Promoting CO₂ Electroreduction Kinetics on Atomically Dispersed Monovalent Zn^I Sites by Rationally Engineering Proton‐Feeding Centers

Abstract

Electrocatalytic reduction of CO 2 (CO 2 RR) to valueadded chemicals is of great significance for CO 2 utilization, however the CO 2 RR process involving multi-electron and proton transfer is greatly limited by poor selectivity and low yield. Herein, We have developed an atomically dispersed monovalent zinc catalyst anchored on nitrogenated carbon nanosheets (Zn/NC NSs). Benefiting from the unique coordination environment and atomic dispersion, the Zn/NC NSs exhibit as uperior CO 2 RR performance,f eaturing ah igh current density up to 50 mA cm À2 with an outstanding CO Faradaic efficiency of % 95 %. The center Zn I atom coordinated with three Natoms and one Natom that bridges over two adjacent graphitic edges (Zn-N 3+1 )isidentified as the catalytically active site.Experimental results reveal that the twisted Zn-N 3+1 structure accelerates CO 2 activation and protonation in the rate-determining step of *CO 2 to *COOH, while theoretical calculations elucidate that atomically dispersed Zn-N 3+1 moieties decrease the potential barriers for intermediate COOH* formation, promoting the proton-coupled CO 2 RR kinetics and boosting the overall catalytic performance.

Heterogeneous Electrocatalysts for Metal–CO2 Batteries and CO2 Electrolysis

“…(d) Diagram for the synthesis of Zn/NC NSs. Adapted with permission from ref . Copyright 2022, Wiley-VCH.…”

“…The well-defined structure also exhibits advantages for improving the electrocatalytic performance of M–N–C. The novel Zn–N 4 /C electrocatalyst with a twisted structure is obtained by a molten salt-assisted solid-phase method; the process is shown in Figure d . The Zn–N 3+1 active site is constructed by forming the coordination between a Zn I atom and four N atoms, which shows an improved ability in comparison to other dispersed Zn–N–C electrocatalysts reported so far.…”

“…The novel Zn−N 4 /C electrocatalyst with a twisted structure is obtained by a molten salt-assisted solid-phase method; the process is shown in Figure 4d. 113 The Zn−N 3+1 active site is constructed by forming the coordination between a Zn I atom and four N atoms, which shows an improved ability in comparison to other dispersed Zn−N−C electrocatalysts reported so far. The electrochemical results demonstrate the Zn−N 3+1 active site supported by the carbon nanosheet can enhance dissociation of H 2 O and facilitate protonation of *CO 2 ; this is reflected in a lower potential barrier for formation of the *COOH intermediate.…”

“…Overview of different types of electrocatalysts for metal–CO 2 batteries and CO 2 electrolysis. The inserted graphics are adapted with permission from ref , American Chemical Society 2021; ref , Wiley 2019; ref , Elsevier 2020; ref , Wiley 2022; ref , American Chemical Society 2019; ref , Wiley 2017; ref , American Chemical Society 2022; ref , Wiley 2019; ref , Wiley 2021; ref , Wiley 2021; ref , Wiley 2022; ref , American Chemical Society 2022; ref , Wiley 2021; ref , Wiley 2020; ref , Wiley 2022; ref , Wiley 2019; ref , The Royal Society of Chemistry 2018; ref , Wiley 2019.…”

Boosting the Ni–Zn interplay via O/N dual coordination for high‐efficiency CO2 electroreduction

“…7,[19][20][21][22][23] More importantly, their surface properties can be extensively tuned by mediating the coordination microenvironment of atomic metal species. [24][25][26][27][28][29] It is well known that the atomic non-precious transition metals (TMs) in a TM-N 4 coordination structure show reasonably high activity and Faraday efficiency (FE) in converting CO 2 into CO, 30 as demonstrated by various nonprecious TMs including Ni, 31 Co, 32 Fe, 25 Mn, 33 Cu, 34,35 Zn, 36 and so forth. Furthermore, the activity and selectivity of the carbon dioxide reduction reaction (CO 2 RR) can be tuned by establishing asymmetric or nonplanar coordination structures.…”