A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts, Mechanisms and Kinetics

Recent literature on synthesis gas conversion to higher alcohols over Mo-based catalysts is reviewed. Density functional theory calculations show that Mo-CO adsorption is weakened by C, P, or S ligands and this facilitates CO dissociation, either directly on Mo2C, or by H-assisted dissociation on MoS2, Mo2C, and MoP. Consequently, Mo-based catalysts have high hydrocarbon selectivity unless they are promoted with alkali metals and/or Group VIII metals. Promoted MoS2 and MoP have alcohol selectivities of ∼80 C atom % (CO2-free basis) at typical operating conditions (5–8 MPa, H2/CO = 2–1, 537–603 K), whereas on promoted Mo2C, alcohol selectivities are ∼60%. The kinetics of the synthesis gas conversion reactions over Mo-based catalysts have mostly been described by empirical power law models and the alcohol and hydrocarbon product distributions are consistent with a CO insertion mechanism for chain growth.