Field Heterogeneities and their Impact on Photocatalysis: Combining optical and kinetic Monte Carlo Simulations on the Nanoscale

Please always quote using this URN: urn:nbn:de:0297-zib-63690
  • Gaining insights into the working principles of photocatalysts on an atomic scale is a challenging task. The obviously high complexity of the reaction mechanism involving photo-excited electrons and holes is one reason. Another complicating aspect is that the electromagnetic field, driving photocatalysis, is not homogeneous on a nanoscale level for particle based catalysts as it is influenced by the particle’s shape and size. We present a simple model, inspired by the CO2 reduction on titania anatase, which addresses the impact of these heterogeneities on the photocatalytic kinetics by combining kinetic Monte Carlo with electromagnetic wave simulations. We find that average activity and especially efficiency might differ significantly between different particles. Moreover, we find sizable variation of the catalytic activity on a single facet of a nanocrystal. Besides this quantitative heterogeneity, the coverage situation in general changes laterally on this facet and we observe a concomitant change of the rate-determining steps. This heterogeneity on all levels of photocatalytic activity is masked in experimental studies, where only the spatially averaged activity can be addressed. Microkinetic models based on experimental findings might therefore not represent the true micro- scopic behavior, and mechanistic conclusion drawn from these need to be handled with care.

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Author:Martin Hammerschmidt, Sandra Döpking, Sven Burger, Sebastian Matera
Document Type:ZIB-Report
MSC-Classification:70-XX MECHANICS OF PARTICLES AND SYSTEMS (For relativistic mechanics, see 83A05 and 83C10; for statistical mechanics, see 82-XX)
78-XX OPTICS, ELECTROMAGNETIC THEORY (For quantum optics, see 81V80)
Date of first Publication:2017/04/19
Series (Serial Number):ZIB-Report (17-20)