Core/Shell Ruthenium–Halloysite Nanocatalysts for Hydrogenation of Phenol

Винокуров, В. А.; Glotov, Aleksandr; Chudakov, Yaroslav A.; Stavitskaya, Anna; Иванов, Е. В.; Гущин, П. А.; Zolotukhina, A. V.; Maximov, A. L.; Караханов, Э. А.; Lvov, Yuri

doi:10.1021/acs.iecr.7b03282

Cited by 85 publications

(21 citation statements)

References 50 publications

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“…Combination of silver nanoparticles with DCOIT loaded into an antifouling coating show synergetic effects against fouling [30]. Naturally excavated cheap halloysite nanotubes can be used as a container for DCOIT antifouling agent and serve as a template for Ag-particles formation preventing their undesirable aggregation [31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

Development of Marine Antifouling Epoxy Coating Enhanced with Clay Nanotubes

Wang

Zhang

et al. 2019

Materials

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An antifouling epoxy resin doped with natural clay nanotubes that are loaded with biocide or silver allowed extended protection against the proliferation of marine microorganisms. Compared to the 2-3 months of protection with antifoulant dichlorooctylisothiazolone (DCOIT) directly admixed into epoxy resin, the DCOIT release time of the halloysite formulations was extended to 12 months by incorporating biocide-loaded nanoclay in the polymer matrix. The protective properties of the epoxy-halloysite nanocomposites showed much less adhesion and proliferation of marine bacteria Vibrio natriegens on the resin surface after a two-month exposure to seawater than the coating formulations directly doped with non-encapsulated DCOIT. The coating formulation protection efficiency was further confirmed by twelve-month shallow field tests in the South China Sea. Replacing 2 wt.% biocide in the traditional formula with DCOIT-loaded natural environmentally friendly halloysite clay drastically improved the antifouling properties of the epoxy coating, promising scalable applications in protective marine coating. The antifouling property of epoxy resin was enhanced with silver particles synthesized on halloysite nanotubes. A natural mixture of MnO particles and halloysite could also be used as a nonbiocide additive to marine coating. The short-term White Sea water test of epoxy coating with 5% of Ag-halloysite composite of MnO-halloysite natural mixture showed no visible fouling.

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Section: Introductionmentioning

confidence: 99%

Development of Marine Antifouling Epoxy Coating Enhanced with Clay Nanotubes

Wang

Zhang

et al. 2019

Materials

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“…The promoting effect of noble metals in alloys was explained here in terms of generation of additional hydrogen by these metals, which prevented coke formation, reacting with the cracked reaction intermediates . The catalytic activity of halloysite@Ru catalysts were tested in reaction of phenol hydrogenation to form cyclohexanole . This catalyst is also active in other hydrogenation reactions of aromatic hydrocarbons (Scheme ).…”

Section: Halloysite – Metal Nanoparticles Architecturesmentioning

confidence: 99%

Nanoparticles Formed onto/into Halloysite Clay Tubules: Architectural Synthesis and Applications

Винокуров

Stavitskaya

Glotov

et al. 2018

The Chemical Record

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Nanoparticles, being objects with high surface area are prone to agglomeration. Immobilization onto solid supports is a promising method to increase their stability and it allows for scalable industrial applications, such as metal nanoparticles adsorbed to mesoporous ceramic carriers. Tubular nanoclay - halloysite - can be an efficient solid support, enabling the fast and practical architectural (inside / outside) synthesis of stable metal nanoparticles. The obtained halloysite-nanoparticle composites can be employed as advanced catalysts, ion-conducting membrane modifiers, inorganic pigments, and optical markers for biomedical studies. Here, we discuss the possibilities to synthesize halloysite decorated with metal, metal chalcogenide, and carbon nanoparticles, and to use these materials in various fields, especially in catalysis and petroleum refinery.

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“…Recently, we showed that metal nanoparticles could be synthesized selectively inside halloysite using azines as complexing agents [17]. Ru loaded inside halloysite by complexation of RuCl 3 with 1,2-bis(2-furylmethylene)hydrazine was found to be efficient in the hydrogenation of mono-aromatics [18][19][20]. No works were performed on the complexing agent's effect on morphology, physico-chemical properties, and catalytic activity of ruthenium-loaded halloysite.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium-Loaded Halloysite Nanotubes as Mesocatalysts for Fischer–Tropsch Synthesis

et al. 2020

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Halloysite aluminosilicate nanotubes loaded with ruthenium particles were used as reactors for Fischer–Tropsch synthesis. To load ruthenium inside clay, selective modification of the external surface with ethylenediaminetetraacetic acid, urea, or acetone azine was performed. Reduction of materials in a flow of hydrogen at 400 °C resulted in catalysts loaded with 2 wt.% of 3.5 nm Ru particles, densely packed inside the tubes. Catalysts were characterized by N2-adsorption, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray fluorescence, and X-ray diffraction analysis. We concluded that the total acidity and specific morphology of reactors were the major factors influencing activity and selectivity toward CH4, C2–4, and C5+ hydrocarbons in the Fischer–Tropsch process. Use of ethylenediaminetetraacetic acid for ruthenium binding gave a methanation catalyst with ca. 50% selectivity to methane and C2–4. Urea-modified halloysite resulted in the Ru-nanoreactors with high selectivity to valuable C5+ hydrocarbons containing few olefins and a high number of heavy fractions (α = 0.87). Modification with acetone azine gave the slightly higher CO conversion rate close to 19% and highest selectivity in C5+ products. Using a halloysite tube with a 10–20-nm lumen decreased the diffusion limitation and helped to produce high-molecular-weight hydrocarbons. The extremely small C2–C4 fraction obtained from the urea- and azine-modified sample was not reachable for non-templated Ru-nanoparticles. Dense packing of Ru nanoparticles increased the contact time of olefins and their reabsorption, producing higher amounts of C5+ hydrocarbons. Loading of Ru inside the nanoclay increased the particle stability and prevented their aggregation under reaction conditions.

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Core/Shell Ruthenium–Halloysite Nanocatalysts for Hydrogenation of Phenol

Cited by 85 publications

References 50 publications

Development of Marine Antifouling Epoxy Coating Enhanced with Clay Nanotubes

Development of Marine Antifouling Epoxy Coating Enhanced with Clay Nanotubes

Nanoparticles Formed onto/into Halloysite Clay Tubules: Architectural Synthesis and Applications

Ruthenium-Loaded Halloysite Nanotubes as Mesocatalysts for Fischer–Tropsch Synthesis

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