高稳定性无膦配体乙烯氢甲酰化催化体系研究

高活性、高稳定性的无膦配体多相氢甲酰化催化体系研究是催化化学领域的重要课题。本文以乙烯氢甲酰化这一反应为目标，发展出含有不同含氧官能团的活性炭为载体的负载纳米铑催化材料。其中，当以Rh/C-3这一材料为催化剂时，乙烯氢甲酰化反应的转化频率可以达到57889 mol/mol/h。该催化剂可以在固定床反应器上稳定运行2500小时保持活性稳定。表征发现，碳材料表面的内酯基团 (-CO2-)对催化材料的活性和稳定性具有重要的作用。这一研究对高活性、高稳定性的非膦配体多相氢甲酰化催化体系研究具有一定的启示。

Exploration of Stable and Phosphine Ligand Free Heterogeneous Catalyst for Ethylene Hydroformylation

The development of highly active, stable and phosphine ligand free heterogeneous catalyst for hydroformylation reaction remains an open challenge. Herein, we developed highly active, stable and phosphine ligand free heterogeneous catalyst for ethylene hydroformylation reaction by replacing single strongly coordinating phosphine ligand with multiple weakly coordinating oxygen functional groups on the activated carbon surface. Applying of the typical Rh/C-3 catalyst in hydroformylation of ethylene affords unprecedented turnover frequencies (TOFs) up to 57889 per hour. Besides, the Rh/C-3 catalyst exhibited substantially improved stability in the hydroformylation of ethylene in a fixed-bed reactor (at least 2,500 h). For the first time, detailed characterizations revealed that lactone group (-CO2-) on the surface of activated carbon might play a crucial role to gain this catalyst with remarkable activity and stability, which facilitate the homogeneous dispersion and stability of Rh nanoparticles. This work provides a general guidance for the design of highly active, stable and phosphine ligand free heterogeneous catalysts for hydroformylation of olefins.