrocatalyzed Carbon Dioxide Reduction

“…In Figure 3d, Zn 2 P 2 O 7 exhibits high EE of 52.3 %, 58.0 %, and 45.0 % at the j of −50, −100, and −150 mA cm −2 , respectively, with optimal FE CO of 93.9 % at the j of −100 mA cm −2 (see details in Supporting Information). This high EE is also comparable to the classic precious and nonprecious electrocatalysts at similar current densities, such as Ag, Au, and CoPc‐based materials (Figure 3e and Table S2) [4, 9b, 27] . The long‐term stability test of Zn 2 P 2 O 7 at the j of −100 mA cm −2 was also implemented in the MEA configuration (Figure 3f).…”

Design of Quasi‐MOF Nanospheres as a Dynamic Electrocatalyst toward Accelerated Sulfur Reduction Reaction for High‐Performance Lithium–Sulfur Batteries

“…The deligandation of the quasi‐MOF triggers the electron transfer and rearranges the electron distribution during SRR, potentially allowing Zn atoms to release more electrons from the d orbital in addition to the two electrons in the s orbital, which could result in electron density depletion around Zn nodes to enhance the catalytic activity of active sites for accelerated SRR. [ 32 ] In addition, the bond length and coordination number of quasi‐MOF NS switched back to its original state at stage 4, corresponding to the religandation of the well‐retained quasi‐MOF structure, which indicates a dynamic and reversible structure evolution over electrochemical process. Therefore, the evolved active sites during discharge process are conducive to strengthen LiPs interaction and reduce the activation energy for SRR, rendering greatly improved Li 2 S transformation.…”

Engineering Electrochemical Surface for Efficient Carbon Dioxide Upgrade

“…Ternary Zn-Ag-O catalysts with a design strategy of "two ships in a bottle," where ZnO and Ag phases are impregnated inside nanopores of carbon matrix, enhances the stabilization of the *COOH intermediate favorable for CO production. [88] a) The Sn-based materials are not listed in this table, which is listed in Table 2; b) Maximum current density at the potential where the maximum FE is obtained. Most of the catalysts were tested in H-cell; c) Maximum FE; d) Cathodic energy efficiency, [40b] because most measurements were tests in a three-electrode cell; e) Potential where the maximum FE is achieved.…”

“…Ternary Zn–Ag–O catalysts with a design strategy of “two ships in a bottle,” where ZnO and Ag phases are impregnated inside nanopores of carbon matrix, enhances the stabilization of the *COOH intermediate favorable for CO production. [ 88 ]…”