Function relay design of single Rh site catalyst and its application in efficient heterogeneous hydroformylation of olefins with CO2

Rational designing the structure of catalysts is an effective but challenging way to optimize catalytic performance for target reaction, which is especially significative in the field of single site catalysts. In this work, a kind of single Rh catalysts for heterogeneous hydroformylation of olefins with CO 2 as substituted carbonyl sources was designed. By simply doping N sites surround Rh P active sites, Rh 1 /POPs-P&N were endowed with better catalytic performance even than homogeneous Rh P complex catalysts. Our study showed that the fine fabricated skeleton structure of Rh 1 /POPs-P&N could endow the N sites with function promotion effect on the adjacent Rh P active sites to different degrees. Consequently, the Rh 1 / m -POP-PPh 3 &PMPD, which formed more HRh(CO) 2 (P) 2 species during the reaction, exhibited the highest yield of aldehydes (conversion of 89 %, selectivity toward aldehydes of 87.1 %, l/b ratio of 13.1), good stability (5 recycling runs without activity loss) and extensive substrate applicability (12 kinds of olefins) in heterogeneous hydroformylation of olefins with CO 2 , surpassing all homogeneous and heterogeneous catalysts that only contain Rh P sites (Table 5). Multiple characterization techniques (EXAFS, STEM, in-situ FTIR etc. ) were employed to get insights into this effective strategy to rationally design efficient single site catalysts.