Understanding FTS selectivity: the crucial role of surface hydrogen

Abstract

Monomeric forms of carbon play a central role in the synthesis of long chain hydrocarbons via the Fischer–Tropsch synthesis (FTS). We explored the chemistry of C₁H_xad species on the close-packed surface of cobalt. Our findings on this simple model catalyst highlight the important role of surface hydrogen and vacant sites for product selectivity. We furthermore find that CO_ad affects hydrogen in multiple ways. It limits the adsorption capacity for H_ad, lowers its adsorption energy and inhibits dissociative H₂ adsorption. We discuss how these findings, extrapolated to pressures and temperatures used in applied FTS, can provide insights into the correlation between partial pressure of reactants and product selectivity. By combining the C₁H_x stability differences found in the present work with literature reports of the reactivity of C₁H_x species measured by steady state isotope transient kinetic analysis, we aim to shed light on the nature of the atomic carbon reservoir found in these studies.