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Title: From Active-Site Models to Real Catalysts: Importance of the Material Gap in the Design of Pd Catalysts for Methane Oxidation

Journal Article · · ChemCatChem
 [1];  [1];  [2]; ORCiD logo [1]
  1. Univ. of Houston Houston TX (United States). Dept. of Chemical and Biomolecular Engineering
  2. Univ. of Houston Houston TX (United States). Dept. of Chemical and Biomolecular Engineering; Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemical Engineering
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Rapid computational screening to aid novel catalyst design has evolved into an important and ubiquitous tool in modern heterogeneous catalysis. A possible shortcoming of this approach, however, is the material gap, that is, simplified computational models used for catalyst screening do not always capture the complexity of real catalytic systems. Here we investigate the importance of the material gap for complete methane oxidation over supported Pd/γ-Al2O3 catalysts using a combination of DFT simulations and temperature-programmed oxidation experiments. The Pd/γ-Al2O3 active site was approximated by four models of increasing complexity, namely Pd(1 0 0), Pd(2 1 1), PdO(1 0 1), and Pd10/γ-Al2O3(1 1 0), and each was also modified with metal promoters to discover reactivity trends. Although the unpromoted Pd model surfaces exhibit different methane activation activities, our DFT results indicate that an experimentally verified performance trend can be predicted for their promoted counterparts irrespective of the active-site representation. We attribute the robustness of the trend predictions in this particular system to localized changes in the electron density during methane activation. Overall, our work supports the commonly practiced active-site model simplifications during computational catalyst screening and provides fundamental insight into the qualitative agreement between theory and experiment for methane oxidation over promoted Pd catalysts.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357
OSTI ID:
1461652
Journal Information:
ChemCatChem, Vol. 9, Issue 9; ISSN 1867-3880
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

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Cited By (2)

Catalytic Oxidation of Methane: Pd and Beyond: Catalytic Oxidation of Methane: Pd and Beyond journal June 2018
Shape selection through epitaxy of supported platinum nanocrystals journal January 2018

Figures / Tables (12)

Figure 1(p. 3)figure Figure 1
Figure 2(p. 3)figure Figure 2
Figure 3(p. 4)figure Figure 3
Table 1(p. 4)table Table 1
Figure 4(p. 5)figure Figure 4
Figure 5(p. 5)figure Figure 5
Figure S1(p. 9)figure Figure S1
Table 1: Part 2(p. 9)table Table 1: Part 2
Table 1: Part 3(p. 9)table Table 1: Part 3
Table S1: Part 1(p. 9)table Table S1: Part 1
Figure S2(p. 14)figure Figure S2
Figure S3(p. 15)figure Figure S3

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY