Robust and recyclable single-atom and cluster-like Cu-based catalysts for methanol oxidative carbonylation to dimethyl carbonate

Li, Wenjie, Gao, Shanlin, Lai, Chunbo, Li, Xinling, Xiao, Wanjing, Wang, Xinyu, Lin, Huibo, Zhang, Yang, Liu, Haijun, Yang, Gan, Xu, Chenghua, Higgins, Luke J. R., Beale, Andrew M., Pera Titus, Marc and Deng, Zhiyong 2025. Robust and recyclable single-atom and cluster-like Cu-based catalysts for methanol oxidative carbonylation to dimethyl carbonate. ACS Sustainable Chemistry & Engineering 10.1021/acssuschemeng.5c04760

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Abstract

Methanol oxidative carbonylation is a highly desired reaction for the industrial production of dimethyl carbonate (DMC), offering a more sustainable alternative to the conventional, environmentally unfriendly phosgene-methanol process. Although supported copper nanoparticle catalysts can facilitate this reaction, their rapid deactivation due to Cu sintering and overoxidation limits their industrial applicability. In this study, we present robust and reusable single-atoms and cluster-like Cu catalysts (catalyst loading up to 6.5 wt %) supported on N-doped carbon, synthesized via pyrolysis of Cu-doped ZIF-8 precursors. The formation and stability of highly dispersed Cu species during the reaction was confirmed using a comprehensive suite of characterization techniques, including X-ray diffraction (XRD), Fourier transform infrared (FT-IR), high-resolution transmission electron microscopy (HR-TEM), aberration corrected high angle annular dark field-scanning transmission electron microscopy (AC-HAADF-STEM), X-ray photoelectron spectroscopy (XPS), NH3-TPD, H2-TPR, and X-ray absorption spectroscopy (XAS). This unique copper architecture achieved an exceptional DMC selectivity of 99.4% and a space-time yield of 3249 mg DMC·g–1·h–1 (TOFDMC,B = 34.4 h–1; TOFDMC,S = 294 h–1) at 120 °C for 2 h. The catalysts demonstrated excellent reusability, maintaining their performance over at least seven consecutive runs without deactivation. Postreaction analysis of the spent catalyst after seven runs revealed that Cu was largely free of leaching, sintering, and overoxidation.

Item Type:	Article
Date Type:	Publication
Status:	In Press
Schools:	Schools > Chemistry
Publisher:	American Chemical Society (ACS)
ISSN:	2168-0485
Date of First Compliant Deposit:	21 July 2025
Date of Acceptance:	1 July 2025
Last Modified:	21 Jul 2025 13:00
URI:	https://orca.cardiff.ac.uk/id/eprint/179929

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