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Title: Controlling interfacial properties in supported metal oxide catalysts through metal–organic framework templating

Abstract

Precise control over the chemical structure of hard-matter materials is a grand challenge of basic science and a prerequisite for the development of advanced catalyst systems. In this work we report the application of a sacrificial metal-organic framework (MOF) template for the synthesis of a porous supported metal oxide catalyst, demonstrating proof-of-concept for a highly generalizable approach to the preparation new catalyst materials. Application of 2,2’-bipyridine-5,5’-dicarboxylic acid as the organic strut in the Ce MOF precursor results in chelation of Cu 2+ and affords isolation of the metal oxide precursor. Following pyrolysis of the template, homogeneously dispersed CuO nanoparticles are formed in the resulting porous CeO 2 support. By partially substituting non-chelating 1,1’-biphenyl-4,4’-dicarboxylic acid, the Cu 2+ loading and dispersion can be finely tuned, allowing precise control over the CuO/CeO 2 interface in the final catalyst system. Characterization by x-ray diffraction, x-ray absorption fine structure spectroscopy, and in situ IR spectroscopy/mass spectrometry confirm control over interface formation to be a function of template composition, constituting the first report of a MOF template being used to control interfacial properties in a supported metal oxide. Using CO oxidation as a model reaction, the system with the greatest number of interfaces possessed themore » lowest activation energy and better activity under differential conditions, but required higher temperature for catalytic onset and displayed inferior efficiency at 100 °C than systems with higher Cu-loading. This finding is attributable to greater CO adsorption in the more heavily-loaded systems, and indicates catalyst performance for these supported oxide systems to be a function of at least two parameters: size of adsorption site and extent of interface. In conclusion, optimization of catalyst materials thus requires precise control over synthesis parameters, such as is demonstrated by this MOF-templating method.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1394276
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Materials Chemistry. A; Journal Volume: 5; Journal Issue: 26
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Abney, Carter W., Patterson, Jacob T., Gilhula, James C., Wang, Li, Hensley, Dale K., Chen, Jihua, Foo, Guo Shiou, Wu, Zili, and Dai, Sheng. Controlling interfacial properties in supported metal oxide catalysts through metal–organic framework templating. United States: N. p., 2017. Web. doi:10.1039/C7TA03894A.
Abney, Carter W., Patterson, Jacob T., Gilhula, James C., Wang, Li, Hensley, Dale K., Chen, Jihua, Foo, Guo Shiou, Wu, Zili, & Dai, Sheng. Controlling interfacial properties in supported metal oxide catalysts through metal–organic framework templating. United States. doi:10.1039/C7TA03894A.
Abney, Carter W., Patterson, Jacob T., Gilhula, James C., Wang, Li, Hensley, Dale K., Chen, Jihua, Foo, Guo Shiou, Wu, Zili, and Dai, Sheng. Thu . "Controlling interfacial properties in supported metal oxide catalysts through metal–organic framework templating". United States. doi:10.1039/C7TA03894A.
@article{osti_1394276,
title = {Controlling interfacial properties in supported metal oxide catalysts through metal–organic framework templating},
author = {Abney, Carter W. and Patterson, Jacob T. and Gilhula, James C. and Wang, Li and Hensley, Dale K. and Chen, Jihua and Foo, Guo Shiou and Wu, Zili and Dai, Sheng},
abstractNote = {Precise control over the chemical structure of hard-matter materials is a grand challenge of basic science and a prerequisite for the development of advanced catalyst systems. In this work we report the application of a sacrificial metal-organic framework (MOF) template for the synthesis of a porous supported metal oxide catalyst, demonstrating proof-of-concept for a highly generalizable approach to the preparation new catalyst materials. Application of 2,2’-bipyridine-5,5’-dicarboxylic acid as the organic strut in the Ce MOF precursor results in chelation of Cu2+ and affords isolation of the metal oxide precursor. Following pyrolysis of the template, homogeneously dispersed CuO nanoparticles are formed in the resulting porous CeO2 support. By partially substituting non-chelating 1,1’-biphenyl-4,4’-dicarboxylic acid, the Cu2+ loading and dispersion can be finely tuned, allowing precise control over the CuO/CeO2 interface in the final catalyst system. Characterization by x-ray diffraction, x-ray absorption fine structure spectroscopy, and in situ IR spectroscopy/mass spectrometry confirm control over interface formation to be a function of template composition, constituting the first report of a MOF template being used to control interfacial properties in a supported metal oxide. Using CO oxidation as a model reaction, the system with the greatest number of interfaces possessed the lowest activation energy and better activity under differential conditions, but required higher temperature for catalytic onset and displayed inferior efficiency at 100 °C than systems with higher Cu-loading. This finding is attributable to greater CO adsorption in the more heavily-loaded systems, and indicates catalyst performance for these supported oxide systems to be a function of at least two parameters: size of adsorption site and extent of interface. In conclusion, optimization of catalyst materials thus requires precise control over synthesis parameters, such as is demonstrated by this MOF-templating method.},
doi = {10.1039/C7TA03894A},
journal = {Journal of Materials Chemistry. A},
number = 26,
volume = 5,
place = {United States},
year = {Thu Jun 08 00:00:00 EDT 2017},
month = {Thu Jun 08 00:00:00 EDT 2017}
}