Systematic Enumeration of Elementary Reaction Steps in Surface Catalysis.

Abstract

The direct synthesis of complex chemicals from simple precursors (such as syngas) is one of the main objectives of current research in heterogeneous catalysis. To rationally design catalytic materials for this purpose, it is essential to identify the critical elementary reaction steps that ultimately determine a catalyst’s activity and selectivity with respect to a desired product. Unfortunately, the number of potentially relevant elementary steps is in the thousands, even for relatively simple target species like ethanol. The challenge of identifying the critical steps is thus akin to finding the proverbial needle in a haystack. Recently, a model-reduction scheme has been proposed, which tackles this problem by prescreening the barriers of all potential reactions with computationally inexpensive approximations. Although this route appears highly promising, it raises the question of how the starting point of the model-reduction process can be determined. In this contribution, we present a systematic method for enumerating all intermediates and elementary reactions relevant to a chemical process of interest. Using this approach, we construct reaction networks for C,H,O-containing systems consisting of up to four non-hydrogen atoms (more than 1 million reactions). Importantly, the scheme goes beyond simple bond-breaking reactions and allows considering rearrangement and transfer reactions as well. The presented reaction networks thus cover the chemistry of syngas-based processes (and beyond) to an unprecedented scale.