LAUSR

We report on the formation of chain‐lengthened hydrocarbons through hydrogenation of methyl formate over a Co/MgO heterogeneous catalyst and provide time‐dependent product spectra through Chemical Transient Kinetics. The results bear striking similarities with the CO hydrogenation over the same catalyst under essentially identical reaction conditions. Accordingly, hydrocarbons are mainly composed of straight paraffins besides smaller amounts of iso‐products and olefins. The kinetic analysis demonstrates methyl formate to undergo dissociative chemisorption and reaction rather than hydrogenation as a molecule. The initiation of C2+ hydrocarbon chain lengthening occurs time‐delayed and is correlated with gaseous CO and CO2 formation. Straight paraffins appear sequentially with about 1…2 s time increments between successive homologues. The chain growth follows polymerization‐type kinetics according to Anderson‐Schulz‐Flory, similar to the Fischer‐Tropsch reaction of CO hydrogenation.