Single-atom Catalysis in Space: Computational Exploration of Fischer–Tropsch Reactions in Astrophysical Environments

Context. Gas-phase chemistry at extreme conditions (low densities and temperatures) is difficult, so the presence of interstellar grains is especially important for the synthesis of molecules that cannot form in the gas phase. Interstellar grains are advocated to enhance the encounter rate of the reactive species on their surfaces and to dissipate the energy excess of largely exothermic reactions, but less is known of their role as chemical catalysts that provide low activation energy pathways with enhanced reaction rates. Different materials with catalytic properties are present in interstellar environments, like refractory grains containing space-abundant d-block transition metals. Aims. In this work we report for first time mechanistic insights on the Fischer–Tropsch methanol (CH3OH) synthesis under astrophysical conditions using single-atom Fe-containing silica surfaces as interstellar heterogeneous catalysts. Methods. Quantum chemical calculations considering extended periodic surfaces were carried out in order to search for the stationary points and transitions states to finally construct the reaction potential energy surfaces. Binding energy and kinetic calculations based on the Rice–Ramsperger–Kassel–Marcus (RRKM) scheme were also performed to evaluate the catalytical capacity of the grain and to allocate those reaction processes within the astrochemical framework. Results. Our mechanistic studies demonstrate that astrocatalysis is feasible in astrophysical environments. Thermodynamically the proposed process is largely exergonic, but kinetically it shows energy barriers that would need from an energy input in order to go through. Kinetic calculations also demonstrate the strong temperature dependency of the reaction process as tunnelling is not relevant in the involved energetic barriers. The present results can explain the presence of CH3OH in diverse regions where current models fail to reproduce its observational quantity. Conclusions. The evidence of astrocatalysis opens a completely new spectrum of synthetic routes triggering chemical evolution in space. From the mechanistic point of view the formation of methanol catalysed by a single atom of Fe0 is feasible; however, its dependency on the temperature makes the energetics a key issue in this scenario.