Synergistic engineering of heteronuclear Ni-Ag dual-atom catalysts for high-efficiency CO2 electroreduction with nearly 100% CO selectivity

Guo, Zeyu; Zhu, Huiwen; Yang, Gang; Wu, Angjian; Chen, Quhan; Yan, Zijun; Loon Fow, Kam; Do, Hainam; Hirst, Jonathan D.; Wu, Tao; Xu, Mengxia

Abstract

Single-atom catalysts (SACs) have emerged as attractive materials for the electrocatalytic carbon dioxide reduction (ECO2R). Dual-atom catalysts (DACs), an extension of SACs, exhibit more compelling functionalities due to the synergistic effects between adjacent metal atoms. However, the rational design, clear coordination mode, and in-depth understanding of heteronuclear dual-atom synergistic mechanisms remain elusive. Herein, a heteronuclear Ni-Ag dual-atom catalyst loaded on defective nitrogen-rich porous carbon, denoted as Ni-Ag/PC-N, was synthesized using cascade pyrolysis. The configuration of Ni-Ag dual-atom sites is confirmed as N3-Ni-Ag-N3. Ni-Ag/PC-N demonstrates a remarkable CO Faradaic efficiency (FECO) exceeding 90% over a broad range of applied potentials, i.e., from −0.7 to −1.3V versus reversible hydrogen electrode (RHE). The peak FECO of 99.2% is observed at −0.8V (vs. RHE). Tafel analysis reveals that the rate-determining step of ECO2R-to-CO is the formation of the *COOH intermediate, and Ni-Ag/PC-N exhibits optimal electrokinetics. In situ FTIR and in situ Raman spectra indicate accelerated production of *COOH intermediates during the ECO2R-to-CO process. Density functional theory (DFT) calculations demonstrate that the coordinated Ni atom lowers the energy barrier of *COOH intermediates formation over the Ni-Ag/PC-N surface, while the adjacent Ag atom mitigates the catalyst poisoning caused by the strong *CO affinity on the Ni atomic site.

Citation

Guo, Z., Zhu, H., Yang, G., Wu, A., Chen, Q., Yan, Z., …Xu, M. (2023). Synergistic engineering of heteronuclear Ni-Ag dual-atom catalysts for high-efficiency CO2 electroreduction with nearly 100% CO selectivity. Chemical Engineering Journal, 476, Article 146556. https://doi.org/10.1016/j.cej.2023.146556

• Journal Article Type: Article
• Acceptance Date: Oct 7, 2023
• Online Publication Date: Oct 12, 2023
• Publication Date: Nov 15, 2023
• Deposit Date: Oct 15, 2023
• Publicly Available Date: Oct 19, 2023
• Journal: Chemical Engineering Journal
• Print ISSN: 1385-8947
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 476
• Article Number: 146556
• DOI: https://doi.org/10.1016/j.cej.2023.146556
• Keywords: CO2 electroreduction reaction; Electron transfer; Dual-atom catalyst; In situ spectroscopy; Density functional theory
• Public URL: https://nottingham-repository.worktribe.com/output/25958234
• Publisher URL: https://www.sciencedirect.com/science/article/pii/S1385894723052877?via%3Dihub