Chemical Transient Kinetics in Studies of the Fischer–Tropsch Reaction and Beyond

We demonstrate Chemical Transient Kinetics as a powerful tool for investigating catalytic reaction kinetics and mechanisms at atmospheric pressure. Quantitation of transient molecular flows while switching feed gas compositions allows key mechanistic steps of the Fischer–Tropsch reaction to be elucidated. Evidence is presented for a CO insertion mechanism operating under hydrogen-deficient reaction conditions. Consequently, formate/carboxylate-derived intermediates are likely involved in chain lengthening. This also agrees with the occurrence of characteristic time profiles when replacing CO by methyl formate or adding ammonia to a CO/H2 feed.