A highly efficient Cu/ZnOx/ZrO2 catalyst for selective CO2 hydrogenation to methanol

• Published in: Journal of catalysis 2022-10, Vol.414, p.236-244
• Main Authors: Xu, Yanan, Gao, Zhihong, Peng, Li, Liu, Kang, Yang, Yang, Qiu, Rongxing, Yang, Shuliang, Wu, Chenhao, Jiang, Jiaheng, Wang, Yanliang, Tan, Wenjun, Wang, Hongtao, Li, Jun
• Format: Article
• Language: English
• Subjects: CO2 hydrogenation; Cu/ZnOx/ZrO2; Metal-organic frameworks; Methanol; Thermal catalysis
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2022.09.011

[Display omitted] •A facile co-precipitation method is used to prepare catalysts with particles confined in cheap MOF. After calcination, more catalytic active sites could be exposed, which greatly improves the performance of the catalyst.•Compared with other methods, the co-precipitation method is simple, low-cost, and can better control the metal loading. At the same time, the problem of easy agglomeration of Cu nanoparticles and easy phase separation of Cu and ZnO at high temperature could be alleviated greatly.•The as-prepared Cu/ZnOx/ZrO2 catalyst shows much better performance for CO2 hydrogenation to methanol than the commercialized catalyst and catalyst prepared by double solvents method. The ternary Cu/ZnO/Al2O3 catalyst is usually employed for producing methanol from syngas (CO/CO2/H2) or from CO2 hydrogenation in industry. However, this catalyst often suffers from the aggregation of Cu nanoparticles and the phase separation of Cu and ZnO. In this work, a highly efficient and stable catalyst (Cu/ZnOx/ZrO2) for CO2 hydrogenation to methanol is prepared via co-precipitation method with UiO-66 as structural template. Cu/Zn is effectively combined and encapsulated in the channels of UiO-66, which avoids the aggregation of metal particles. The ZrO2 support derived from UiO-66 enhances the interaction between the support and Cu/Zn, and thus improves the catalytic performance significantly. This catalyst shows a high space–time yield of 216.7 g(MeOH)·kg(cat)−1·h−1 at 260 °C, 4 MPa and GHSV = 12000 h−1. Furthermore, the catalyst shows good stability over a period of 50 h on stream. The performance of Cu/ZnOx/ZrO2 is much better than that of commercial catalysts and most of catalysts previously reported.