Clarifying mechanisms and kinetics of programmable catalysis

Programmable catalysis-the purposeful oscillation of catalytic potential energy surfaces (PES)-has emerged as a promising method for the acceleration of catalyzed reaction rates. However, theoretical study of programmable catalysis has been limited by onerous computational demands of integrating the stiff differential equations that describe periodic cycling between PESs. This work details methods that reduce the computational cost of finding the limit cycle by ≳10⁸×. These methods produce closed-form analytical solutions for didactic case studies, examination of which provides physical insights of programmable catalysis mechanisms. Generalization of these analyses to more complex reaction networks, including CO oxidation on Pt (111) surfaces, exposes the key catalyst properties required to achieve enhanced rates and conversions via one of two programmable catalysis mechanisms: quasi-static (high frequency) and stepwise (intermediate frequency). Analytical description of each mechanism is critical in understanding the consequences of the Sabatier principle on achievable rate enhancement through programmed catalysis.