Epoxidation of cyclohexene with H₂O₂ over efficient water‐tolerant heterogeneous catalysts composed of mono‐substituted phosphotungstic acid on co‐functionalized SBA‐15

Abstract

A series of Keggin‐type heteropolyacid‐based heterogeneous catalysts (Co‐/Fe‐/Cu‐POM‐octyl‐NH3‐SBA‐15) were synthesized via immobilized transition metal mono‐ substituted phosphotungstic acids (Co‐/Fe‐/Cu‐POM) on octyl‐amino‐co‐functionalized mesoporous silica SBA‐15 (octyl‐NH2‐SBA‐15). Characterization results indicated that Co‐/Fe‐/Cu‐POM units were highly dispersed in mesochannels of SBA‐15, and both types of Brønsted and Lewis acid sites existed in Co‐/Fe‐/Cu‐POM‐octyl‐NH3‐SBA‐15 catalysts. Co‐POM‐octyl‐NH3‐SBA‐15 catalyst showed excellent catalytic performance in H2O2‐mediated cyclohexene epoxidation with 83.8% of cyclohexene conversion, 92.8% of cyclohexene oxide selectivity, and 98/2 of epoxidation/allylic oxidation selectivity. The order of catalytic activity was Co‐POM‐octyl‐NH3‐SBA‐15 > Fe‐POM‐octyl‐NH3‐SBA‐15 > Cu‐POM‐octyl‐NH3‐SBA‐15. In order to obtain insights into the role of ‐octyl moieties during catalysis, an octyl‐free catalyst (Co‐POM‐NH3‐SBA‐15) was also synthesized. In comparison with Co‐POM‐NH3‐SBA‐15, Co‐POM‐octyl‐NH3‐SBA‐15 showed enhanced catalytic properties (viz. activity and selectivity) in cyclohexene epoxidation. Strong chemical bonding between ‐NH3+ anchored on the surface of SBA‐15 and heteropolyanions resulted in excellent stability of Co‐POM‐octyl‐NH3‐SBA‐15 catalyst, and it could be reused six times without considerable loss of activity.