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      Diatomite-Metal-Organic Framework Composite with Hierarchical Pore Structures for Adsorption/Desorption of Hydrogen, Carbon Dioxide and Water Vapor

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          Abstract

          Distinctive Cr-MOF@Da composites have been constructed using chromium-based metal-organic frameworks (MOFs) and diatomite (Da). The new materials have hierarchical pore structures containing micropores, mesopores and macropores. We have synthesized various morphologies of the MOF compound Cr-MIL-101 to combine with Da in a one-pot reaction step. These distinctive hierarchical pore networks within Cr-MIL-101@Da enable exceptional adsorptive performance for a range of molecules, including hydrogen (H 2), carbon dioxide (CO 2) and water (H 2O) vapor. Selectivity for H 2 or CO 2 can be moderated by the morphology and composition of the Cr-MIL-101 included in the Cr-MOF@Da composite. The encapsulation and growth of Cr-MIL-101 within and on Da have resulted in excellent water retention as well as high thermal and hydrolytic stability. In some cases, Cr-MIL-101@Da composite materials have demonstrated increased thermal stability compared with that of Cr-MIL-101; for example, decomposition temperatures >340 ℃ can be achieved. Furthermore, these Cr-MIL-101@Da composites retain structural and morphological integrity after 60 cycles of repeated hydration/dehydration, and after storage for more than one year. These characteristics are difficult to achieve with many MOF materials, and thus suggest that MOF–mineral composites show high potential for practical gas storage and water vapor capture.

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          Most cited references55

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          Hydrogen storage in metal-organic frameworks.

          New materials capable of storing hydrogen at high gravimetric and volumetric densities are required if hydrogen is to be widely employed as a clean alternative to hydrocarbon fuels in cars and other mobile applications. With exceptionally high surface areas and chemically-tunable structures, microporous metal-organic frameworks have recently emerged as some of the most promising candidate materials. In this critical review we provide an overview of the current status of hydrogen storage within such compounds. Particular emphasis is given to the relationships between structural features and the enthalpy of hydrogen adsorption, spectroscopic methods for probing framework-H(2) interactions, and strategies for improving storage capacity (188 references).
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            Hydrogen storage in microporous metal-organic frameworks.

            Metal-organic framework-5 (MOF-5) of composition Zn4O(BDC)3 (BDC = 1,4-benzenedicarboxylate) with a cubic three-dimensional extended porous structure adsorbed hydrogen up to 4.5 weight percent (17.2 hydrogen molecules per formula unit) at 78 kelvin and 1.0 weight percent at room temperature and pressure of 20 bar. Inelastic neutron scattering spectroscopy of the rotational transitions of the adsorbed hydrogen molecules indicates the presence of two well-defined binding sites (termed I and II), which we associate with hydrogen binding to zinc and the BDC linker, respectively. Preliminary studies on topologically similar isoreticular metal-organic framework-6 and -8 (IRMOF-6 and -8) having cyclobutylbenzene and naphthalene linkers, respectively, gave approximately double and quadruple (2.0 weight percent) the uptake found for MOF-5 at room temperature and 10 bar.
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              Stable Metal-Organic Frameworks: Design, Synthesis, and Applications

              Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

                Author and article information

                Journal
                Materials (Basel)
                Materials (Basel)
                materials
                Materials
                MDPI
                1996-1944
                22 October 2020
                November 2020
                : 13
                : 21
                : 4700
                Affiliations
                [1 ]Institute for Future Environments and Science and Engineering Faculty, Queensland University of Technology (QUT), Brisbane, Queensland 4001, Australia; wanggaofeng@ 123456gig.ac.cn (G.W.); ian.mackinnon@ 123456qut.edu.au (I.D.R.M.)
                [2 ]CAS Key Laboratory of Mineralogy and Metallogeny, Guangdong Provincial Key Laboratory of Mineral Physics and Material Research and Development, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China; e6.graham@ 123456qut.edu.au (E.G.); zhujx@ 123456gig.ac.cn (J.Z.); zhurl@ 123456gig.ac.cn (R.Z.); hehp@ 123456gig.ac.cn (H.H.)
                [3 ]School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing 100083, China; zhengsl@ 123456cumtb.edu.cn (S.Z.); zhimingsun@ 123456cumtb.edu.cn (Z.S.)
                Author notes
                [* ]Correspondence: y.xi@ 123456qut.edu.au ; Tel.: +61-07-3138-1995
                Author information
                https://orcid.org/0000-0001-9818-1994
                https://orcid.org/0000-0002-0732-8987
                https://orcid.org/0000-0003-2924-9494
                Article
                materials-13-04700
                10.3390/ma13214700
                7659967
                33105589
                9a38f128-1a0d-484e-a836-955b10bf1ffd
                © 2020 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 05 October 2020
                : 19 October 2020
                Categories
                Article

                metal-organic frameworks,diatomite,hydrogen,carbon dioxide,water vapor

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