Size‐Dependent Copper Nanoparticles Supported on Carbon Nanotubes with Balanced Cu+ and Cu0 Dual Sites for the Selective Hydrogenation of Ethylene Carbonate

• Published in: Chemistry : a European journal 2024-12, Vol.30 (71), p.e202402699-n/a
• Main Authors: Li, Huabo, Ji, Deyuan, Zhang, Yanfei, Cui, Yuanyuan, Cheng, Yinfeng, Wang, Songlin, Dai, Wei‐Lin
• Format: Article
• Language: English
• Subjects: Carbon cycle; Carbon dioxide; Carbon nanotube; Carbon nanotubes; Catalysts; Catalytic activity; Catalytic converters; Copper; Density functional theory; Ethylene carbonate; Ethylene glycol; Functional groups; Hydrogenation; Inert atmospheres; Methanol; Nanoparticles; Nanotechnology; Nanotubes; Physicochemical properties; Silica; Structure-function relationships; Synergetic effect
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202402699

Cyclic carbonate hydrogenation offers an alternative for the efficient indirect CO2 utilization. In this study, a series of carbon nanotubes (CNTs) supported xCu/CNTs catalysts with different Cu loadings were fabricated using a convenient impregnation method, and exhibited excellent catalytic activity for the hydrogenation of ethylene carbonate to methanol and ethylene glycol. The structural and physicochemical properties revealed that acid treatment of CNTs resulted in plentiful oxygen‐containing functional groups, providing sufficient anchoring sites for copper species. The calcination process conducted under an inert atmosphere resulted in the formation of ternary CuO, Cu2O, and Cu composites, enhancing the metal‐support interaction and facilitating the formation of balanced Cu0 and Cu+ dual sites as well as high active surface area after reduction. Contributed to the synergetic effect of balanced Cu+ and Cu0 species proved by density functional theory calculation and the electron‐rich CNTs surface, the 40Cu/CNTs catalyst achieved strengthened catalytic performance with methanol yield of 83 %, ethylene glycol yield of 99 % at ethylene carbonate conversion of >99 %, and 150 h of long‐term running stability. Consequently, CNTs supported Cu serve as efficient non‐silica based catalyst for ester hydrogenation. Cu nanoparticles supported on surface modified carbon nanotubes with defects and oxygen‐containing functional groups catalysts were prepared via a convenient impregnation method. The 40Cu/CNTs catalysts revealed remarkable methanol and ethylene glycol yields for the vapor‐phase hydrogenation of ethylene carbonate. The synergistic effect of Cu0 and Cu+ dual sites contributed to the satisfactory catalytic performance of ethylene carbonate hydrogenation.