期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 8, 页码 2739-2748出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b12688
关键词
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资金
- U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences [DE-SC-0012702]
- NSF through MRSEC program
- NSF through ERC program
- NSF through MRI program
- NSF through NNIN program
- Catalysis Center for Energy Innovation, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0001004]
- Ministry of Economy and Knowledge (Catalan Government) [BP-DGR 2014]
- DOE Office of Science by Argonne National Laboratory [DE-AC02-06CH11357]
Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOP-based catalytic single sites, preventing their aggregation even after exposure to air at 600 degrees C. We describe the nanocasting of NU-1000, a MOP with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 degrees C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.
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