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      Nanostructured Nickel Aluminate as a Key Intermediate for the Production of Highly Dispersed and Stable Nickel Nanoparticles Supported within Mesoporous Alumina for Dry Reforming of Methane

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          Abstract

          Two routes of preparation of mesoporous Ni-alumina materials favoring the intermediate formation of nanostructured nickel-aluminate are presented. The first one involves an aluminum containing MOF precursor used as sacrificial template to deposit nickel while the second is based on a one-pot synthesis combined to an EISA method. As shown by a set of complementary techniques, the nickel-aluminate nanospecies formed after calcination are homogeneously distributed within the developed mesoporous alumina matrices whose porous characteristics vary depending on the preparation method. A special attention is paid to electron-microscopy observations using especially STEM imaging with high chemical sensitivity and EDS elemental mapping modes that help visualizing the extremely high nickel dispersion and highlight the strong metal anchoring to the support that persists after reduction. This leads to active nickel nanoparticles particularly stable in the reaction of dry reforming of methane.

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          A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration.

          Aluminum 1,4-benzenedicarboxylate Al(OH)[O(2)C-C(6)H(4)-CO(2)]. [HO(2)C-C(6)H(4)-CO(2)H](0.70) or MIL-53 as (Al) has been hydrothermally synthesized by heating a mixture of aluminum nitrate, 1,4-benzenedicarboxylic acid, and water, for three days at 220 degrees C. Its 3 D framework is built up of infinite trans chains of corner-sharing AlO(4)(OH)(2) octahedra. The chains are interconnected by the 1,4-benzenedicarboxylate groups, creating 1 D rhombic-shaped tunnels. Disordered 1,4-benzenedicarboxylic acid molecules are trapped inside these tunnels. Their evacuation upon heating, between 275 and 420 degrees C, leads to a nanoporous open-framework (MIL-53 ht (Al) or Al(OH)[O(2)C-C(6)H(4)-CO(2)]) with empty pores of diameter 8.5 A. This solid exhibits a Langmuir surface area of 1590(1) m(2)g(-1) together with a remarkable thermal stability, since it starts to decompose only at 500 degrees C. At room temperature, the solid reversibly absorbs water in its tunnels, causing a very large breathing effect and shrinkage of the pores. Analysis of the hydration process by solid-state NMR ((1)H, (13)C, (27)Al) has clearly indicated that the trapped water molecules interact with the carboxylate groups through hydrogen bonds, but do not affect the hydroxyl species bridging the aluminum atoms. The hydrogen bonds between water and the oxygen atoms of the framework are responsible for the contraction of the rhombic channels. The structures of the three forms have been determined by means of powder X-ray diffraction analysis. Crystal data for MIL-53 as (Al) are as follows: orthorhombic system, Pnma (no. 62), a = 17.129(2), b = 6.628(1), c = 12.182(1) A; for MIL-53 ht (Al), orthorhombic system, Imma (no. 74), a = 6.608(1), b = 16.675(3), c = 12.813(2) A; for MIL-53 lt (Al), monoclinic system, Cc (no. 9), a = 19.513(2), b = 7.612(1), c = 6.576(1) A, beta = 104.24(1) degrees.
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            CO2Reforming of CH4

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              CO2-Reforming of Methane over Transition Metals

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                Author and article information

                Journal
                Molecules
                Molecules
                molecules
                Molecules
                MDPI
                1420-3049
                14 November 2019
                November 2019
                : 24
                : 22
                : 4107
                Affiliations
                [1 ]Sorbonne Université, Campus UPMC, CNRS UMR-7197, Laboratoire de Réactivité de Surface, 4 Place Jussieu, F-75005 Paris, France; laylakaram_22@ 123456hotmail.com (L.K.); julien.reboul@ 123456upmc.fr (J.R.)
                [2 ]Department of Chemical Engineering, Faculty of Engineering, University of Balamand, P.O. Box 33, Amioun, 33 El Koura, Lebanon; nissrine.hassan@ 123456balamand.edu.lb
                [3 ]Laboratoire Matériaux et Phénomènes Quantiques, Université de Paris, CNRS, F-75013 Paris, France; jaysen.nelayah@ 123456univ-paris-diderot.fr
                Author notes
                Author information
                https://orcid.org/0000-0002-7340-8969
                https://orcid.org/0000-0001-7349-7394
                https://orcid.org/0000-0003-4089-438X
                Article
                molecules-24-04107
                10.3390/molecules24224107
                6891692
                31739418
                380c3d35-da88-48b4-8da7-e0adcda2d79b
                © 2019 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
                : 02 October 2019
                : 07 November 2019
                Categories
                Article

                nickel aluminate,mesoporous alumina,heterogenous catalysis,mof,haadf,dry reforming of methane (drm)

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