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      Preparation of palladated porous nitrogen-doped carbon using halloysite as porogen: disclosing its utility as a hydrogenation catalyst

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          Abstract

          In this article, halloysite nanoclay (Hal) was used as porogen for the synthesis of nitrogen doped porous carbon material with high specific surface area and pore volume. To this purpose, polymerization of melamine and terephthalaldehyde (MT) was performed in the presence of amine-functionalized carbon coated Hal (Hal@Glu-2N) that was prepared from hydrothermal treatment of Hal and glucose. Then, the prepared nanocomposite was palladated and carbonized to afford Pd@Hal@C. To further improve the textural properties of the nanocomposite, and introduce more pores in its structure, Hal nanotubes were etched. The characterization of the resulting compound, Pd@C, and comparing it with Pd@Hal@C, showed that etching of Hal significantly increased the specific surface area and pore volume in Pd@C. Pd@C was successfully used as a heterogeneous catalyst for promoting hydrogenation of nitroarens in aqueous media using hydrogen with atmospheric pressure as a reducing agent. The comparison of the structural features and catalytic activity of the catalyst with some control catalysts, including, Pd@Hal, Pd@Hal@Glu, Pd@Hal@Glu-MT and Pd@Hal@C confirmed that nitrogen groups in C could improve the Pd anchoring and suppress its leaching, while etching of Hal and introduction of more pores could enhance the catalytic activity through facilitating the mass transfer.

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          Most cited references55

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          Hierarchical porous nitrogen-doped carbon nanosheets derived from silk for ultrahigh-capacity battery anodes and supercapacitors.

          Hierarchical porous nitrogen-doped carbon (HPNC) nanosheets (NS) have been prepared via simultaneous activation and graphitization of biomass-derived natural silk. The as-obtained HPNC-NS show favorable features for electrochemical energy storage such as high specific surface area (SBET: 2494 m(2)/g), high volume of hierarchical pores (2.28 cm(3)/g), nanosheet structures, rich N-doping (4.7%), and defects. With respect to the multiple synergistic effects of these features, a lithium-ion battery anode and a two-electrode-based supercapacitor have been prepared. A reversible lithium storage capacity of 1865 mA h/g has been reported, which is the highest for N-doped carbon anode materials to the best of our knowledge. The HPNC-NS supercapacitor's electrode in ionic liquid electrolytes exhibit a capacitance of 242 F/g and energy density of 102 W h/kg (48 W h/L), with high cycling life stability (9% loss after 10,000 cycles). Thus, a high-performance Li-ion battery and supercapacitors were successfully assembled for the same electrode material, which was obtained through a one-step and facile large-scale synthesis route. It is promising for next-generation hybrid energy storage and renewable delivery devices.
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            Halloysite Clay Nanotubes for Loading and Sustained Release of Functional Compounds.

            Halloysite is an alumosilicate tubular clay with a diameter of 50 nm, an inner lumen of 15 nm and a length of 600-900 nm. It is a natural biocompatible nanomaterial available in thousands of tons at low price, which makes it a good candidate for nanoarchitectural composites. The inner lumen of halloysite may be adjusted by etching to 20-30% of the tube volume and loading with functional agents (antioxidants, anticorrosion agents, flame-retardant agents, drugs, or proteins) allowing for formulations with sustained release tuned by the tube end-stoppers for hours and days. Clogging the tube ends in polymeric composites allows further extension of the release time. Thus, antioxidant-loaded halloysite doped into rubber enhances anti-aging properties for at least 12 months. The addition of 3-5 wt% of halloysite increases the strength of polymeric materials, and the possibility of the tube's orientation promises a gradient of properties. Halloysite nanotubes are a promising mesoporous media for catalytic nanoparticles that may be seeded on the tube surface or synthesized exclusively in the lumens, providing enhanced catalytic properties, especially at high temperatures. In vitro and in vivo studies on biological cells and worms indicate the safety of halloysite, and tests for efficient adsorption of mycotoxins in animals' stomachs are also carried out.
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              Properties and applications of halloysite nanotubes: recent research advances and future prospects

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                Author and article information

                Contributors
                s.sadjadi@ippi.ac.ir
                M.Heravi@alzahra.ac.ir
                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group UK (London )
                2045-2322
                6 February 2020
                6 February 2020
                2020
                : 10
                : 2039
                Affiliations
                [1 ]Gas Conversion Department, Faculty of Petrochemicals, Iran Polymer and Petrochemicals Institute, PO Box 14975-112, Tehran, Iran
                [2 ]ISNI 0000 0001 0097 6984, GRID grid.411354.6, Department of Chemistry, School of Science, , Alzahra University, ; PO Box 1993891176, Vanak, Tehran Iran
                [3 ]ISNI 0000 0004 1762 5517, GRID grid.10776.37, Dipartimento di Fisica e Chimica, , Università degli Studi di Palermo, Viale delle Scienze, pad. 17, ; 90128 Palermo, Italy
                [4 ]GRID grid.182470.8, Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, INSTM, Via G. Giusti, 9, ; I-50121 Firenze, Italy
                Article
                59003
                10.1038/s41598-020-59003-5
                7005045
                32029834
                ad5e2bc3-a96f-41fa-a683-1b67199fc5b2
                © The Author(s) 2020

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 8 November 2019
                : 23 January 2020
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                © The Author(s) 2020

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                chemistry,materials science
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                chemistry, materials science

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