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摩擦:英文版 2023年第12期11卷 2238-2252页

作者： Yanling WANG Zhaozhu ZHANG Meng LIU Yaohui HE Peilong LI Junya YUAN Mingming YANG Weimin LIU State Key Laboratory of Solid Lubrication Lanzhou Institute of Chemical PhysicsChinese Academy of SciencesLanzhou 730000China Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of SciencesBeijing 100049China

Polymer-textile liner composites have potential applications in aerospace applications for reducing the abrasion damage of moving parts during operation owing to their self-lubrication,light weight,and high loading capacity.Herein,Au nanoparticles(AuNPs)are successfully loaded into the lumen of halloysite nanotubes(HNTs)to construct an HNTs‒Au peasecod core‒shell nanosystem to optimize the wear resistance of phenolic resin-based poly(p-phenylene benzobisoxazole)(PBO)/polytetrafluoroethylene(PTFE)textile composites.Transmission electron microscope(TEM)characterization reveals that the AuNPs are well-dispersed inside the HNTs,with an average diameter of 6‒9 nm.The anti-wear performance of the HNTs and Au-reinforced PBO/PTFE composites is evaluated using a pin-on-disk friction tester at 100 MPa.Evidently,the addition of HNTs‒Au induces a 27.9%decrease in the wear rate of the composites.Possible anti-wear mechanisms are proposed based on the analyzed results of the worn surface morphology and the cross-section of the tribofilm obtained by focused ion beam transmission electron microscopy.

关键词： textiles composites core‒shell wear halloysite

Efficient anion immobilization enabled by structurally controllable halloysite for dendrite-free sodium metal anode

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中国科学:化学英文版 2023年第9期66卷 2600-2611页

作者： Caihong Yang Yicheng Hua Ying Zhang Jie Wang Huanwen Wang Liangjie Fu Aidong Tang Huaming Yang Engineering Research Center of Nano-Geomaterials of Ministry of Education China University of GeosciencesWuhan 430074China Laboratory of Advanced Mineral Materials China University of GeosciencesWuhan 430074China Faculty of Materials Science and Chemistry China University of GeosciencesWuhan 430074China College of Chemistry and Chemical Engineering Central South UniversityChangsha 410083China Hunan Key Laboratory of Mineral Materials and Application School of Minerals Processing and BioengineeringCentral South UniversityChangsha 410083China

Sodium metal has shown great potential as an inexpensive anode for rechargeable batteries. However, the growth of sodium dendrites continues to hinder the commercialization of Na metal batteries. Herein, an effective strategy using anion-anchoring halloysite nanotube(HNT) coating was proven to prevent the diffusion of anions and trigger uniform Na deposition. Through theoretical calculation, a model of active site of fixed anions exposed from HNTs after acid activation was established for the first time, revealing that Si–Al sites are effective active site of acid-activated HNTs. Furthermore, HNTs with strong and effective adsorption capacity for anions were obtained by controlling the structure of HNTs to regulate the exposure of Si–Al sites. The strong interaction between sites of acid-activated HNTs and the SO_(3)CF_(3)^(-) anion effectively promotes the dissociation of sodium salts, the release of Na^(+) and subsequent migration. As a result, HNTs acid activation for 4 h shows a steady sodium deposition process and displays high Coulombic efficiency in half cell, long cycle life in symmetric cell and full cell. This work provides a basic theoretical basis for the design of nanoclay with abundant and effective active site to fix anions for dendritic free metal batteries.

关键词： halloysite anion immobilization ion transport sodium dendrites sodium metal batteries

Stretchable and Superhydrophilic Polyaniline/halloysite Decorated Nanofiber Composite Evaporator for High Efficiency Seawater Desalination

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Advanced Fiber Materials 2022年第5期4卷 1233-1245页

作者： Jiang Han Wenqian Xing Jun Yan Jing Wen Yuntao Liu Yuqing Wang Zefeng Wu Longcheng Tang Jiefeng Gao School of Chemistry and Chemical Engineering Yangzhou UniversityYangzhou 225002JiangsuChina Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education Hangzhou Normal UniversityHangzhou 311121China

Here,authors report on composition of a stretchable,mechanically durable and superhydrophilic polyaniline(PANI)/hal-loysite nanotubes(HNTs)decorated PU nanofiber(PANI/HNTs@PU).The polymer nanofibers are placed as the core and PANI/HNTs makes the shell section.The PANI/HNTs creates a membrane with outstanding light absorption and photo-thermal conversion performance.The strong solar absorption capability and superhydrophilicity of the PANI/HNTs@PU remain almost unchanged during stretching,abrasion,and ultrasonic washing tests,exhibiting superior surface stability and durability.When the PANI/HNTs@PU is used for the interfacial evaporation,the evaporation rate and efficiency reach as high as 1.61 kg m^(-2) h^(-1) and 94.7%,respectively.No salt precipitation is observed on the solar absorber surface even under a high salinity or during the long term or cyclic evaporation test.Furthermore,the excellent interfacial evaporation function is maintained when the nanofiber composite is mechanically stretched.The PANI/HNTs@PU based evaporation device shows promising applications in high performance solar desalination.

关键词： Solar interface desalination Superhydrophilic Stretchable nanofiber composite Salt rejection halloysite

Electroless deposition of Ni on template of halloysite and its magnetic property

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中国有色金属学会会刊：英文版 2004年第Z1期14卷 152-156页

作者： FU Yu-bin ZHANG Li-de ZHENG Ji-yong Institute of Solid State Physics Chinese Academy of Sciences Hefei 230031 China Luoyang Ship Material Research Institute Luoyang 471039 China Institute of Solid State Physics Chinese Academy of Sciences Hefei 230031 China Luoyang Ship Material Research Institute Luoyang 471039 China

halloysite template, a ceramic substrate, is of a hollow cylindric structure, on which the fine Pd nanoparticles are uniformly formed by the reduction of palldate chloride to initiate electroless deposition. The electroless deposition of Ni is catalyzed by the Pd particles, which results in a uniform layer of Ni-P alloy on halloysite. The alloy is of a nanocrystalline structure, of which the average diameter is about 6 nm. After being heat-treated at 400 ℃, it contains both Ni and Ni12P5 crystal, meanwhile, the Ni crystal gets larger with an average size of 51.9 nm.The content of phosphorous in the Ni layer has a great influence on crystal structure. The metallized halloysite has a higher inherent coercive force, and a much lower saturation magnetization in its as-plated state, while after heattreatment, the inherent coercive force decreases drastically. These magnetic properties have great relationship with the superparamagnetism of Ni nanocrystalline and the stress anisotropy in Ni layer.

关键词： halloysite template electroless deposition Ni nanocrystalline inherent coercive force

Engineering a tubular mesoporous silica nanocontainer with well-preserved clay shell from natural halloysite

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Nano Research 2017年第8期10卷 2782-2799页

作者： Liangjie Fu Huaming Yang Aidong Tang Yuehua Hu Centre for Mineral Materials School of Minerals Processing and Bioengineering Central South University Changsha 410083 China Peter A. Rock Thermochemistry Laboratory and NEATORU University of California Davis One Shields Avenue Davis CA 95616 USA Hunan Key Lab of Mineral Materials & Application Central South University Changsha 410083 China School of Chemistry and Chemical Engineering Central South University Changsha 410083 China

The in situ synthesis of mesoporous nanotubes from natural minerals remains a great challenge. Herein, we report the successful synthesis of mesoporous silica nanotubes （MNTs） with a varying inner-shell thickness and a preserved clay outer shell from natural-halloysite nanotubes （HNTs）. After the enlargement of the lumen diameter of the tubular aluminosilicate clay by acid leaching, uniform mesopores were introduced by a modified pseudomorphic transformation approach, while the clay outer shell was well-preserved. Using density functional theory calculations, the atomic structure evolution and the energetics during A1 leaching and Si-OH condensation were studied in detail. After the leaching of A1 ions from the HNTs, local structural changes from Al（Oh） to A1（V） at a medium leaching level and to AI（Td） at a high leaching level were confirmed. The calculated hydroxylation energy of two kinds of silica components in the acid-leached HNTs （the distorted two-dimensional silica source in the inner shell and the intact aluminosilicate structure in the outer shell） was 0.5 eV lower or 1.0 eV higher than that of bulk silica, which clarifies the different behavior of the silica components in the hydrothermal process. The successful synthesis of reactive MNTs from HNTs introduces a new strategy for the synthesis of mesoporous nanocontainers with a special morphology using natural minerals. In particular, MNT samples with numerous reactive AI（V） species and a specific surface area up to 583 m^2/g （increased by a factor of 10） are promising drugloading nanocontainers and nanoreactors.

关键词： halloysite mesoporous nanotubes acid leaching hydrothermal synthesis density functional theory （DFT） calculation nanocontainer

Ion shielding functional separator using halloysite containing a negative functional moiety for stability improvement of Li–S batteries

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Journal of Energy Chemistry 2021年第9期30卷 334-340页

作者： Yong Min Kwon Jihoon Kim Kuk Young Cho Sukeun Yoon Division of Advanced Materials Engineering&Institute for Rare Metals Kongju National UniversityChungnam 31080Republic of Korea Department of Materials Science and Chemical Engineering Hanyang UniversityGyeonggi 15588Republic of Korea

Lithium–sulfur batteries are one of the attractive next-generation energy storage systems owing to theienvironmental friendliness,low cost,and high specific energy densities.However,the low electrical conductivity of sulfur,shuttling of soluble intermediate polysulfides between electrodes,and low capacitretention have hampered their commercial use.To address these issues,we use a halloysitemodulated(H-M)separator in a lithium–sulfur battery to mitigate the shuttling problem.The H-M separator acts as a mutual Coulombic repulsion in lithium-sulfur batteries,thereby selectively permitting Lions and efficiently suppressing the transfer of undesired lithium polysulfides to the Li anode sideMoreover,the use of halloysite switches the surface of the separator from hydrophobic to hydrophilicconsequently improving the electrolyte wettability and adhesion between the separator and cathodeWhen sulfur-multi-walled carbon nanotube(S-MWCNT)composites are used as cathode active materialsa lithium–sulfur battery with an H-M separator exhibits first discharge and charge capacities of 1587 an1527 m Ah g-1,respectively.Moreover,there is a consistent capacity retention up to 100 cyclesAccordingly,our approach demonstrates an economical and easily accessible strategy for commercialization of lithium–sulfur batteries.

关键词： Li–S batteries halloysite Ion shielding Negative functional moiety Lithium polysulfides

Enhancement of thermal stability and UV resistance of halloysite nanotubes using zinc oxide functionalization via a solvent-free approach

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International Journal of Minerals,Metallurgy and Materials 2019年第6期26卷 787-795页

作者： Keemi Lim Wen Shyang Chow Swee Yong Pung School of Materials and Mineral Resources Engineering Engineering Campus Universiti Sains Malaysia

The aim of this study was to synthesize and evaluate the thermal properties and ultraviolet(UV)resistance of zinc oxide-functionalized halloysite nanotubes(HNT–ZnO).The HNT–ZnO was synthesized using a facile solvent-free route.The properties of the HNT–ZnO nanofillers were characterized using zeta-potential measurement,X-ray diffraction(XRD),field-emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),Fourier transform infrared spectroscopy(FTIR),and thermogravimetric analysis(TGA).The immobilization of ZnO nanoparticles onto HNT is feasible even at the lowest mass ratio of HNT/ZnO.The TGA results indicate that the thermal stability of the HNT–ZnO nanofillers is higher than that of the HNT.Furthermore,UV?Vis diffuse reflectance spectroscopy(UV-DRS)results show that the HNT–ZnO achieve a total reflectance as high as approximately 87.5%in the UV region,as compare with 66.9%for the HNT.In summary,the immobilization of ZnO onto HNT is a viable approach for increasing the thermal stability and improving the UV shielding of HNT.

关键词： halloysite nanotubes zinc oxide nanoparticle ultraviolet shielding thermal properties

Surface Modifications of halloysite Nanotubes with Superparamagnetic Fe304 Nanoparticles and Carbonaceous Layers for Efficient Adsorption of Dyes in Water Treatment

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Chemical Research in Chinese Universities 2014年第6期30卷 971-977页

作者： JIANG Ling ZHANG Chao WEI Junchao TJIU Wengweei PAN Jisheng CHEN Yiwang LIU Tianxi State Key Laboratory of Molecular Engineering of Polymers Department of Macromolecular Science Fudan University Shanghai 200433 P. R. China" Institute of Polymers Department of Chemistry Nanchang University Nanchang 330031 P. R. China" Institute of Materials Research and Engineering Agency for Science Technology and Research Singapore 117602 Singapore

Surface modification of halloysite nanotube（HNT） with in situ grown Fe304 nanoparticles and carbona- ceous layers introduced by a hydrotbermal carbonization process of glucose has been achieved. Structure and mor- phology investigations demonstrate that iron oxide nanoparticles are uniformly anchored on the halloysite and pre- vent the aggregations of halloysite and carbon, forming a protective layer that stabilizes and improves the property of HNT/Fe3OdC nanocomposite. Magnetism characterization proves the superparamagnetic behavior of HNT/Fe304/C hybrid at room temperature, which makes it easily separated from dye solution under an external magnetic field. Ex- ploration of adsorption ability demonstrates that the maximum adsorption capacity of the as-prepared HNT/Fe304/C nanoeomposite for methylene blue（MB） is about twice and 1.5 times those of HNT/Fe304 and HNT according to Langmuir equation, respectively. The adsorption behavior investigations indicate that HNT/Fe304/C hybrid has a he- terogeneous structure and shows a non-ideal monolayer adsorption that fits the Redlich-Peterson isotherm, and the adsorption process follows a pseudo-second-order kinetic model. Therefore, the as-prepared HNT/Fe304/C hybrid is a fast, separatable and superparamagnetic adsorbent with a good adsorption ability, demonstrating great potential in the application of water treatment.

关键词： halloysite Hydrothermal carbonization Superparamagnetic iron oxide Water purification

Low-Temperature Synthesis of Crystalline Inorganic/Metallic Nanocrystal-halloysite Composite Nanotubes

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Chinese Journal of Chemistry 2014年第7期32卷 599-606页

作者： Cuiping Li Jiaqiang Wang Siquan Feng Zan Liu Department of Applied Chemistry Key Laboratory of Medicinal Chemistry for Natural ResourceMinistry of EducationSchool of Chemical Science and TechnologyYunnan UniversityKunmingYunnan 650091China Kunming Cable Co. LtdKunmingYunnan 650100China

We have demonstrated a facile approach for the low-temperature synthesis of crystalline inorganic/metallic nanocrystal-halloysite composite nanotubes by employing the bulk controlled synthesis of inorganic/metallic nanocrystals on halloysite nanotubes.The halloysite clay nanotubes can adsorb the target precursor and induce inorganic/metallic nanocrystals to grow in situ.The crystalline phase and morphology of the composite clay nanotubes is tunable.By simply tuning the acidity of the titania sol,the crystalline titania-clay nanotubes with tunable crystalline phases of anatase,a mixture of anatase and rutile or rutile are achieved.The approach is general and has been extended to synthesize the representative perovskite oxide(barium and strontium titanate)-halloysite composite nanotubes.Metallic nickel nanocrystal can also be grown on the surface of halloysite nanotubes at low temperature.The traditional thermal treatment for crystallite transformation is not required,thus intact contour of halloysite nanotubes and the crystallinity structure of halloysite nanotubes can be guaranteed.The combined properties from inorganic/metallic nanocrystal(high refractive index,high dielectric constant and catalytic ability)and the halloysite clay nanotubes are promising for applications such as photonic crystals,high-k-gate dielectrics,photocatalysis and purification.

关键词： composite nanotubes halloysite inorganic nanocrystal perovskite oxide low temperature synthesis

Microstructure and Photocatalytic Decomposition of Methylene Blue by TiO2-Mounted halloysite, a Natural Tubular Mineral

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Acta Geologica Sinica(English Edition) 2006年第2期80卷 278-284页

作者： LU Xianchu CHUAN Xiuyun WANG Aiping KANG Feiyu School of Earth and Space Sciences Peking University Beijing 100871 Institute of Process and Engineering Chinese Academy of Sciences Beijing 100080 Department of Material Science and Engineering Tsinghua University Beijing 100084

On the basis of analysis of structure and properties, halloysite, a natural tubular mineral, was developed for an environmental treatment. TiO2 was mounted into halloysite by using hydrolysis of tetrabutyl titanate at room temperature. The adsorption and photocatalytic performance of halloysite and TiO2-mounted halloysite have been examined in methylene blue aqueous solution in the dark and under ultraviolet ray irradiation, respectively. Their performance of adsorption and photodecomposition was evaluated from the adsorbed and degraded amounts of methylene blue （MB）. Due to the mixture of adsorption and photodecomposition, the concentration of MB, organic pollution, in water decreased rapidly with TiO2-mounted halloysite powder, which is a faster reaction than that with halloysite-only adsorption. This new use of halloysite is leading to many interesting applications in the decomposition and elimination of various pollutants in air and water.

关键词： halloysite TiO2-mounted halloysite methylene blue photodecomposition anti-pollution