Co鈥揅o2C and Co鈥揅o2C/AC Catalysts for Hydroformylation of 1-Hexene under Low Pressure: Experimental and Theoretical Studies

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• 作者：Wenda Dong ; Jinxun Liu ; Hejun Zhu ; Yunjie Ding ; Yanpeng Pei ; Jia Liu ; Hong Du ; Miao Jiang ; Tao Liu ; Haiyan Su ; Weixue Li
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：August 21, 2014
• 年：2014
• 卷：118
• 期：33
• 页码：19114-19122
• 全文大小：494K
• ISSN：1932-7455

文摘

Unsupported Co鈥揅o₂C catalyst and active carbon supported Co鈥揅o₂C (Co鈥揅o₂C/AC) catalysts were prepared and have been first proven to be highly active for 1-hexene hydroformylation under low pressure (P = 3.0 MPa and T = 453 K). It is found that the catalytic performances over the Co鈥揅o₂C and Co鈥揅o₂C/AC catalysts were strongly dependent on the ratio of Co₂C to Co. Highly catalytic performances were achieved with the XRD intensity ratio of Co₂C to Co ranging from 0.7 to 1.2. Co鈥揅o₂C/AC catalyst with carburization for 20 h has a highly catalytic stability for 1-hexene hydroformylation with a time stream of 140 h, indicating that no dissolved cobalt carbonyl species were formed and thus led to no cobalt elusion during hydroformylation under reaction conditions. Density functional theory (DFT) calculations have been conducted to understand the nature of the catalytic performance. We found that the interface between Co and Co₂C plays a significant role in ethylene hydroformylation. Metallic Co sites are used for olefin adsorption and activation to form surface carbonaceous species, while Co₂C sites, for CO molecular adsorption, activation, and insertion. Our results have provided a strategy for designing highly active bifunctional non-noble metal catalysts.