Molecular-scale CO spillover on a dual-site electrocatalyst enhances methanol production from CO2 reduction

• Published in: Nature nanotechnology Vol. 20; no. 4; pp. 515 - 522
• Main Authors: Li, Jing, Zhu, Quansong, Chang, Alvin, Cheon, Seonjeong, Gao, Yuanzuo, Shang, Bo, Li, Huan, Rooney, Conor L., Ren, Longtao, Jiang, Zhan, Liang, Yongye, Feng, Zhenxing, Yang, Shize, Robert Baker, L., Wang, Hailiang
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.04.2025; Nature Publishing Group
• Subjects: 639/301/357; 639/4077/4057; 639/638/161; Carbon dioxide; Catalysts; Chemistry and Materials Science; Cobalt; Efficiency; Electrocatalysts; Materials Science; Methanol; Multi wall carbon nanotubes; Nanotechnology; Nanotechnology and Microengineering; Nanotubes; Spectroscopy; Spectrum analysis; Stability
• DOI: 10.1038/s41565-025-01866-8
• ISSN: 1748-3387; 1748-3395

Cobalt phthalocyanine (CoPc) is recognized for catalysing electrochemical CO 2 reduction into methanol at high Faradaic efficiency but is subject to deactivation. Cobalt tetraaminophthalocyanine (CoPc-NH 2 ) shows improved stability, but its methanol Faradaic efficiency is below 30%. This study addresses these limitations in selectivity, reactivity and stability by rationally designing a dual-site cascade catalyst. Here we quantify the local concentration of CO, a key intermediate of the reaction, near a working CoPc-NH 2 catalyst and show that co-loading nickel tetramethoxyphthalocyanine (NiPc-OCH 3 ) with CoPc-NH 2 on multiwalled carbon nanotubes increases the generation and local concentration of CO. This dual-site cascade catalyst exhibits substantially higher performance than the original single-site CoPc-NH 2 /carbon nanotube catalyst, reaching a partial current density of 150 mA cm −2 and a Faradaic efficiency of 50% for methanol production. Kinetic analysis and in situ sum-frequency generation vibrational spectroscopy attribute this notable performance improvement to molecular-scale CO spillover from NiPc-OCH 3 sites to methanol-active CoPc-NH 2 sites. A dual-site electrocatalyst is developed to greatly enhance methanol production from CO 2 reduction via a cascade process, taking advantage of molecular-scale CO spillover.