Systematic Enumeration of Elementary Reaction Steps in Surface Catalysis

Area of Science:

• Heterogeneous catalysis
• Computational chemistry
• Chemical reaction engineering

Background:

• Direct synthesis of complex chemicals from simple precursors (e.g., syngas) is a major goal in heterogeneous catalysis.
• Identifying critical elementary reaction steps is crucial for designing efficient catalysts but is challenging due to the vast number of possibilities.

Purpose of the Study:

• To present a systematic method for enumerating all relevant intermediates and elementary reactions for a given chemical process.
• To address the challenge of determining the starting point for model-reduction schemes in catalysis research.

Main Methods:

• Developed a systematic enumeration scheme for chemical intermediates and elementary reactions.
• Constructed large-scale reaction networks, including bond-breaking, rearrangement, and transfer reactions.
• Applied the method to C,H,O-containing systems with up to four non-hydrogen atoms.

Main Results:

• Generated reaction networks comprising over 1 million reactions.
• The scheme comprehensively covers elementary steps beyond simple bond breaking.
• Successfully enumerated reactions relevant to syngas-based processes and beyond.

Conclusions:

• The presented systematic method enables the construction of comprehensive reaction networks for complex chemical systems.
• This work provides a foundation for rationally designing catalytic materials by identifying critical reaction pathways.
• The scale of the generated networks offers unprecedented coverage for studying syngas conversion and related catalytic processes.