RSC Advances
·
2019
·Vol. 9
·期 67
·38935-38942
·
IF 3.049
Liting Zhang,Wen Tang,Tonghao Ma,Lina Zhou,Chenggong Hui,Xiaoli Wang,Ping Wang,Changai Zhang,Chao Chen
Halloysite nanotubes (HNTs) have been pursued as promising carriers for enzyme immobilization, but the lack of functional groups severely limits their applications. Herein, we reported a simple tannic acid (TA)-mediated surface modification strategy for the fabrication of HNT-based efficient enzyme immobilization supports. Particularly, TA was first self-polymerized and deposited onto the surface of HNTs to form a thin active film via a mussel-inspired method, and the model enzyme laccase was directly conjugated via the Michael addition and/or Schiff base condensation between quinone groups on poly(tannic acid) layer surfaces and exposed amine groups on laccase surfaces. Under the optimum conditions, this newly fabricated support retained good enzyme-loading and activity recovery properties with 197.9 mg protein per gram of support and 55.4% of activity recovery being achieved. In addition, this immobilized laccase was less influenced by pH, temperature, and inhibitor changes and exhibited higher storage stability than free laccases as more than 70% of initial activity was retained by the immobilized laccase, while less than 30% was retained for free laccase after one-month storage at 4 °C. Finally, a higher bisphenol-A (BPA) removal efficiency and more reuse cycles were demonstrated for immobilized laccases. As a result, this TA-mediated surface modification is a simple and green method for biological macromolecule immobilization on HNTs in one step.
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PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 13.2
Ming Huang,Luying Zeng,Rawil Fakhrullin,Mingxian Liu
The use of nanomaterials in seed coating offers great advantages, such as increasing the resistance of seeds to physical damage, promoting seed growth, and delivering essential nutrients to seeds. Herein, a functional seed coating material is obtained by anchoring selenium (Se) nanoparticles on the surface of polydopamine (PDA)-modified halloysite nanotubes (HNTs) using an in-situ synthesis method. The SA/HNTs-PDA@Se (SHPS) coating is obtained by mixing HNTs-PDA@Se with sodium alginate (SA) solution as the film-forming agent. HNTs act as supporter for Se nanoparticles to prohibit their aggregation as well as a controlled release for the Se elements. Wheat seeds are selected as a plant model to be coated, and the coating can be formed using Ca 2+ as interfacial crosslinker. HNTs improve the affinity of the composite coating solution on the smooth surface for seeds, as well as improving the hydrophilicity and mechanical property of the coating film. The composite coating improves the resistance of the seeds to physical damage, and the water absorption and water retention capacity. The SHPS coating does not affect seed germination, but rather improves the development of root systems in coated seeds. Seed coating with a nano-Se increases Se content in wheat leaves to 277.8 μg/kg, and the crop become a Se-enriched crop, which improves the quality of the crop. This work extends the application of natural HNTs in functional seed coating technique, which contributes to the research and development of controlled micronutrient delivery system using nanomaterials and nanotechnology.
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RSC Advances
·
2018
·Vol. 8
·期 60
·34232-34240
·
IF 2.936
Peiqi Lun,Zilong Chen,Zhenbao Zhang,Shaozao Tan,Dengjie Chen
Solid composite electrolytes have gained increased attention, thanks to the improved safety, the prolonged service life, and the effective suppression on the lithium dendrites. However, a low ionic conductivity (<10−5 S cm−1) of solid composite electrolytes at room temperature needs to be greatly enhanced. In this work, we employ natural halloysite nanotubes (HNTs) and poly(vinylidene fluoride) (PVDF) to fabricate composite polymer electrolytes (CPEs). CPE-5 (HNTs 5 wt%) shows an ionic conductivity of ∼3.5 × 10−4 S cm−1, which is ∼10 times higher than the CPE-0 (without the addition of HNTs) at 30 °C. The greatly increased ionic conductivity is attributed to the negatively-charged outer surface and a high specific surface area of HNTs, which facilitates the migration of Li+ in PVDF. To make a further illustration, a solid-state lithium-ion battery with CPE-5 electrolyte, LiMn2O4 cathode and Li metal anode was fabricated. An initial discharge capacity of ∼71.9 mA h g−1 at 30 °C in 1C is obtained, and after 250 cycles, the capacity of 73.5 mA h g−1 is still maintained. This study suggests that a composite polymer electrolyte with high conductivity can be realized by introducing natural HNTs, and can be potentially applied in solid-state lithium-ion batteries.
研究领域:
材料科学
·
能源存储
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2022
·Vol. 139
·期 35
·e52863
·
IF 3.057
Xiaofei Yan,Lixiang Song,Chenyan Zhu,Jiawei Li,Dongming Qi
It has become a hotspot that microfibrils with a high aspect ratio have a good reinforcement effect on the composite fibers. To prepare the micro-fibrillation composite fibers with excellent performance and good dispersity, poly (styrene-methyl methacrylate)@grafted halloysite nanotubes(PSM@PMHNTs) microspheres were prepared by suspension polymerization method, and the PSM@PMHNTs reinforced composite fibers were prepared by simple blending with polymethylmethacrylate (PMMA). The structure and mechanical properties of the composite fibers were studied by transmission electron microscopy, scanning electron microscopy, dynamic thermo-mechanical analysis, and universal material testing machine. The results showed that polystyrene grafted halloysite nanotubes (PMHNTs) had good hydrophobicity and were successfully embedded in poly (styrene-methyl methacrylate) (PSM). The mechanical performance of microfibril composite fiber with PSM@PMHNTs is better when compared that with PMHNTs and PSM, and the elongation at break of the composite fiber has dramatically increased by 120.90% compared to that of pure PMMA. In addition, the mechanical properties of the composite fibers were increased firstly and then decreased with the increase of PMHNTs contents and draft ratios, while the glass transition temperature of the composite fibers had no obvious changes. The composite fiber has the best mechanical properties when the content of PMHNTs is 1.0 wt% and the draft ratio is 6, and the tensile strength and elongation at break were 26.94% and 256.36% higher than that of pure PMMA, respectively.
研究领域:
高分子材料科学
·
纳米复合材料
·
纤维增强技术
·
材料化学
·
高分子物理
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DOI
高影响因子
SYNTHETIC METALS
·
2026
·
IF 4.5
Yang Zhu,Wentao Mei,Bo Xu,Juan Huang,Ming Liu,Jiayou Ji,Liang Li,Huabo Huang
HNT enables 3D porous network and suppresses PANI aggregation. • Synergistic enhancement of mechanical and electrochemical properties. • High areal capacitance (285 mF cm –2 ) and energy density (25.33 µWh cm –2 ). • Excellent cycling stability (85.11% after 10,000 cycles) and flexibility. With the rapid advancement of flexible electronics, the demand for energy storage devices capable of withstanding mechanical deformation has become increasingly pressing. To address the challenges of polyaniline agglomeration in conductive polymer hydrogels and the difficulty of synergistically enhancing both mechanical and electrochemical properties, this study presents a PVA/PANI/HNT composite hydrogel fabricated by incorporating hollow nanotubular halloysite (HNT), which not only suppresses PANI agglomeration through electrostatic interactions but also serves as a nanoscale scaffold to construct a 3D nanoporous network structure, significantly enhancing the specific surface area, mechanical strength, and electron/ion transport of the hydrogel. The resulting solid-state supercapacitor exhibits exceptional electrochemical performance, including an areal capacitance of 285 mF cm –2 , energy and power densities of 25.33 µWh cm –2 and 3991.65 µW cm –2 , respectively, and a capacitance retention of 85.11% after 10,000 charge–discharge cycles. Furthermore, the device maintains stable electrochemical performance under 180° bending conditions, demonstrating promising application potential in flexible wearable electronics. Download: Download high-res image (334KB) Download: Download full-size image
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高影响因子
CLAYS AND CLAY MINERALS
·
2026
·
IF 2.8
Yuqi Yao,Shiyong Sun,Xingyun Yang,Pan Zhou,Haoming Tang,Shanshan Pu
Halloysite nanotubes (HNTs), naturally abundant clay minerals with unique tubular
structures and biocompatibility, offer significant potential as an enzyme immobilization
matrix. Conventional functionalization methods often involve energy-intensive
processes or compromise enzyme activity, however. The study offers an approach to
functionalizing HNTs via alkali activation and polydopamine (PDA) coating for
efficient immobilization of β-glucosidase (BG). Alkali treatment enhanced surface
hydroxyl density and defect sites, while PDA deposition through mild oxidative
polymerization provided a reactive interface for covalent enzyme conjugation mediated
by N-(3-Dimethylaminopropyl)-N’-ethylcarbodiimide hydrochloride (EDC)
crosslinking. Structural characterization (XRD, FTIR, SEM-EDS) confirmed
successful PDA coating and enzyme binding while preserving the crystalline integrity
of HNTs. At an optimal loading of 167mg·g
–1
support, the immobilization efficiency was
83% with retained activity. The immobilized BG not only exhibited optimal catalytic
performance at pH 6.0 and 60°C but also enhanced stability against pH/temperature
fluctuations through immobilization. Kinetic analysis revealed a 39% increase in Vmax
(4.73 vs. 3.40 mM·L
–1
·min–1
) and sustained substrate affinity (Km=10.4 mM·L
–1
). The
biocatalyst retained ≧84% activity after 30 days of storage at 4℃ and 53% activity
over six reuse cycles, attributed to the rigid enzyme conformation stabilized by covalent
PDA coupling and HNTs confinement. The research results presented are expected to
broaden the application scope of halloysite in the field of enzyme catalysis and provide
a feasible solution for improving the catalytic stability of β-glucosidase.
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高影响因子
Minerals
·
2025
·Vol. 15
·期 7
·739
·
IF 2.2
Ying Li,Xingzhong Yuan,Xiuying Wei,Yao Long
Halloysite nanotubes, a naturally occurring nanomaterial with a unique tubular morphology, have shown considerable potential for heavy metal remediation. However, significant inconsistencies in the reported maximum adsorption capacities (qmax) for heavy metal ions—such as Pb2+, which ranges from 7.5 to 84.0 mg/g with a coefficient of variation (CV) of 68%—have severely hindered both scientific understanding and practical application of this promising material. To address this critical knowledge gap, we conducted a reassessment using carefully selected halloysite specimens from three geologically distinct deposits (Utah, USA; Henan and Yunnan, China). Under rigorously controlled experimental conditions, we precisely quantified the adsorption capacities of halloysite for Cd2+, Zn2+, and Pb2+. Through an integrated multi-technique characterization approach involving XRF, XRD, FTIR, TEM, and BET analyses, we identified two fundamental crystallochemical parameters that govern the adsorption performance of halloysite: the degree of lattice substitution and the density of surface hydroxyl groups. Our findings reveal that optimal heavy metal adsorption occurs in halloysite with lower lattice substitution and higher surface hydroxyl density. This work not only provides a reliable range of adsorption capacities for halloysite but, more importantly, establishes a scientific foundation for optimizing the application of halloysite in heavy metal remediation.
研究领域:
环境科学
·
纳米材料
·
吸附
·
粘土矿物学
·
修复技术
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DOI
高影响因子
APPLIED CLAY SCIENCE
·
2025
·
IF 5.8
Yuqi Zhang,Yunan Zhong,Pengfei Zhang,Yang Zheng,Chunfang Du
Halloysite nanotubes (HNTs) served as the support and aluminum source for in-situ synthesizing CoAl 2 O 4 /HNTs (CAO/HNTs), which acted as an effective catalyst to activate peroxymonosulfate (PMS) for degrading tetracycline hydrochloride (TC). To achieve the optimal removal performance, various parameters were optimized. The final CAO/HNTs demonstrated a high degradation efficiency of 88 % toward TC within 40 min, which was 1.69 times as high as that of pure CAO. The existence of HNTs made CAO highly dispersed, increasing the number of exposed active sites and the contact opportunities between CAO and TC molecules, which enabled CAO to participate in the reaction more effectively and thus improved the degradation efficiency. Additionally, the formation of Co-O-Al bonds facilitated the growth of CAO into a three-dimensional (3D) spherical structure with more active sites other than the tetrahedral structure on HNTs. In the CAO/HNTs/PMS system, O 2 •– and 1 O 2 contributed mostly to the catalytic process. This work not only provides a novel catalyst for the treatment of antibiotic pollution, but also offers an innovative strategy for fabricating functional materials on the basis of chemical composition and morphology characteristics of natural minerals.
研究领域:
环境科学
·
纳米技术
·
催化
·
材料科学
·
化学工程
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高影响因子
Surfaces and Interfaces
·
2025
·
IF 6.3
Xinnian Meng,Jingqi Chen,Zeyang Liu,Yongming Tang
An important issue regarding halloysite nanotubes as inhibitor containers is the stimuli-responsive performance. A novel approach to constructing pH-sensitive halloysite nanocontainers is developed in this study. The silicate-mediated tannic acid complexes (Si-TA) are deposited on the etched halloysite nanotubes (EHNTs) loading Na 2 MoO 4 , endowing the Si-TA/Mo@EHNTs nanocontainers with the high pH-sensitivity. Both the release rate and ratio of the inhibitor increase with increasing pH. The sensitivity of the nanocontainers to the high pH value arises from the rapid hydrolysis of Si-TA encapsulation layers in the basic media. It is evidenced that gallic acid (GA), generated from the hydrolysis of the Si-TA complexes, can further dimerize into ellagic acid (EA) in the basic media. The smart epoxy coatings with the stimuli-responsive performance are prepared by incorporating the Si-TA/Mo@EHNTs nanocontainer, and exhibit better corrosion resistance compared with the epoxy coatings without the nanocontainers as well as directly incorporated with Na 2 MoO 4 . The elevated pH in the cathodic region of corrosion cell trigger the release of MoO 4 2- ions from the nanocontainers, inhibiting the corrosion of the exposed substrates effectively. Furthermore, the EA-Fe(III) depositions could be formed by the combination of the EA compounds from the damage of the encapsulation layers with the Fe 3+ ions, acting as the barrier on the exposed substrates to improve the corrosion resistance of the coating.
研究领域:
材料科学
·
纳米技术
·
表面工程
·
腐蚀科学
·
高分子科学
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DOI
高影响因子
DALTON TRANSACTIONS
·
2025
·
IF 3.3
Lan Yang,Qiyuan Lu,Xiao Zhou,Tao Yang,Chunfang Du
Adsorption is an effective strategy for treating water pollution and natural clay minerals-based materials display the great potential for removing pollutants from wastewater. In this paper, halloysite nanotubes (HNTs) modified with ethylenediaminetetraacetic acid (EDTA) were thermally treated to serve as supports for loading SnS2 to construct SnS2/HNTs(C) (SHCx-y). Methylene blue (MB) was selected as a target pollutant to examine the removal efficiency of the obtained adsorbents. SHC0.04-500 could remove more than 90 % of MB (50 mg∙L-1) within 18 min, which was 9 and 18 times higher than those of SnS2 and HNTs(C)-500, respectively. Moreover, the adsorbent SHC0.04-500 with good pH and temperature adaptability displayed the excellent adsorption performance toward cationic dyes and various antibiotics. The adsorption process of MB over SHC0.04-500 matched well with the Langmuir isotherm and pseudo-first-order kinetic model. The adsorption mechanism investigation suggested that the carbon layer on HNTs made the surface of SHC0.04-500 more negative, which mostly contributed to the improved adsorption performance. This work provides a low-cost, environmental-friendly, and efficient adsorbent for removing pollutants from wastewater, and contributes a new strategy to enhance the removal efficiency by a simple modification method.
研究领域:
环境科学
·
纳米技术
·
材料科学
·
水污染治理
·
吸附技术
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DOI
PubMed
高影响因子
ACS Applied Nano Materials
·
2024
·
IF 5.3
Hui Lin,Yandong Liu,Chenglong Hu,Xuefan Deng,Long Zhang,Shaoyun Chen,Haibo Zhang
In catalytic reactions, the diverse binding sites of nanometals located in nanomaterials considerably influence the activity of nanocatalysts. In this study, the special nanostructure and charge distribution of halloysite nanotubes (HNTs) incorporating a weak reducing agent closo-dodecaborate (closo-[B12H12]2–) were leveraged to immobilize Au nanoparticles (NPs) on the inner and outer surfaces of HNTs. The introduction of closo-[B12H12]2– into HNTs was achieved via vacuum extraction and acid immersion. Subsequently, nanocatalysts loaded with Au NPs on the diverse surfaces of the HNTs were obtained from a direct reaction with a KAuCl4 solution. The Au NPs loaded on the inner surface of the HNTs were found to have highly dispersed and exhibited excellent catalytic activity in the reduction of nitroaromatics. At room temperature, the Au NPs loaded on the inner surface of the HNTs with a mass fraction of 0.02% showed a high turnover frequency value of 47.28 min–1 in a model reaction of the catalytic reduction of 4-nitrophenol to 4-aminophenol and exhibited excellent stability in cycling tests. Therefore, this study provides a new approach for synthesizing nanocomposites for various practical applications.
研究领域:
材料科学
·
催化化学
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DOI
高影响因子
APPLIED CLAY SCIENCE
·
2024
·
IF 5.3
Yanan Wei,Yunlei Zhang
A novel halloysite (Hal) based acidic catalyst was synthesized by anchoring functional alkyl group and Cr site and catalyzed the selective conversion of mannose to 5-hydroxymethylfurfural (HMF) in NaCl-H 2 O/dimethyl sulfoxide/methyl isobutyl ketone (MIBK) biphasic system. Herein, adjusting the hydrophilicity/hydrophobicity of catalyst by modifying the octyl group can facilitate the HMF yield. The density functional theory (DFT) calculation and in-situ FT-IR results revealed that increasing the hydrophobicity of catalyst surface weakened the interaction between HMF, water molecule and acid sites and inhibited the rehydration of HMF. Moreover, the synergistic effect between Cr and sulfonic group active sites remarkedly promoted the isomerization of mannose to fructose and the dehydration of fructose to HMF, and the 48.1% yield of HMF was obtained. This study provides references for the high value conversion of hemicellulose with the high efficiency reaction system.
研究领域:
生物化学
·
催化化学
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高影响因子
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