One of the goals of our research is to connect the kinetics and mechanisms of catalytic surface chemistry under ultrahigh vacuum conditions (on ~1 cm2 flat crystals) to that under molecular flow conditions on nanoparticles with known surface terminations. Here, we establish a general methodology for simulating and fitting the kinetics of temperature programmed reactions (TPR) to gain insight about reaction mechanisms and kinetics in complex reaction networks. Simulation and fitting allows the researcher to investigate the possibility of a particular model (consisting of both the reactions and the kinetic parameters ). We find that the key to successful simulation and fitting of a temperature programmed reaction in this context is the objective function. Consideration of the response surfaces of possible objective functions (i.e., the functional forms of the residuals during fitting), in the context of reaction rates going through peaks, has led us to the conclusion that integrated production should be utilized rather than the rate of reaction. This response surface is monotonic, suppresses effects from noise, requires fewer points to capture the response, and can be simulated numerically with small errors. This methodology is applied to simulate and fit the kinetics and mechanism of TPR following adsorption of methanol on a CeO2(111) thin film under ultrahigh vacuum conditions. Mechanistic information based on this study will also be presented. Research supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.

Simulation of temperature programmed reactions: TPR mechanism following adsorption of methanol on CeO2(111)

251st National Meeting (2016)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.