Ding Yang, Yang Yuxuan, Huo Kefan, Li Yang, Wang Jiasheng, Himeda Yuichiro, Wang Wan-Hui, Bao Ming
School of Chemical Engineering Ocean and Life Sciences, Dalian University of Technology, Liaodongwan New District, Panjin, China.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Ganjingzi District, Dalian, China.
Dalton Trans. 2024 Sep 10;53(35):14839-14847. doi: 10.1039/d4dt01923g.
The catalytic hydrogenation of carbon dioxide to formate is of great interest due to its significant role in CO utilization. In this study, a novel heterogeneous Ru(III) catalyst was prepared by immobilizing RuCl on a porous organic polymer (POP) obtained from 1,4-phthalaldehyde (PTA) and 4,4'-biphenyldicarboxaldehyde (BPDA) with melamine. A copolymerization strategy utilizing monomers of varying lengths was employed to prepare the POP-supported Ru catalyst with adjustable porosity. The optimization of the framework porosity resulted in enhanced CO affinity, accelerated mass transfer, and a remarkable enhancement in catalytic activity. A high turnover number (TON) of 2458 was achieved for the CO hydrogenation to formate in 2 h with catalyst Cat-3 under 3 MPa (CO/H = 1 : 1) at 120 °C in 1 M EtN aqueous solution. Moreover, the Cat-3 demonstrated good recyclability and was able to be reused for five consecutive runs, resulting in a high total TON of 9971.
由于二氧化碳催化加氢生成甲酸盐在一氧化碳利用中具有重要作用，因此备受关注。在本研究中，通过将RuCl固定在由1,4-苯二甲醛（PTA）、4,4'-联苯二甲醛（BPDA）与三聚氰胺制得的多孔有机聚合物（POP）上，制备了一种新型多相Ru(III)催化剂。采用利用不同长度单体的共聚策略制备了具有可调孔隙率的POP负载Ru催化剂。骨架孔隙率的优化导致一氧化碳亲和力增强、传质加速以及催化活性显著提高。在120℃、3MPa（CO/H = 1∶1）的条件下，于1M乙胺水溶液中，催化剂Cat-3在2小时内实现了二氧化碳加氢生成甲酸盐的高周转数（TON）为2458。此外，Cat-3表现出良好的可回收性，能够连续重复使用五次，总TON高达9971。
