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      Exploring the Brønsted acidity of UiO-66 (Zr, Ce, Hf) metal–organic frameworks for efficient solketal synthesis from glycerol acetalization

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          Abstract

          Zr, Ce, Hf-based isostructural UIO-66 MOFs exhibited varying degree of Brønsted acidity (UiO-66(Hf) > UiO-66(Ce) > UiO-66(Zr)) on their secondary building units owing to the differences in their oxophilities.

          Abstract

          Zr, Ce, Hf-based isostructural UIO-66 MOFs exhibited varying degree of Brønsted acidity (UiO-66(Hf) > UiO-66(Ce) > UiO-66(Zr)) on their secondary building units owing to the differences in their oxophilicities. UIO-66(Hf) showed remarkable catalytic activity for solketal synthesis with a turnover frequency as high as 13 886 h −1, which is 90 times higher than that of UiO-66(Zr) and several orders of magnitude higher than that of H 2SO 4 or Zeolites.

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          Ultrahigh porosity in metal-organic frameworks.

          Hiroyasu Furukawa, Nakeun Ko, Yong Bok Go … (2010)
          Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 unit was joined with either one or two kinds of organic link, 4,4',4''-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4',44''-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (BBC), 4,4',44''-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4'-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.
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            Metal-organic frameworks (MOFs).

            Hong-Cai Zhou, Susumu Kitagawa (2014)
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              Applications of metal-organic frameworks in heterogeneous supramolecular catalysis.

              Jiewei Liu, Lianfen Chen, Jing-Hao Cui … (2014)
              This review summarizes the use of metal-organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal-organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.
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                Author and article information

                Journal
                Journal ID (publisher-id): ICHBD9
                Title: Dalton Transactions
                Abbreviated Title: Dalton Trans.
                Publisher: Royal Society of Chemistry (RSC)
                ISSN (Print): 1477-9226
                ISSN (Electronic): 1477-9234
                Publication date Created: January 15 2019
                Publication date (Electronic): 2019
                Volume: 48
                Issue: 3
                Pages: 843-847
                Affiliations
                [1 ]Materials Science Division
                [2 ]Poornaprajna Institute of Scientific Research
                [3 ]Bangalore Rural- 562164
                [4 ]India
                [5 ]Manipal Academy of Higher Education
                Article
                DOI: 10.1039/C8DT03512A
                SO-VID: 6ff81bed-f9ca-4226-85a5-e21779c769a8
                Copyright © © 2019
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                http://rsc.li/journals-terms-of-use

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