Journal of Catalysis, Vol.377, 400-408, 2019
Insight into the stability of binuclear Ir-La catalysts for efficient heterogeneous methanol carbonylation
Heterogeneous single-site catalysts are ideal alternatives to their homogenous counterparts. Methanol carbonylation to produce acetic acid is a typical homogeneous catalytic process. Here, we investigate the stability of a heterogeneous single-site catalyst for vapor methanol carbonylation constituted by an lr-La binuclear complex on activated carbon (lr(1)-La-1/AC). Through the structure of the binuclear complex on the lr(1)-La-1/AC catalyst, the La promoter could protect the Ir+. species from reduction by H-2, favor the single-atom dispersion of Ir metal, and also increase the reaction rate of methanol carbonylation. Furthermore, the apparent activation energy of the lr(1)-La-1/AC catalyst was 12.2 kJ/mol lower than that of the lr(1)/AC catalyst. A density functional theory calculation showed that reductive elimination of acetyl iodide was the rate-determining step for the lr(1)/AC catalyst, leading to a severe carbon deposition problem, while CO migration insertion was believed to be the rate-determining step on the lr(1)-La-1/AC catalyst, which can reduce the carbon deposition to a great extent. (C) 2019 Elsevier Inc. All rights reserved.
Keywords:Heterogeneous single-site catalyst;Binuclear Ir-La complex;Methanol carbonylation;Stability;Density functional theory