文献类型：期刊文献

英文题名：Controlling interfacial properties in supported metal oxide catalysts through metal-organic framework templating

作者：Abney, Carter W.[1];Patterson, Jacob T.[1,4];Gilhula, James C.[1,5];Wang, Li[1,6];Hensley, Dale K.[2];Chen, Jihua[2];Foo, Guo Shiou[1];Wu, Zili[1];Dai, Sheng[1,3]

机构：[1]Oak Ridge Natl Lab, Div Chem Sci, Oak Ridge, TN 37831 USA;[2]Oak Ridge Natl Lab, Ctr Nanophase Mat Sci, Oak Ridge, TN 37831 USA;[3]Univ Tennessee Knoxville, Dept Chem, Knoxville, TN 37916 USA;[4]Allegheny Coll, Meadville, PA 16355 USA;[5]MIT, 77 Massachusetts Ave, Cambridge, MA 02139 USA;[6]East China Univ Sci & Technol, Shanghai 200237, Peoples R China

年份：2017

卷号：5

期号：26

起止页码：13565

外文期刊名：JOURNAL OF MATERIALS CHEMISTRY A

收录：;EI(收录号：20172803925685);WOS:【SCI-EXPANDED(收录号:WOS:000404618200030)】；

基金：CWA was supported by the Oak Ridge National Laboratory Lab-Directed Research & Development Program. JTP and JCG were supported by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Science Undergraduate Laboratory Internship (SULI) program. GSF, ZW and SD are supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Electron microscopy and in situ DRIFTS experiments were conducted at ORNL's Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy.

语种：英文

外文关键词：Catalyst activity - Catalyst supports - Activation energy - Copper oxides - Metals - Organometallics - Crystalline materials - Dispersions - Absorption spectroscopy - X ray absorption - Catalytic oxidation - Cerium oxide

摘要：Precise control over the chemical structure of hard-mattermaterials 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 of 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 degrees 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. Optimization of catalyst materials thus requires precise control over synthesis parameters, such as is demonstrated by this MOF-templating method.