Introducing inorganic nanomaterials into a polymer matrix greatly improves the anticorrosion performance of epoxy coatings(EP);however,poor compatibility between the materials can limit the improvement in properties.I...Introducing inorganic nanomaterials into a polymer matrix greatly improves the anticorrosion performance of epoxy coatings(EP);however,poor compatibility between the materials can limit the improvement in properties.In this work,based on the high interface compatibility of two-dimensional(2D)Co_(2)(OH)_(2)BDC(BDC=1,4-benzenedicarboxylate)in the epoxy coating that we reported in previous work,we fabricated a 2D Co_(2)(OH)_(2)BDC-halloysite nanotube(HNT)nanocomposite have a structure consisting of alternating of nanosheets and nanotube by in situ synthesis.The nanocomposite was characterized by Fourier transform infrared spectroscopy,X-ray diffraction,and scanning electron microscopy.The mechanical and anticorrosion performance of the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was evaluated by mechanical tests and electrochemical impedance spectroscopy spectra.Compared with a conventional unreinforced epoxy coating,the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating had higher mechanical strength and toughness,and the low-frequency impedance modulus of 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was increased by three orders of magnitude,demonstrating the high corrosion resistance of our reinforced coating.展开更多
Layered assembled membranes of 2D leaf-like zeolitic imidazolate frameworks(ZIF-L)nanosheets have received great attention in the field of water treatment due to the porous structure and excellent antibacterial abilit...Layered assembled membranes of 2D leaf-like zeolitic imidazolate frameworks(ZIF-L)nanosheets have received great attention in the field of water treatment due to the porous structure and excellent antibacterial ability,but the dense accumulation on the membrane surface and the low permeate flux greatly hinder their application.Herein,we synthesized m HNTs(modified halloysite nanotubes)/ZIF-L nanocomposites on modified m HNTs by in situ growth method.Interestingly,due to the different size of m HNTs and ZIF-L,m HNTs were packed in ZIF-L nanosheets.The hollow m HNTs provided additional transport channels for water molecules,and the accumulation of the ZIF-L nanosheets was decreased after assembling m HNTs/ZIF-L nanocomposites into membrane by filtration.The prepared m HNTs/ZIF-L membrane presented high permeate flux(59.6 L·m^(-2)·h^(-1)),which is 2-4 times of the ZIF-L membranes(14.8 L·m^(-2)·h^(-1)).Moreover,m HNTs/ZIF-L membranes are intrinsically antimicrobial,which exhibit extremely high bacterial resistance.We provide a controllable strategy to improve 2D ZIF-L assembles,and develops novel membranes using 2D package structure as building units.展开更多
Halloysite nanotubes were used as nanocontainers to hold corrosion inhibitors such as Ce^(3+)-Zr^(4+),2-mercaptobenzothiazole and 8-hydroxyquinoline in their lumen.An acid assisted etching of the nanotubes was carried...Halloysite nanotubes were used as nanocontainers to hold corrosion inhibitors such as Ce^(3+)-Zr^(4+),2-mercaptobenzothiazole and 8-hydroxyquinoline in their lumen.An acid assisted etching of the nanotubes was carried out with a view to increase the lumen diameter and thereby,increase the amount of loading of the corrosion inhibitor.The morphology of as-received and etched halloysite nanotubes was ob-served using TEM analysis.The loading of corrosion inhibitors was confirmed using SEM-EDS and BET analysis.Polymeric microcapsules were used as capping agents for the ends of the loaded HNTs following which,they were dispersed into a hybrid sol-gel silica matrix.Dip coating method was used to generate coatings on AZ91D substrates followed by heat treatment at 130℃ for 1 h.The release rate kinetics of corrosion inhibitors from as-received and etched nanotubes was investigated in buffer solutions of 3.5 wt%NaCl at different pH.The release mechanism of corrosion inhibitors from the HNT lumen was validated using various semi-empirical models.Coatings were also evaluated for their corrosion protection ability using electrochemical techniques after exposure to 3.5 wt%NaCl solution for 120 h.Coatings generated using Ce^(3+)-Zr^(4+)loaded into as-received halloysite nanotubes have shown more effective corrosion protection when compared to other corrosion inhibitors after 120 h exposure to the corrosive medium.展开更多
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...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.展开更多
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...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.展开更多
A natural nanotubular material,halloysite nanotubes(HNTs),was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube(SBR/m-HNT) nanocomposites.Complex of resorcinol and hexamethylenetetramine (RH)...A natural nanotubular material,halloysite nanotubes(HNTs),was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube(SBR/m-HNT) nanocomposites.Complex of resorcinol and hexamethylenetetramine (RH) was used as the interfacial modifier.The structure,morphology and mechanical properties of SBR/m-HNT nanocomposites,especially the interfacial interactions,were investigated.SEM and TEM observations showed that RH can not only facilitate the dispersion and orientation of HNTs in SBR matrix ...展开更多
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 elect...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.展开更多
1 Introduction The weathered crust rare earth deposits is one of the most significant rare earth deposits,which are mostly distributed in southern China,especially in the south of Jiangxi province(Chi et al.,2007).The...1 Introduction The weathered crust rare earth deposits is one of the most significant rare earth deposits,which are mostly distributed in southern China,especially in the south of Jiangxi province(Chi et al.,2007).The compositions of these deposits,which are weathered from igneous rocks such as granite through biological,physical or展开更多
The environmental stress cracking resistance of halloysite nanoclay-polyester nanocomposites was investigated using fracture mechanics approach. The incorporation of halloysite nanoclay was found to improve the enviro...The environmental stress cracking resistance of halloysite nanoclay-polyester nanocomposites was investigated using fracture mechanics approach. The incorporation of halloysite nanoclay was found to improve the environmental stress cracking resistance of the nano-composites. The storage modulus of nano-composites measured by dynamic mechanical analysis increased remarkably as a function of halloysite nanoclay content. At 0.7 wt% nanoclay, the Tg improved from 72°C to 76°C. The fracture toughness increased up to 33% and time to failure improved 155% with the addition of 0.7 wt% of halloysite nanoclay. The maximum microhardness was found 119% higher for the same nano-filler concentration compared to monolithic polyester. The reinforcement with 1 wt% showed lower fracture toughness due to agglomerations of nanoclay which act as flaws. The presence of agglomerates weakened the bond between nano-particles and matrix hence reduces the environmental stress cracking resistance by halloysite nanoclay reinforcement.展开更多
The diffusion permeability through new hybrid materials based on a Nafion-type membrane (MF- 4SC) and nanotubes of halloysite is investigated using the Nernst-Planck approach. A method of quantitative evaluation of ph...The diffusion permeability through new hybrid materials based on a Nafion-type membrane (MF- 4SC) and nanotubes of halloysite is investigated using the Nernst-Planck approach. A method of quantitative evaluation of physicochemical parameters (averaged and individual diffusion coefficients and averaged distribution coefficients of ion pairs in the membrane) of system “electrolyte solution—ion-exchange membrane—water”, which was proposed earlier, is further developed. The parameters of hybrid membranes on the base of MF-4SC and nanotubes of halloysite (5% wt and 8% wt) are obtained from experimental data on diffusion permeability of NaCl solutions using theoretical calculations. New model of three-layer membrane system can be used for refining calculated results with taking into account both diffusive layers. It is shown that adding of halloysite nanotubes into the membrane volume noticeably affects exchange capacity as well as structural and transport characteristics of original perfluorinated membranes. Hybrid membranes on the base of MF-4SC and halloysite nanotubes can be used in fuel cells and catalysis.展开更多
In this study,we demonstrated the effects of chemical treatments for Halloysite nanotubes(HNTs)under acid and alkaline conditions using sulfuric acid and sodium hydroxide.XRD results indicate that alkaline treatment d...In this study,we demonstrated the effects of chemical treatments for Halloysite nanotubes(HNTs)under acid and alkaline conditions using sulfuric acid and sodium hydroxide.XRD results indicate that alkaline treatment destroyed the crystalline structure and morphology for HNTs because the XRD spectrum shows the typical peaks for montmorillonite.For the acid treatment using H2SO4,XRD spectrum indicates an intensity reduction for the peak(001)showing a lower concentration of aluminium in the structure.Diffuse reflectance analysis shows a reduction of 40 and 15%for reflectance with H2SO4 and NaOH treatments respectively.A terephthalic acid adsorption test was realized with the HNTs,modified halloysites(HNT-H2SO4)and(HNT-NaOH)samples with a kinetic study and it was quantified with UV spectroscopy at 240 nm where results shown a lower adsorption for HNTs treated with H2SO4 in comparison with alkaline treatment and not treated HNT.A decrease of 58%±0.3was achieved with the sulfuric acid treatment with not crystalline structure modification using ICP technique to quantify the sample compositions.展开更多
In this work a three-dimensional, time-quantified Monte Carlo model that efficiently describes diffusion through and from nanotubes is implemented. Controlled delivery from Halloysite Nano-tubes (HNT) is modeled based...In this work a three-dimensional, time-quantified Monte Carlo model that efficiently describes diffusion through and from nanotubes is implemented. Controlled delivery from Halloysite Nano-tubes (HNT) is modeled based on interactions between the HNT’s inner wall and the nanoparticles (NPs) and among NPs themselves. The model was validated using published experimental data. The validated model is then used to study the effect of multiples parameter like HNT diameter and length, particle charge, and ambient temperature on the release of encapsulated NPs. The results show that release profiles depend on the size distribution of the HNT batch used for the experiment, as delivery is sensitive to HNT lumen and length. A very good agreement with the experiment is observed when a weighted average release profile is compared to the experimental profile. Although the NP dynamics is temperature-dependent, the effect is minimum within the range of temperatures relevant to biomedical applications, but will be relevant for other applications at temperatures significantly different from room temperature. This model can be used to predict the best conditions for a particular delivery need.展开更多
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 ...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.展开更多
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 ca...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.展开更多
Halloysite nanotubes(HNTs)have been considered as a promising flame retardant fillers for polymers.In this work,the polyhedral oligomericsilsesquioxane(POSS)containing amino group was covalently grafted on the surface...Halloysite nanotubes(HNTs)have been considered as a promising flame retardant fillers for polymers.In this work,the polyhedral oligomericsilsesquioxane(POSS)containing amino group was covalently grafted on the surface of HNTs with 3-(2,3-epoxypropoxy)propytrimethoxysilane as a chemical bridge.The POSS modified HNTs(HNTs-POSS)dispersed uniformly in the thermoplastic polyurethane(TPU)matrix and endowed TPU nanocomposites with enhanced tensile properties and fire safety.Cone calorimeter tests revealed that the introduction of 2 wt%HNTs-POSS to TPU matrix remarkably reduced the peak of heat release rate(PHRR)and total heat release(THR)by 60.0%and 18.3%,respectively.In addition,the peak CO production rate and total smoke release(TSR)could be significantly suppressed by the addition of HNTsPOSS.The well dispersed HNTs in combination with the ceramified silicon network from the thermal decomposition of POSS contributed to the formation of a continuous and compact char layer,exhibiting a tortuous effect by inhibiting heat diffusion and evaporation of volatile gaseous.In addition,the released crystal water from HNTs could dilute the combustible volatiles and then decline the combustion intensity.The tensile tests demonstrated that introduction of 2 wt%HNTs-POSS would enhance the maximum stress of TPU nanocomposite with a slight decrease of elongation at break.The combination of HNTs and POSS through the construction of effective interfacial interactions provides a feasible way to effectively enhance the fire safety of TPU nanocomposites without scarifying ductility.展开更多
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 na...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.展开更多
It is challenging for antibacterial polymer scaffolds to achieve the drug sustained-release through directly coating or blending.In this work,halloysite nanotubes(HNTs),a natural aluminosilicate nanotube,were utilized...It is challenging for antibacterial polymer scaffolds to achieve the drug sustained-release through directly coating or blending.In this work,halloysite nanotubes(HNTs),a natural aluminosilicate nanotube,were utilized as a nano container to load nano silver(Ag)into the lumen through vacuum negativepressure suction&injection and thermal decomposition of silver acetate.Then,the nano Ag loaded HNTs(HNTs@Ag)were introduced to poly-l-lactic acidide)(PLLA)scaffolds prepared by additive manufacturing for the sustained-release of Ag^+.Acting like a’shield’,the tube walls of HNTs not only retarded the erosion of external aqueous solution on internal nano Ag to generate Ag^+but also postponed the generated Ag^+to diffuse outward.The results indicated the PLLA-HNTs@Ag nanocomposite scaffolds achieved a sustained-release of Ag^+over 28 days without obvious initial burst release.Moreover,the scaffolds exhibited a long-lasting antibacterial property without compromising the cytocompatibility.Besides,the degradation properties,biomineralization ability and mechanical properties of the scaffolds were increased.This study suggests the potential application of inorganic nanotubes as drug carrier for the sustained-release of functional polymer nanocomposite scaffolds.展开更多
All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrol...All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrolyte still faces challenges.In this study,a thin solid polymer composite electrolyte(SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane(TPU),lithium salt(LiTFSI or LiFSI),and halloysite nanotubes(HNTs) in a porous framework of polyethylene separator(PE)(TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE).The composition,electrochemical performance,and especially the effect of anions(TFSI-and FSI-) on cycling performance are investigated.The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V(vs.Li+/Li) at 60℃,respectively.Reduction in FSI-tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode,thus enhancing the interfacial stability.As a result,cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase(SEI) with a distinct decrease in charge-transfer resistance during cycling.Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately39 mV at a current density of 0.1 mA cm-2,while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE.The initial capacities of NCMITPU-HNTs-LiTFSIPEILi and NCMITPU-HNTs-LiFSI-PEILi cells were 149 and 114 mAh g-1,with capacity retention rates of 83.52% and89.99% after 300 cycles at 0.5 C,respectively.This study provides a valuable guideline for designing flexible SPCE,which shows great application prospect in the practice of ASSLB.展开更多
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 ...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.展开更多
文摘Introducing inorganic nanomaterials into a polymer matrix greatly improves the anticorrosion performance of epoxy coatings(EP);however,poor compatibility between the materials can limit the improvement in properties.In this work,based on the high interface compatibility of two-dimensional(2D)Co_(2)(OH)_(2)BDC(BDC=1,4-benzenedicarboxylate)in the epoxy coating that we reported in previous work,we fabricated a 2D Co_(2)(OH)_(2)BDC-halloysite nanotube(HNT)nanocomposite have a structure consisting of alternating of nanosheets and nanotube by in situ synthesis.The nanocomposite was characterized by Fourier transform infrared spectroscopy,X-ray diffraction,and scanning electron microscopy.The mechanical and anticorrosion performance of the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was evaluated by mechanical tests and electrochemical impedance spectroscopy spectra.Compared with a conventional unreinforced epoxy coating,the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating had higher mechanical strength and toughness,and the low-frequency impedance modulus of 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was increased by three orders of magnitude,demonstrating the high corrosion resistance of our reinforced coating.
基金supported by the Excellent Youth Foundation of Henan Scientific Committee,China(222300420018)Key Scientific Research Projects in Universities of Henan Province,China(21zx006)。
文摘Layered assembled membranes of 2D leaf-like zeolitic imidazolate frameworks(ZIF-L)nanosheets have received great attention in the field of water treatment due to the porous structure and excellent antibacterial ability,but the dense accumulation on the membrane surface and the low permeate flux greatly hinder their application.Herein,we synthesized m HNTs(modified halloysite nanotubes)/ZIF-L nanocomposites on modified m HNTs by in situ growth method.Interestingly,due to the different size of m HNTs and ZIF-L,m HNTs were packed in ZIF-L nanosheets.The hollow m HNTs provided additional transport channels for water molecules,and the accumulation of the ZIF-L nanosheets was decreased after assembling m HNTs/ZIF-L nanocomposites into membrane by filtration.The prepared m HNTs/ZIF-L membrane presented high permeate flux(59.6 L·m^(-2)·h^(-1)),which is 2-4 times of the ZIF-L membranes(14.8 L·m^(-2)·h^(-1)).Moreover,m HNTs/ZIF-L membranes are intrinsically antimicrobial,which exhibit extremely high bacterial resistance.We provide a controllable strategy to improve 2D ZIF-L assembles,and develops novel membranes using 2D package structure as building units.
文摘Halloysite nanotubes were used as nanocontainers to hold corrosion inhibitors such as Ce^(3+)-Zr^(4+),2-mercaptobenzothiazole and 8-hydroxyquinoline in their lumen.An acid assisted etching of the nanotubes was carried out with a view to increase the lumen diameter and thereby,increase the amount of loading of the corrosion inhibitor.The morphology of as-received and etched halloysite nanotubes was ob-served using TEM analysis.The loading of corrosion inhibitors was confirmed using SEM-EDS and BET analysis.Polymeric microcapsules were used as capping agents for the ends of the loaded HNTs following which,they were dispersed into a hybrid sol-gel silica matrix.Dip coating method was used to generate coatings on AZ91D substrates followed by heat treatment at 130℃ for 1 h.The release rate kinetics of corrosion inhibitors from as-received and etched nanotubes was investigated in buffer solutions of 3.5 wt%NaCl at different pH.The release mechanism of corrosion inhibitors from the HNT lumen was validated using various semi-empirical models.Coatings were also evaluated for their corrosion protection ability using electrochemical techniques after exposure to 3.5 wt%NaCl solution for 120 h.Coatings generated using Ce^(3+)-Zr^(4+)loaded into as-received halloysite nanotubes have shown more effective corrosion protection when compared to other corrosion inhibitors after 120 h exposure to the corrosive medium.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(No.2018R1C1B6004689)the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(No.2020R1I1A306182111)the Electronics and Telecommunications Research Institute(ETRI)grant funded by the Korean government(21ZB1200,Development of ICT Materials,Components and Equipment Technologies)。
文摘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.
基金Universiti Sains Malaysia for Bridging Fund(grant No.304.PBAHAN.6316090)
文摘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.
基金supported by the National Natural Science Foundation of China(Nos.50573021 and 50603005)
文摘A natural nanotubular material,halloysite nanotubes(HNTs),was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube(SBR/m-HNT) nanocomposites.Complex of resorcinol and hexamethylenetetramine (RH) was used as the interfacial modifier.The structure,morphology and mechanical properties of SBR/m-HNT nanocomposites,especially the interfacial interactions,were investigated.SEM and TEM observations showed that RH can not only facilitate the dispersion and orientation of HNTs in SBR matrix ...
文摘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.
基金supported by the National Natural Science Foundation of China (Grant No. 41302030)Fundamental Research Project of Chinese Academy of Geological Sciences (Grant No. YYWF201619)+1 种基金National Key R&D Program of China (Grant No.2016YFC0600605)China Geological Survey Program (DD20179152)
文摘1 Introduction The weathered crust rare earth deposits is one of the most significant rare earth deposits,which are mostly distributed in southern China,especially in the south of Jiangxi province(Chi et al.,2007).The compositions of these deposits,which are weathered from igneous rocks such as granite through biological,physical or
文摘The environmental stress cracking resistance of halloysite nanoclay-polyester nanocomposites was investigated using fracture mechanics approach. The incorporation of halloysite nanoclay was found to improve the environmental stress cracking resistance of the nano-composites. The storage modulus of nano-composites measured by dynamic mechanical analysis increased remarkably as a function of halloysite nanoclay content. At 0.7 wt% nanoclay, the Tg improved from 72°C to 76°C. The fracture toughness increased up to 33% and time to failure improved 155% with the addition of 0.7 wt% of halloysite nanoclay. The maximum microhardness was found 119% higher for the same nano-filler concentration compared to monolithic polyester. The reinforcement with 1 wt% showed lower fracture toughness due to agglomerations of nanoclay which act as flaws. The presence of agglomerates weakened the bond between nano-particles and matrix hence reduces the environmental stress cracking resistance by halloysite nanoclay reinforcement.
文摘The diffusion permeability through new hybrid materials based on a Nafion-type membrane (MF- 4SC) and nanotubes of halloysite is investigated using the Nernst-Planck approach. A method of quantitative evaluation of physicochemical parameters (averaged and individual diffusion coefficients and averaged distribution coefficients of ion pairs in the membrane) of system “electrolyte solution—ion-exchange membrane—water”, which was proposed earlier, is further developed. The parameters of hybrid membranes on the base of MF-4SC and nanotubes of halloysite (5% wt and 8% wt) are obtained from experimental data on diffusion permeability of NaCl solutions using theoretical calculations. New model of three-layer membrane system can be used for refining calculated results with taking into account both diffusive layers. It is shown that adding of halloysite nanotubes into the membrane volume noticeably affects exchange capacity as well as structural and transport characteristics of original perfluorinated membranes. Hybrid membranes on the base of MF-4SC and halloysite nanotubes can be used in fuel cells and catalysis.
文摘In this study,we demonstrated the effects of chemical treatments for Halloysite nanotubes(HNTs)under acid and alkaline conditions using sulfuric acid and sodium hydroxide.XRD results indicate that alkaline treatment destroyed the crystalline structure and morphology for HNTs because the XRD spectrum shows the typical peaks for montmorillonite.For the acid treatment using H2SO4,XRD spectrum indicates an intensity reduction for the peak(001)showing a lower concentration of aluminium in the structure.Diffuse reflectance analysis shows a reduction of 40 and 15%for reflectance with H2SO4 and NaOH treatments respectively.A terephthalic acid adsorption test was realized with the HNTs,modified halloysites(HNT-H2SO4)and(HNT-NaOH)samples with a kinetic study and it was quantified with UV spectroscopy at 240 nm where results shown a lower adsorption for HNTs treated with H2SO4 in comparison with alkaline treatment and not treated HNT.A decrease of 58%±0.3was achieved with the sulfuric acid treatment with not crystalline structure modification using ICP technique to quantify the sample compositions.
文摘In this work a three-dimensional, time-quantified Monte Carlo model that efficiently describes diffusion through and from nanotubes is implemented. Controlled delivery from Halloysite Nano-tubes (HNT) is modeled based on interactions between the HNT’s inner wall and the nanoparticles (NPs) and among NPs themselves. The model was validated using published experimental data. The validated model is then used to study the effect of multiples parameter like HNT diameter and length, particle charge, and ambient temperature on the release of encapsulated NPs. The results show that release profiles depend on the size distribution of the HNT batch used for the experiment, as delivery is sensitive to HNT lumen and length. A very good agreement with the experiment is observed when a weighted average release profile is compared to the experimental profile. Although the NP dynamics is temperature-dependent, the effect is minimum within the range of temperatures relevant to biomedical applications, but will be relevant for other applications at temperatures significantly different from room temperature. This model can be used to predict the best conditions for a particular delivery need.
基金supported by the National Key R&D Program of China (2022YFE0201300)the China Postdoctoral Science Foundation (2022M712948)+2 种基金the CUG Scholar Scientific Research Funds at China University of Geosciences (Wuhan) (2019152)the Fundamental Research Funds for the Central Universities at China University of Geosciences (Wuhan)the National Science Fund for Distinguished Young Scholars (51225403)。
文摘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.
基金The authors acknowledge the financial support of the National Natural Science Foundation of China(Nos.52075523 and 52005487).
文摘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.
基金This work was supported by the National Natural Science Foundation of China （Nos. 41572036 and 51225403）, the Hunan Provincial Science and Technology Project （Nos. 2016RS2004 and 2015TP1006） and the National ＂Ten Thousand Talents Program＂ in China. Computing resources were provided by High Performance Computing Centre of Central South University and the National Supercomputing Center of China in Shenzhen. We acknowledge Yalin Xia, Huilin Lun and Binbin Guo for their kind help in sample preparation, characterization and drug loading experiment.
基金financially supported by the National Key Research and Development Program of China(No.2016YFB0302300)the International Collaboration Programs of Guangdong Province(No.2020A0505100010)+4 种基金the Fundamental Research Funds for the Central Universities(No.2019MS062)the Natural Science Foundation of Guangdong Province(No.2021A1515012425)the Overseas Famous Scholar Funds of Guangdong Province(No.2020A1414010372)City University of Hong Kong(No.9678103)the Opening Project of Key Laboratory of Polymer Processing Engineering(South China University of Technology),Ministry of Education of China(No.KFKT1904)。
文摘Halloysite nanotubes(HNTs)have been considered as a promising flame retardant fillers for polymers.In this work,the polyhedral oligomericsilsesquioxane(POSS)containing amino group was covalently grafted on the surface of HNTs with 3-(2,3-epoxypropoxy)propytrimethoxysilane as a chemical bridge.The POSS modified HNTs(HNTs-POSS)dispersed uniformly in the thermoplastic polyurethane(TPU)matrix and endowed TPU nanocomposites with enhanced tensile properties and fire safety.Cone calorimeter tests revealed that the introduction of 2 wt%HNTs-POSS to TPU matrix remarkably reduced the peak of heat release rate(PHRR)and total heat release(THR)by 60.0%and 18.3%,respectively.In addition,the peak CO production rate and total smoke release(TSR)could be significantly suppressed by the addition of HNTsPOSS.The well dispersed HNTs in combination with the ceramified silicon network from the thermal decomposition of POSS contributed to the formation of a continuous and compact char layer,exhibiting a tortuous effect by inhibiting heat diffusion and evaporation of volatile gaseous.In addition,the released crystal water from HNTs could dilute the combustible volatiles and then decline the combustion intensity.The tensile tests demonstrated that introduction of 2 wt%HNTs-POSS would enhance the maximum stress of TPU nanocomposite with a slight decrease of elongation at break.The combination of HNTs and POSS through the construction of effective interfacial interactions provides a feasible way to effectively enhance the fire safety of TPU nanocomposites without scarifying ductility.
基金National Natural Science Foundation of China(No.51003091)the Applied Basic Foundation of Yunnan Province(No.2013FB002)+2 种基金the Education Research Foundation of Yunnan Province(Nos.2013Y361,2010Y240)the Research Foundation of Yunnan University(No.2009B06Q)the Backbone Teacher Training Program of Yunnan University(No.XT412003).
文摘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.
基金the National Natural Science Foundation of China(Nos.51935014,51905553,81871494,81871498,51705540)the Hunan Provincial Natural Science Foundation of China(Nos.2019JJ50774,2018JJ3671 and 2019JJ50588)+5 种基金the Jiang Xi Provincial Natural Science Foundation of China(No.20192ACB20005)the Guangdong Province Higher Vocational Colleges&Schools Pearl River Scholar Funded Scheme(2018)the Open Sharing Fund for the Large-scale Instruments and Equipments of Central South Universitythe Project of Hunan Provincial Science and Technology Plan(No.2017RS3008)the Hunan Provincial Innovation Foundation For Postgraduate(No.CX2018B093)the Fundamental Research Funds for the Central Universities of Central South University(Nos.2018zzts022 and 2019zzts725)。
文摘It is challenging for antibacterial polymer scaffolds to achieve the drug sustained-release through directly coating or blending.In this work,halloysite nanotubes(HNTs),a natural aluminosilicate nanotube,were utilized as a nano container to load nano silver(Ag)into the lumen through vacuum negativepressure suction&injection and thermal decomposition of silver acetate.Then,the nano Ag loaded HNTs(HNTs@Ag)were introduced to poly-l-lactic acidide)(PLLA)scaffolds prepared by additive manufacturing for the sustained-release of Ag^+.Acting like a’shield’,the tube walls of HNTs not only retarded the erosion of external aqueous solution on internal nano Ag to generate Ag^+but also postponed the generated Ag^+to diffuse outward.The results indicated the PLLA-HNTs@Ag nanocomposite scaffolds achieved a sustained-release of Ag^+over 28 days without obvious initial burst release.Moreover,the scaffolds exhibited a long-lasting antibacterial property without compromising the cytocompatibility.Besides,the degradation properties,biomineralization ability and mechanical properties of the scaffolds were increased.This study suggests the potential application of inorganic nanotubes as drug carrier for the sustained-release of functional polymer nanocomposite scaffolds.
基金financially supported by the National Natural Science Foundation of China(No.21673051)the Department of Science and Technology of Guangdong Province,China(No.2019A050510043)。
文摘All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrolyte still faces challenges.In this study,a thin solid polymer composite electrolyte(SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane(TPU),lithium salt(LiTFSI or LiFSI),and halloysite nanotubes(HNTs) in a porous framework of polyethylene separator(PE)(TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE).The composition,electrochemical performance,and especially the effect of anions(TFSI-and FSI-) on cycling performance are investigated.The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V(vs.Li+/Li) at 60℃,respectively.Reduction in FSI-tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode,thus enhancing the interfacial stability.As a result,cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase(SEI) with a distinct decrease in charge-transfer resistance during cycling.Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately39 mV at a current density of 0.1 mA cm-2,while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE.The initial capacities of NCMITPU-HNTs-LiTFSIPEILi and NCMITPU-HNTs-LiFSI-PEILi cells were 149 and 114 mAh g-1,with capacity retention rates of 83.52% and89.99% after 300 cycles at 0.5 C,respectively.This study provides a valuable guideline for designing flexible SPCE,which shows great application prospect in the practice of ASSLB.
基金This work was financially supported by Natural Science Foundation of China(No.51873178)the Opening Project of State Key Laboratory of Polymer Materials Engineering(Sichuan University)(No.sklpme2020-4-03)+1 种基金Qing Lan Project of Yangzhou University and Jiangsu Province,High-end Talent Project of Yangzhou University,the Priority Academic Program Development of Jiangsu Higher Education Institutions,Postgraduate Research&Practice Innovation Program of Jiangsu province(No.KYCX18_2364,No.KYCX20_2977)Outstanding Doctoral Dissertation Fund of Yangzhou University.
文摘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.
