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This content will become publicly available on February 16, 2017

Title: Local Platinum Environments in a Solid Analogue of the Molecular Periana Catalyst

Combining advantages of homogeneous and heterogeneous catalysis by incorporating active species on a solid support is often an effective strategy for improving overall catalyst performance, although the influences of the support are generally challenging to establish, especially at a molecular level. In this paper, we report the local compositions, and structures of platinum species incorporated into covalent triazine framework (Pt-CTF) materials, a solid analogue of the molecular Periana catalyst, Pt(bpym)Cl2, both of which are active for the selective oxidation of methane in the presence of concentrated sulfuric acid. By using a combination of solid-state 195Pt nuclear magnetic resonance (NMR) spectroscopy, aberration-corrected scanning transmission electron microscopy (AC-STEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), important similarities and differences are observed between the Pt-CTF and Periana catalysts, which are likely related to their respective macroscopic reaction properties. In particular, wide-line solid-state 195Pt NMR spectra enable direct measurement, identification, and quantification of distinct platinum species in as-synthesized and used Pt-CTF catalysts. The results indicate that locally ordered and disordered Pt sites are present in as-synthesized Pt-CTF, with the former being similar to one of the two crystallographically distinct Pt sites in crystalline Pt(bpym)Cl2. A distribution of relatively disordered Pt moieties ismore » also present in the used catalyst, among which are the principal active sites. Similarly XAS shows good agreement between the measured data of Pt-CTF and a theoretical model based on Pt(bpym)Cl2. Analyses of the absorption spectra of Pt-CTF used for methane oxidation suggests ligand exchange, as predicted for the molecular catalyst. XPS analyses of Pt(bpym)Cl2, Pt-CTF, as well as the unmodified ligands, further corroborate platinum coordination by pyridinic N atoms. Aberration-corrected high-angle annular dark-field STEM proves that Pt atoms are distributed within Pt-CTF before and after catalysis. Finally, the overall results establish the close similarities of Pt-CTF and the molecular Periana catalyst Pt(bpym)Cl2, along with differences that account for their respective properties.« less
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [4] ;  [4] ;  [5] ;  [1] ;  [4] ;  [3] ;  [6] ;  [2] ;  [1]
  1. Max-Planck-Institut fur Kohlenforschung, Mulheim an der Ruhr (Germany)
  2. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemical Engineering
  3. Max Planck Inst. for Solid State Research, Stuttgart (Germany)
  4. Max Planck Inst. of Colloids and Interfaces, Potsdam (Germany)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. Max-Planck-Institut fur Kohlenforschung, Mulheim an der Ruhr (Germany); RWTH Aachen Univ. (Germany)
Publication Date:
OSTI Identifier:
1261298
Grant/Contract Number:
AC05-00OR22725; MSN-CHE-1059108; DMR-1121053
Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 4; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC); National Science Foundation (NSF) (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY atomic dispersion; methane oxidation; Periana catalyst; solid analogue vs molecular catalyst; solid-state 195Pt NMR