Selective Catalytic Oxidation of Alcohols over Supported Metal Nanoparticles and Atomically-Dispersed Metal Cations

2018 Spring Symposium

Robert J. Davis, Depart­ment of Chem­i­cal Engi­neer­ing, Uni­ver­si­ty of Vir­ginia, Char­lottesville, VA, USA

Abstract — Selec­tive oxi­da­tion of alco­hols to car­bonyl com­pounds is an impor­tant reac­tion in organ­ic syn­the­sis and will like­ly play a sig­nif­i­cant role in the devel­op­ment of val­ue-added chem­i­cals from bio­mass. The indus­tri­al appli­ca­tion of a pre­cious met­al cat­a­lyst such as Pt, how­ev­er, can be hin­dered by deac­ti­va­tion and high price. We have there­fore explored the mode of deac­ti­va­tion dur­ing alco­hol oxi­da­tion on Pt by in-situ spec­troscopy and stud­ied the role of var­i­ous pro­mot­ers on cat­a­lyst per­for­mance. Results con­firm that slow decar­bony­la­tion of prod­uct alde­hyde deposit­ed unsat­u­rat­ed hydro­car­bon on the sur­face that blocked access to the active sites. Addi­tion of Bi as a pro­mot­er did not pre­vent the decar­bony­la­tion side reac­tion, but instead enhanced the acti­va­tion of dioxy­gen dur­ing the cat­alyt­ic cycle. In an effort to avoid the use of pre­cious met­als alto­geth­er, the oxi­da­tion of alco­hols over atom­i­cal­ly-dis­persed, non-pre­cious met­al cations (Fe, Cu, and Co) locat­ed in a nitro­gen-doped car­bon matrix was demon­strat­ed. Exten­sive char­ac­ter­i­za­tion of these non-pre­cious met­al cat­a­lysts revealed impor­tant insights into the oxi­da­tion mech­a­nism and sta­bil­i­ty of this new class of atom­i­cal­ly-dis­persed met­al cat­a­lyst.