Tuning the framework flexibility and equilibrium of HRh(CO)2P2 active isomers in single-atom Rh/P&N-POPs catalysts for hydroformylation reactions

作者：Ji, Guangjun; Li, Cunyao; Gao, Pan; Jiang, Miao; Ma, Lei; Wang, Guoqing; Hou, Guangjin^*; Yan, Li^*; Ding, Yunjie^*

来源：Chemical Engineering Journal, 2023, 470: 144334.

DOI：10.1016/j.cej.2023.144334

• Single atom catalysts
• Surrounding microenvironment
• Framework flexibility
• Coordination ability
• Hydroformylation

Tuning the microenvironment surrounding single atom metals is an effective but challenging way to regulate the performance of single atom catalysts (SACs). Herein, we prepared a series of P, N-abundant porous organic polymers (P & N-POPs) with diverse framework flexibility and coordination ability to serve as SACs' carriers. The microenvironment (coordination site, coordination number) surrounding Rh and the equilibrium of ea/ee-HRh (CO)2P2 active species were effectively regulated in Rh/P & N-POPs catalysts. Our study shows that the specific active ee-HRh(CO)2(P)2 species confined in the flexible polymeric skeleton endowed the Rh/mPPh3 & PPD-POP with superior activity (TOF = 2000 h-1), selectivity of aldehydes (93.5 %), ratio of linear aldehyde to branched aldehyde (l/b ratio = 15.9), favorable stability (10 recycling runs without activity loss) and extensive substrate applicability (19 kinds of olefins) in hydroformylation reactions. Multiple characterization techniques (EXAFS, STEM, in-situ FTIR etc.) were employed to get insights into this effective strategy to regulate the performance of single atom catalysts (SACs).

• 单位
  催化基础国家重点实验室; 中国科学院大连化学物理研究所