Applied Clay Science最新文献

Novel extruded 3D printed potassium geopolymer composites containing chitosan 新型挤压3D打印含壳聚糖钾地聚合物复合材料

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-02-01 DOI: 10.1016/j.clay.2026.108144

Angelo Oliveira Silva , Marco D'Agostini , Dachamir Hotza , Paolo Colombo

This study investigates the development and characterization of 3D printed potassium-based geopolymers reinforced with chitosan, aiming to enhance material properties for environmental applications. The addition of chitosan improved the microstructure, pore morphology, dimensional accuracy, and rheological properties of the printed samples. X-ray diffraction (XRD) analysis confirmed successful geopolymerization across all chitosan concentrations, with shifts in the amorphous halo indicating structural transformation. Scanning electron microscopy (SEM) revealed fewer cracks and unreacted particles, leading to a dense, homogeneous matrix. Pore morphology analysis, using nitrogen physisorption, showed that the low-water (LW) system had a higher specific surface area (up to 111 m²/g) and more monodisperse mesopores, while the high-water (HW) system exhibited broader pore distributions and macroporosity. Dimensional accuracy analysis revealed deviations, with LW formulations maintaining better geometric precision. Chitosan improved the height-to-width ratios in the manufactured samples, enhancing printability. Rheological tests, including flow curves and amplitude sweeps, confirmed shear-thinning behavior and significant thixotropic recovery for the feedstock, ensuring shape retention and dimensional stability in 3D printing. These findings highlight the potential of chitosan-enhanced potassium-based geopolymers for environmental applications, especially in adsorption processes, by combining tunable porosity, high surface area, and improved printability for sustainable material solutions.

本研究研究了3D打印壳聚糖增强钾基地聚合物的开发和表征，旨在提高材料的环境应用性能。壳聚糖的加入改善了打印样品的微观结构、孔隙形态、尺寸精度和流变性能。x射线衍射（XRD）分析证实了壳聚糖在所有浓度下都能成功地聚合，无定形晕的变化表明结构发生了转变。扫描电子显微镜（SEM）显示较少的裂纹和未反应颗粒，导致致密，均匀的基体。利用氮气物理吸附法对孔隙形态进行分析，发现低水体系具有更高的比表面积（可达111 m2/g）和更多的单分散介孔，而高水体系具有更广泛的孔隙分布和宏观孔隙。尺寸精度分析揭示了偏差，LW配方保持了更好的几何精度。壳聚糖改善了制造样品的高宽比，提高了可印刷性。流变学测试，包括流动曲线和振幅扫描，证实了剪切变薄行为和明显的触变恢复，确保了3D打印的形状保持和尺寸稳定性。这些发现突出了壳聚糖增强钾基地聚合物在环境应用方面的潜力，特别是在吸附过程中，通过结合可调孔隙率、高表面积和改进的可印刷性来实现可持续材料解决方案。

{"title":"Novel extruded 3D printed potassium geopolymer composites containing chitosan","authors":"Angelo Oliveira Silva , Marco D'Agostini , Dachamir Hotza , Paolo Colombo","doi":"10.1016/j.clay.2026.108144","DOIUrl":"10.1016/j.clay.2026.108144","url":null,"abstract":"<div><div>This study investigates the development and characterization of 3D printed potassium-based geopolymers reinforced with chitosan, aiming to enhance material properties for environmental applications. The addition of chitosan improved the microstructure, pore morphology, dimensional accuracy, and rheological properties of the printed samples. X-ray diffraction (XRD) analysis confirmed successful geopolymerization across all chitosan concentrations, with shifts in the amorphous halo indicating structural transformation. Scanning electron microscopy (SEM) revealed fewer cracks and unreacted particles, leading to a dense, homogeneous matrix. Pore morphology analysis, using nitrogen physisorption, showed that the low-water (LW) system had a higher specific surface area (up to 111 m<sup>2</sup>/g) and more monodisperse mesopores, while the high-water (HW) system exhibited broader pore distributions and macroporosity. Dimensional accuracy analysis revealed deviations, with LW formulations maintaining better geometric precision. Chitosan improved the height-to-width ratios in the manufactured samples, enhancing printability. Rheological tests, including flow curves and amplitude sweeps, confirmed shear-thinning behavior and significant thixotropic recovery for the feedstock, ensuring shape retention and dimensional stability in 3D printing. These findings highlight the potential of chitosan-enhanced potassium-based geopolymers for environmental applications, especially in adsorption processes, by combining tunable porosity, high surface area, and improved printability for sustainable material solutions.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"285 ","pages":"Article 108144"},"PeriodicalIF":5.8,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146090768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Impact of chemical, textural and swelling properties of bentonite on the adsorption of trimethoprim and chlorphenamine from water 膨润土的化学性质、结构及溶胀特性对水中吸附甲氧苄啶和氯苯那敏的影响

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-29 DOI: 10.1016/j.clay.2026.108143

Uziel Ortiz-Ramos , Roberto Leyva-Ramos , Esmeralda Mendoza-Mendoza , Francisco Carrasco-Marin , Génesis Derith Valdez-García , Antonio Aragon-Piña , Carolina Vazquez-Mendoza

The influence of textural, chemical, and swelling properties of bentonite toward trimethoprim (TMP) and chlorphenamine (CPA) adsorption was investigated. Samples of bentonite and bentonite saturated with different uptakes of these pharmaceuticals were characterized by N₂ physisorption, Zeta potential, SEM, and XRD, and the uptake of cations exchanged was assessed. TMP and CPA were adsorbed within bentonite mesopores, causing pore blockage. Adsorption modified the surface charge, making it less negative as TMP and CPA uptake increased. XRD patterns showed that the d₀₀₁-value expanded from 1.50 to 1.70 nm as TMP uptake increased, while no significant shift was observed for CPA. These values were consistent with the molecular sizes of both compounds, suggesting intercalation within the interlayer space of bentonite in different orientations. Cation exchange occurred with an approximate 1:1 ratio of cations exchanged. Adsorption capacities were strongly influenced by pH. Maximum uptake adsorbed was attained at pH 5 for TMP (186.6 mg/g) and pH 9 for CPA (159.8 mg/g), diminishing at higher pH. Ionic strength emphasized the role of electrostatic attractions in the adsorption mechanisms, while solution temperature had negligible effects. Reversibility studies revealed that adsorption was governed by physical and chemical interactions and demonstrated that bentonite could be reused for at least 5 cycles with adsorption percentages remaining above 85%. Experiments in wastewater treatment plant effluent confirmed effective adsorption under realistic conditions, with TMP removal being limited by speciation at pH > 7.16 and CPA efficiently adsorbed, also improving general water quality parameters.

研究了膨润土的结构、化学性质和溶胀性质对甲氧苄啶和氯苯那明吸附的影响。采用N2吸附、Zeta电位、SEM、XRD等方法对膨润土和不同吸收量的膨润土样品进行了表征，并对交换阳离子的吸收量进行了评价。TMP和CPA在膨润土介孔内吸附，造成孔隙堵塞。吸附改变了表面电荷，随着TMP和CPA吸收量的增加，表面电荷的负电荷减少。XRD谱图显示，随着TMP吸收量的增加，d001值从1.50 nm增大到1.70 nm，而CPA的d001值变化不明显。这些值与两种化合物的分子大小一致，表明膨润土在不同取向的层间空间内插入。阳离子交换以大约1:1的比例发生。吸附量受pH影响较大，TMP在pH 5时吸附量最大（186.6 mg/g）， CPA在pH 9时吸附量最大（159.8 mg/g）， pH越高吸附量越小。离子强度强调静电吸引在吸附机制中的作用，而溶液温度对吸附机制的影响可以忽略不计。可逆性研究表明，膨润土的吸附受物理和化学相互作用的支配，并且可以重复使用至少5次，吸附率保持在85%以上。污水处理厂出水实验证实了在现实条件下的有效吸附，在pH >； 7.16时，TMP的去除受到形态的限制，CPA的有效吸附也改善了一般水质参数。

{"title":"Impact of chemical, textural and swelling properties of bentonite on the adsorption of trimethoprim and chlorphenamine from water","authors":"Uziel Ortiz-Ramos , Roberto Leyva-Ramos , Esmeralda Mendoza-Mendoza , Francisco Carrasco-Marin , Génesis Derith Valdez-García , Antonio Aragon-Piña , Carolina Vazquez-Mendoza","doi":"10.1016/j.clay.2026.108143","DOIUrl":"10.1016/j.clay.2026.108143","url":null,"abstract":"<div><div>The influence of textural, chemical, and swelling properties of bentonite toward trimethoprim (TMP) and chlorphenamine (CPA) adsorption was investigated. Samples of bentonite and bentonite saturated with different uptakes of these pharmaceuticals were characterized by N<sub>2</sub> physisorption, Zeta potential, SEM, and XRD, and the uptake of cations exchanged was assessed. TMP and CPA were adsorbed within bentonite mesopores, causing pore blockage. Adsorption modified the surface charge, making it less negative as TMP and CPA uptake increased. XRD patterns showed that the <em>d</em><sub>001</sub>-value expanded from 1.50 to 1.70 nm as TMP uptake increased, while no significant shift was observed for CPA. These values were consistent with the molecular sizes of both compounds, suggesting intercalation within the interlayer space of bentonite in different orientations. Cation exchange occurred with an approximate 1:1 ratio of cations exchanged. Adsorption capacities were strongly influenced by <em>pH</em>. Maximum uptake adsorbed was attained at <em>pH</em> 5 for TMP (186.6 mg/g) and <em>pH</em> 9 for CPA (159.8 mg/g), diminishing at higher <em>pH</em>. Ionic strength emphasized the role of electrostatic attractions in the adsorption mechanisms, while solution temperature had negligible effects. Reversibility studies revealed that adsorption was governed by physical and chemical interactions and demonstrated that bentonite could be reused for at least 5 cycles with adsorption percentages remaining above 85%. Experiments in wastewater treatment plant effluent confirmed effective adsorption under realistic conditions, with TMP removal being limited by speciation at <em>pH</em> > 7.16 and CPA efficiently adsorbed, also improving general water quality parameters.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108143"},"PeriodicalIF":5.8,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Evolution of thermo-hydro-mechanical behaviour of bentonite buffer at high temperature 高温下膨润土缓冲液热-水-力学行为的演化

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-26 DOI: 10.1016/j.clay.2026.108128

Alex Spetz , Daniel Malmberg , Chang Seok Kim

The HotBENT experiment at the Grimsel Test Site investigates the Thermo-Hydro-Mechanical (THM) behaviour of bentonite clay at temperatures exceeding 100 °C. It consists of four heaters with a temperature of between 175 °C and 200 °C, encapsulated in two types of bentonites, Na dominated Wyoming bentonite and a Mg/Ca dominated BCV bentonite. Complementary to the field test, a multi-team modelling platform was established to develop numerical models of the experiment. This work presents the authors contribution to that platform, focusing on comparing how two different hydraulic parameterizations of Wyoming bentonite affected the numerical results compared with experimental measurements. The first parameterizations consisted of parameters provided to the HotBENT modelling platform and the second setup was based on parameters used in previous simulations of Wyoming bentonite, in for example, the license application for the Swedish nuclear waste repository.

2D axisymmetric THM simulations were carried out using COMSOL Multiphysics® and simulated the evolution during the first five years. Both parameter setups could successfully reproduce the general evolution in the test in terms of temperature and pore pressure evolution. However, significant differences could be seen in the modelled relative humidity (RH) evolution and dry density state.

The results highlight the importance of parameter selection when modelling coupled THM processes and the importance of using experimentally validated data.

Grimsel试验场的HotBENT实验研究了膨润土在温度超过100°C时的热-水-力学（THM）行为。它由四个温度在175℃至200℃之间的加热器组成，封装在两种膨润土中，Na为主的Wyoming膨润土和Mg/Ca为主的BCV膨润土。与现场试验相辅相成，建立了一个多团队建模平台来开发试验的数值模型。这项工作介绍了作者对该平台的贡献，重点是比较怀俄明州膨润土的两种不同水力参数化如何影响与实验测量相比的数值结果。第一次参数化包括提供给HotBENT建模平台的参数，第二次设置基于先前怀俄明州膨润土模拟中使用的参数，例如，瑞典核废料处置库的许可证申请。使用COMSOL Multiphysics®进行了二维轴对称THM模拟，并模拟了前五年的演变。这两种参数设置都可以成功地再现试验中温度和孔隙压力的一般演化过程。然而，在模拟的相对湿度（RH）演变和干密度状态中可以看到显着差异。结果强调了在模拟耦合THM过程时参数选择的重要性，以及使用实验验证数据的重要性。

{"title":"Evolution of thermo-hydro-mechanical behaviour of bentonite buffer at high temperature","authors":"Alex Spetz , Daniel Malmberg , Chang Seok Kim","doi":"10.1016/j.clay.2026.108128","DOIUrl":"10.1016/j.clay.2026.108128","url":null,"abstract":"<div><div>The HotBENT experiment at the Grimsel Test Site investigates the Thermo-Hydro-Mechanical (THM) behaviour of bentonite clay at temperatures exceeding 100 °C. It consists of four heaters with a temperature of between 175 °C and 200 °C, encapsulated in two types of bentonites, Na dominated Wyoming bentonite and a Mg/Ca dominated BCV bentonite. Complementary to the field test, a multi-team modelling platform was established to develop numerical models of the experiment. This work presents the authors contribution to that platform, focusing on comparing how two different hydraulic parameterizations of Wyoming bentonite affected the numerical results compared with experimental measurements. The first parameterizations consisted of parameters provided to the HotBENT modelling platform and the second setup was based on parameters used in previous simulations of Wyoming bentonite, in for example, the license application for the Swedish nuclear waste repository.</div><div>2D axisymmetric THM simulations were carried out using COMSOL Multiphysics® and simulated the evolution during the first five years. Both parameter setups could successfully reproduce the general evolution in the test in terms of temperature and pore pressure evolution. However, significant differences could be seen in the modelled relative humidity (RH) evolution and dry density state.</div><div>The results highlight the importance of parameter selection when modelling coupled THM processes and the importance of using experimentally validated data.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108128"},"PeriodicalIF":5.8,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Adsorption and intercalation of benznidazole and nifurtimox in montmorillonite: An experimental-theoretical study 苯并硝唑和硝呋替莫在蒙脱土中的吸附与插层：实验-理论研究

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-24 DOI: 10.1016/j.clay.2026.108142

Alexander Pérez de la Luz , Alfredo Jiménez-Mondragón , Miriam Soriano-Santiago , Julio C. Alva-Ensastegui , Ana María Soto-Estrada , José Luis Ortiz-Quiñonez , Linda Campos-Fernández , Carolina Barrientos-Salcedo , Víctor Hugo Lara-Corona , Edtson E. Herrera-Valencia , Catalina Soriano-Correa , C. Ignacio Sainz-Díaz

American trypanosomiasis or Chagas disease, caused by Trypanosoma cruzi, remains a therapeutic challenge worldwide. Benznidazole (BNZ) and Nifurtimox (NFX) are drugs used for its treatment; however, they are not efficacy in the chronic phase of the disease, which leads to high toxicity due to prolonged use. This research addresses the use of nanomaterials (Nano clay and VHS) as natural systems capable of adsorbing drugs with low water solubility, allowing improved release to reduce adverse effects. The objectives were to study the crystal structures of NFX and BNZ at the atomic scale, using quantum mechanics calculations and experimental techniques (XRD, FTIR, TGA, SEM-EDS), to understand their physicochemical characteristics in the crystalline state, as well as to explore their hydration by molecular dynamics simulations. The intercalation of these drugs in the confined space between the montmorillonite layers was evaluated by DFT calculations to propose novel clay-drug nanocomplexes for enhancing the solubility and bioavailability. The results showed that NFX intercalation in both clays presented a loss of crystallinity, with a displacement of the (001) plane, while BNZ exhibited slight intercalation being adsorbed mainly on the external surfaces of clay mineral solids. Montmorillonite enhanced the stability of these drugs through interactions (hydrogen bonding, electrostatic interactions, and coordination with Na⁺ cations), adopting parallel orientations with the clay layers. The intercalation of NFX and BNZ into the interlaminar space of montmorillonite was energetically favorable. The design of clay-drug nanocomplexes could be a potential alternative for developing new, more effective and safer therapeutic schemes against Chagas disease.

由克氏锥虫引起的美洲锥虫病或恰加斯病仍然是世界范围内的治疗挑战。苯并硝唑（BNZ）和硝呋替莫（NFX）是用于治疗的药物；然而，它们在疾病的慢性期没有疗效，由于长期使用而导致高毒性。本研究解决了纳米材料（纳米粘土和VHS）作为能够吸附低水溶性药物的天然系统的使用，允许改善释放以减少不良反应。目的是在原子尺度上研究NFX和BNZ的晶体结构，利用量子力学计算和实验技术（XRD， FTIR， TGA, SEM-EDS），了解它们在晶体状态下的物理化学特征，并通过分子动力学模拟探索它们的水化作用。通过DFT计算评估这些药物在蒙脱土层之间的有限空间内的嵌入，以提出新的粘土-药物纳米复合物，以提高溶解度和生物利用度。结果表明：NFX在两种黏土中均表现出结晶度损失，（001）面发生位移；BNZ则表现出轻微的嵌入，主要吸附在粘土矿物固体的外表面。蒙脱土通过相互作用（氢键、静电相互作用以及与Na+阳离子的配位）增强了这些药物的稳定性，与粘土层呈平行取向。NFX和BNZ在蒙脱土层间空间的插层在能量上是有利的。粘土-药物纳米复合物的设计可能是开发针对恰加斯病的新的、更有效和更安全的治疗方案的潜在替代方案。

{"title":"Adsorption and intercalation of benznidazole and nifurtimox in montmorillonite: An experimental-theoretical study","authors":"Alexander Pérez de la Luz , Alfredo Jiménez-Mondragón , Miriam Soriano-Santiago , Julio C. Alva-Ensastegui , Ana María Soto-Estrada , José Luis Ortiz-Quiñonez , Linda Campos-Fernández , Carolina Barrientos-Salcedo , Víctor Hugo Lara-Corona , Edtson E. Herrera-Valencia , Catalina Soriano-Correa , C. Ignacio Sainz-Díaz","doi":"10.1016/j.clay.2026.108142","DOIUrl":"10.1016/j.clay.2026.108142","url":null,"abstract":"<div><div>American trypanosomiasis or Chagas disease, caused by <em>Trypanosoma cruzi</em>, remains a therapeutic challenge worldwide. Benznidazole (BNZ) and Nifurtimox (NFX) are drugs used for its treatment; however, they are not efficacy in the chronic phase of the disease, which leads to high toxicity due to prolonged use. This research addresses the use of nanomaterials (Nano clay and VHS) as natural systems capable of adsorbing drugs with low water solubility, allowing improved release to reduce adverse effects. The objectives were to study the crystal structures of NFX and BNZ at the atomic scale, using quantum mechanics calculations and experimental techniques (XRD, FTIR, TGA, SEM-EDS), to understand their physicochemical characteristics in the crystalline state, as well as to explore their hydration by molecular dynamics simulations. The intercalation of these drugs in the confined space between the montmorillonite layers was evaluated by DFT calculations to propose novel clay-drug nanocomplexes for enhancing the solubility and bioavailability. The results showed that NFX intercalation in both clays presented a loss of crystallinity, with a displacement of the (001) plane, while BNZ exhibited slight intercalation being adsorbed mainly on the external surfaces of clay mineral solids. Montmorillonite enhanced the stability of these drugs through interactions (hydrogen bonding, electrostatic interactions, and coordination with Na<sup>+</sup> cations), adopting parallel orientations with the clay layers. The intercalation of NFX and BNZ into the interlaminar space of montmorillonite was energetically favorable. The design of clay-drug nanocomplexes could be a potential alternative for developing new, more effective and safer therapeutic schemes against Chagas disease.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108142"},"PeriodicalIF":5.8,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Functionalized halloysite nanotube–alginate composites as clay based platforms for real-time adsorption and QCM detection of hydrophobic biomolecule 功能化高岭土纳米管-海藻酸盐复合材料在疏水生物分子实时吸附和QCM检测中的应用

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-22 DOI: 10.1016/j.clay.2026.108130

Mervenur Kirazoğlu , Birgül Benli

Hydrophobic biomolecules such as vitamin D₃ are difficult to detect in aqueous systems because of low solubility and weak affinity to hydrophilic surfaces. In this study, halloysite nanotube–alginate composites were functionalized and evaluated by Quartz Crystal Microbalance (QCM) for real-time monitoring of vitamin D₃ adsorption. Two routes were compared: ball milling of halloysite (MBHA), generating fragmented surfaces with more active sites, and HTAB-assisted surfactant functionalization (MHHA), promoting hydrophobic interactions. FTIR, XRD, SEM, and AFM confirmed successful modification and morphological changes. The zeta potential shifted from −19.33 ± 1.25 mV (pristine HNTs) to 0.095 ± 0.12 mV after 3 h ball milling, while HTAB increased it to +29.44 ± 0.50 mV. QCM showed markedly improved sensing performance: at 75 ng/mL, the unmodified crystal exhibited 600 Hz (4.162 ng), while MBHA and MHHA reached 1100 Hz (7.631 ng) and 965 Hz (6.695 ng), respectively; MBHA thus provided an 83% higher signal than the unmodified crystal. Langmuir analysis indicated higher capacity for HTAB-modified HNTs (q_max = 5935.263) than ball-milled HNTs (5318.108), whereas ball milling showed stronger affinity (K_L = 0.48 vs 0.23). At higher vitamin D₃ levels, Avrami and PSO fits supported nucleation–growth and chemisorption, whereas at lower levels Boyd and intraparticle diffusion fits reflected diffusion-controlled uptake. Desorption was biphasic, with faster release for MBHA at higher loadings and more sustained release for MHHA under dilute conditions. Moreover, functionalized halloysite–alginate composites offer dual-functionality for real-time biosensing and controlled delivery of poorly soluble biomolecules in aqueous environments.

像维生素D₃这样的疏水生物分子很难在水系统中检测到，因为它们的溶解度低，对亲水表面的亲和力弱。本研究采用石英晶体微平衡（QCM）对高岭土纳米管-海藻酸盐复合材料进行功能化和评价，实时监测其对维生素D3的吸附。比较了两种途径：高岭土球磨（MBHA），产生具有更多活性位点的碎片状表面，以及htab辅助表面活性剂功能化（MHHA），促进疏水相互作用。FTIR， XRD， SEM和AFM证实了成功的修饰和形态变化。经3 h球磨后，zeta电位由- 19.33±1.25 mV（原始HNTs）增加到0.095±0.12 mV，而HTAB使zeta电位增加到+29.44±0.50 mV。QCM在75 ng/mL时，未修饰的晶体表现为600 Hz (4.162 ng)，而MBHA和MHHA分别达到1100 Hz （7.631 ng）和965 Hz (6.695 ng)；因此，MBHA提供的信号比未修饰的晶体高83%。Langmuir分析表明，htaba修饰HNTs的qmax为5935.263，高于球磨HNTs(5318.108)，而球磨HNTs的KL为0.48比0.23。在较高的维生素D₃水平上，Avrami和PSO配合支持成核生长和化学吸附，而在较低水平上，Boyd和颗粒内扩散配合反映了扩散控制的摄取。解吸是双相的，在高负荷条件下，MBHA释放更快，在稀释条件下，MHHA释放更持久。此外，功能化的高岭土-海藻酸盐复合材料提供了双重功能，用于实时生物传感和水环境中难溶生物分子的控制递送。

{"title":"Functionalized halloysite nanotube–alginate composites as clay based platforms for real-time adsorption and QCM detection of hydrophobic biomolecule","authors":"Mervenur Kirazoğlu , Birgül Benli","doi":"10.1016/j.clay.2026.108130","DOIUrl":"10.1016/j.clay.2026.108130","url":null,"abstract":"<div><div>Hydrophobic biomolecules such as vitamin D₃ are difficult to detect in aqueous systems because of low solubility and weak affinity to hydrophilic surfaces. In this study, halloysite nanotube–alginate composites were functionalized and evaluated by Quartz Crystal Microbalance (QCM) for real-time monitoring of vitamin D<sub>3</sub> adsorption. Two routes were compared: ball milling of halloysite (MBHA), generating fragmented surfaces with more active sites, and HTAB-assisted surfactant functionalization (MHHA), promoting hydrophobic interactions. FTIR, XRD, SEM, and AFM confirmed successful modification and morphological changes. The zeta potential shifted from −19.33 ± 1.25 mV (pristine HNTs) to 0.095 ± 0.12 mV after 3 h ball milling, while HTAB increased it to +29.44 ± 0.50 mV. QCM showed markedly improved sensing performance: at 75 ng/mL, the unmodified crystal exhibited 600 Hz (4.162 ng), while MBHA and MHHA reached 1100 Hz (7.631 ng) and 965 Hz (6.695 ng), respectively; MBHA thus provided an 83% higher signal than the unmodified crystal. Langmuir analysis indicated higher capacity for HTAB-modified HNTs (q<sub>max</sub> = 5935.263) than ball-milled HNTs (5318.108), whereas ball milling showed stronger affinity (K<sub>L</sub> = 0.48 vs 0.23). At higher vitamin D₃ levels, Avrami and PSO fits supported nucleation–growth and chemisorption, whereas at lower levels Boyd and intraparticle diffusion fits reflected diffusion-controlled uptake. Desorption was biphasic, with faster release for MBHA at higher loadings and more sustained release for MHHA under dilute conditions. Moreover, functionalized halloysite–alginate composites offer dual-functionality for real-time biosensing and controlled delivery of poorly soluble biomolecules in aqueous environments.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108130"},"PeriodicalIF":5.8,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Superhydrophobic halloysite-based porous foamed geopolymer for efficient phase change material encapsulation with enhanced thermal management performance 基于超疏水高岭土的多孔泡沫地聚合物，用于高效相变材料封装，具有增强的热管理性能

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-21 DOI: 10.1016/j.clay.2026.108133

Heqiu Chen , Yinze Yang , Wenya Wei , Giuseppe Cavallaro , Zhuhe Zhai , Yafei Zhao , Dan Wang , Shengqiang Chen , Huishan Shang , Bing Zhang

Exploiting inexpensive and highly porous materials for phase change materials (PCMs) encapsulation is identified as a promising strategy for addressing the shape collapse and leakage of organic PCMs. Herein, a hierarchical porous foamed geopolymer (MH) was prepared by alkali activation of meta-halloysite (MHNT) with hollow glass spheres as templates, which was then modified by polydimethylsiloxane (PDMS) to obtain superhydrophobic MH (PMH). The PMH demonstrates excellent encapsulation efficiency of 67.23% for paraffin wax (PW), exceeding that of MH (57.74%) and most reported geopolymers. The reason is attributable to the highly porous structure and superhydrophobic feature of PMH, which provides enough space for PW encapsulation and enhances the affinity between PW and PMH, respectively. Additionally, PW@PMH reveals remarkable thermal cycling stability, good thermal storage and thermal insulation performance. This work proposes a creative strategy to prepare highly porous geopolymer for PCMs encapsulation for application in thermal energy storage and thermal insulation fields.

利用廉价的高多孔材料封装相变材料（PCMs）是解决有机相变材料形状塌陷和泄漏的一种很有前途的策略。本文以中空玻璃球为模板，通过碱法活化元高岭土（MHNT）制备了层次化多孔泡沫地聚合物（MH），然后用聚二甲基硅氧烷（PDMS）对其进行改性，得到了超疏水MH （PMH）。PMH对石蜡（PW）的包封率为67.23%，超过了MH（57.74%）和大多数已报道的地聚合物。这是由于PMH的高孔隙结构和超疏水特性，为PW的包封提供了足够的空间，增强了PW和PMH之间的亲和度。此外，PW@PMH具有显著的热循环稳定性，良好的储热和保温性能。本工作提出了一种创造性的策略，制备高多孔性地聚合物用于PCMs封装，用于储热和保温领域。

{"title":"Superhydrophobic halloysite-based porous foamed geopolymer for efficient phase change material encapsulation with enhanced thermal management performance","authors":"Heqiu Chen , Yinze Yang , Wenya Wei , Giuseppe Cavallaro , Zhuhe Zhai , Yafei Zhao , Dan Wang , Shengqiang Chen , Huishan Shang , Bing Zhang","doi":"10.1016/j.clay.2026.108133","DOIUrl":"10.1016/j.clay.2026.108133","url":null,"abstract":"<div><div>Exploiting inexpensive and highly porous materials for phase change materials (PCMs) encapsulation is identified as a promising strategy for addressing the shape collapse and leakage of organic PCMs. Herein, a hierarchical porous foamed geopolymer (MH) was prepared by alkali activation of meta-halloysite (MHNT) with hollow glass spheres as templates, which was then modified by polydimethylsiloxane (PDMS) to obtain superhydrophobic MH (PMH). The PMH demonstrates excellent encapsulation efficiency of 67.23% for paraffin wax (PW), exceeding that of MH (57.74%) and most reported geopolymers. The reason is attributable to the highly porous structure and superhydrophobic feature of PMH, which provides enough space for PW encapsulation and enhances the affinity between PW and PMH, respectively. Additionally, PW@PMH reveals remarkable thermal cycling stability, good thermal storage and thermal insulation performance. This work proposes a creative strategy to prepare highly porous geopolymer for PCMs encapsulation for application in thermal energy storage and thermal insulation fields.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108133"},"PeriodicalIF":5.8,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Swelling-induced fracture closure in Opalinus Clay: An inert particle tracking approach 蛋白石粘土中膨胀诱导的裂缝闭合：一种惰性颗粒跟踪方法

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-21 DOI: 10.1016/j.clay.2026.108134

Lukas M. Keller , Ali Seiphoori , Paul Marschall , Silvio Giger

This study examines permeability reduction in fractured Opalinus Clay material due to swelling-induced self-sealing mechanisms under controlled triaxial state conditions. An artificial continuous fracture, oriented parallel to natural fractures, was introduced to simulate an extreme scenario. Inert particle tracking was used to quantify material displacement during swelling, allowing derivation of swelling factors, porosity, and density changes. These parameters were applied to calculate spatially resolved permeability, including a swelling-induced micro-fractured damage zone modeled using a fractal scaling approach. Micro-fracture apertures ranged from pore size at the swollen region boundary up to ∼300 nm at the fracture surface. Application to 3D X-ray Computed Tomography derived fracture geometries predicted permeability reduction from ∼1 × 10⁻¹¹ m² (open) to ∼5 × 10⁻¹⁷ m² (swollen), consistent with experimental results. Achieving this reduction required a swollen volume approximately seven times greater than the initial fracture volume. With continued swelling, micro-fracture apertures may shrink to ∼80 nm, further reducing bulk permeability to ∼1 × 10⁻¹⁸ m², only slightly higher than that of intact material.

本研究考察了受控制的三轴状态条件下，由于膨胀引起的自密封机制，裂缝性蛋白石粘土材料的渗透率降低。引入与天然裂缝平行的人工连续裂缝来模拟极端情况。惰性颗粒跟踪用于量化膨胀过程中的材料位移，从而推导膨胀因素、孔隙率和密度变化。这些参数用于计算空间分辨渗透率，包括使用分形尺度方法建模的膨胀微裂缝损伤区。微裂缝的孔径范围从膨胀区边界的孔径到裂缝表面的~ 300 nm。应用三维x射线计算机断层扫描导出的裂缝几何形状预测渗透率从~ 1 × 10 - 11 m2（开放）降至~ 5 × 10 - 17 m2（肿胀），与实验结果一致。实现这种复位所需的膨胀体积大约是初始裂缝体积的7倍。随着持续膨胀，微裂缝孔径可能缩小至~ 80 nm，进一步将整体渗透率降低至~ 1 × 10−18 m2，仅略高于完整材料。

{"title":"Swelling-induced fracture closure in Opalinus Clay: An inert particle tracking approach","authors":"Lukas M. Keller , Ali Seiphoori , Paul Marschall , Silvio Giger","doi":"10.1016/j.clay.2026.108134","DOIUrl":"10.1016/j.clay.2026.108134","url":null,"abstract":"<div><div>This study examines permeability reduction in fractured Opalinus Clay material due to swelling-induced self-sealing mechanisms under controlled triaxial state conditions. An artificial continuous fracture, oriented parallel to natural fractures, was introduced to simulate an extreme scenario. Inert particle tracking was used to quantify material displacement during swelling, allowing derivation of swelling factors, porosity, and density changes. These parameters were applied to calculate spatially resolved permeability, including a swelling-induced micro-fractured damage zone modeled using a fractal scaling approach. Micro-fracture apertures ranged from pore size at the swollen region boundary up to ∼300 nm at the fracture surface. Application to 3D X-ray Computed Tomography derived fracture geometries predicted permeability reduction from ∼1 × 10<sup>−11</sup> m<sup>2</sup> (open) to ∼5 × 10<sup>−17</sup> m<sup>2</sup> (swollen), consistent with experimental results. Achieving this reduction required a swollen volume approximately seven times greater than the initial fracture volume. With continued swelling, micro-fracture apertures may shrink to ∼80 nm, further reducing bulk permeability to ∼1 × 10<sup>−18</sup> m<sup>2</sup>, only slightly higher than that of intact material.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108134"},"PeriodicalIF":5.8,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025143","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tracer transport in claystones at the core scale: Experiments and modelling 粘土中示踪剂在核心尺度上的传输：实验和模型

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-20 DOI: 10.1016/j.clay.2026.108131

Andreas Jenni , Thomas Gimmi , Johannes C.L. Meeussen , Mirjam Kiczka , Urs Mäder

Within the Swiss deep drilling campaign 2019–2022, a series of Jurassic (Dogger, Lias) claystone samples were mineralogically and geochemically characterised and used in small-scale transport experiments. The advective-diffusive transport experiments clearly showed a faster breakthrough of anions relative to neutral tracers, which agrees with the accumulation of anions in a relatively faster moving porewater fraction due to anion repulsion by negatively charged clay surfaces. Electroneutral tracers were not affected by the clay charge and thus evenly distributed in all porewater domains, including stationary ones, and were transported more slowly than anions. The experiments showed consistently a faster breakthrough of Br relative to Cl, which was intuitively not expected based on the equal charge and chemical behaviour of these ions. Simulations with a continuum finite volume model approach that considers electrostatic effects in clay accurately described the different breakthrough curves of charged and neutral tracers. Matching of breakthrough behaviour required a model explicitly considering heterogeneous flow, because the simple Fickian advection-dispersion equation failed to predict the experimental data of all tracers in a consistent way. The model indicated that although the exclusion behaviour of Cl and Br as a function of concentration and surface potential is the same, the effective retardation factor (and thus breakthrough) of each ion depends on the difference in concentration of initial in-situ porewater and that of the infiltrating solution. Heterogeneous flow, electrostatic interactions, and multicomponent transport are key processes governing solute transport in claystone cores under large hydraulic gradients. These mechanisms were therefore incorporated into the presented model, enabling successful simulation of the experimental data.

在瑞士2019-2022年的深部钻探活动中，对一系列侏罗纪（多格尔，利亚斯）粘土岩样品进行了矿物学和地球化学表征，并用于小规模运输实验。平流-扩散输运实验清楚地表明，阴离子相对于中性示踪剂的突破速度更快，这与阴离子在带负电荷的粘土表面的排斥作用下在相对较快移动的孔隙水中的积累是一致的。电中性示踪剂不受粘土电荷的影响，因此均匀分布在所有孔隙水域中，包括固定的孔隙水域中，并且比阴离子的运输速度慢。实验一致表明，Br相对于Cl的突破速度更快，这是基于这些离子的等电荷和化学行为而直观地预料不到的。采用考虑粘土中静电效应的连续有限体积模型方法进行模拟，准确地描述了带电示踪剂和中性示踪剂的不同突破曲线。突破行为的匹配需要一个明确考虑非均匀流动的模型，因为简单的菲克式平流-色散方程无法以一致的方式预测所有示踪剂的实验数据。该模型表明，虽然Cl和Br的排斥性作为浓度和表面电位的函数是相同的，但每个离子的有效阻滞因子（从而突破）取决于初始原位孔隙水和渗透溶液浓度的差异。非均质流动、静电相互作用和多组分输运是大水力梯度下粘土岩心溶质输运的关键过程。因此，这些机制被纳入到所提出的模型中，从而能够成功地模拟实验数据。

{"title":"Tracer transport in claystones at the core scale: Experiments and modelling","authors":"Andreas Jenni , Thomas Gimmi , Johannes C.L. Meeussen , Mirjam Kiczka , Urs Mäder","doi":"10.1016/j.clay.2026.108131","DOIUrl":"10.1016/j.clay.2026.108131","url":null,"abstract":"<div><div>Within the Swiss deep drilling campaign 2019–2022, a series of Jurassic (Dogger, Lias) claystone samples were mineralogically and geochemically characterised and used in small-scale transport experiments. The advective-diffusive transport experiments clearly showed a faster breakthrough of anions relative to neutral tracers, which agrees with the accumulation of anions in a relatively faster moving porewater fraction due to anion repulsion by negatively charged clay surfaces. Electroneutral tracers were not affected by the clay charge and thus evenly distributed in all porewater domains, including stationary ones, and were transported more slowly than anions. The experiments showed consistently a faster breakthrough of Br relative to Cl, which was intuitively not expected based on the equal charge and chemical behaviour of these ions. Simulations with a continuum finite volume model approach that considers electrostatic effects in clay accurately described the different breakthrough curves of charged and neutral tracers. Matching of breakthrough behaviour required a model explicitly considering heterogeneous flow, because the simple Fickian advection-dispersion equation failed to predict the experimental data of all tracers in a consistent way. The model indicated that although the exclusion behaviour of Cl and Br as a function of concentration and surface potential is the same, the effective retardation factor (and thus breakthrough) of each ion depends on the difference in concentration of initial in-situ porewater and that of the infiltrating solution. Heterogeneous flow, electrostatic interactions, and multicomponent transport are key processes governing solute transport in claystone cores under large hydraulic gradients. These mechanisms were therefore incorporated into the presented model, enabling successful simulation of the experimental data.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108131"},"PeriodicalIF":5.8,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

CuO-decorated metakaolin-based geopolymer foams for catalytic degradation of tetracycline 过氧化氢修饰的偏高岭土聚合物泡沫用于四环素的催化降解

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-20 DOI: 10.1016/j.clay.2026.108126

Chengying Bai , Jingwa Gao , Hongxue Chen , Ting Zheng , Xiaodong Wang , Xinyu Li , Hongqiang Li , Paolo Colombo , Bin Wang

This study utilized polyurethane foam as a template to prepare a metakaolin-based geopolymer matrix with highly interconnected porosity via the replica template method. Subsequently, nano-CuO was successfully deposited onto the porous geopolymer (PG) through a direct precipitation (DP) method. The resulting CuO/geopolymer catalyst (CG) was employed to activate peroxymonosulfate (PMS) under UV light irradiation for the degradation of tetracycline hydrochloride (TCH). The CG-DP catalyst achieved a degradation efficiency of up to 94.80% within 1 h while maintaining sufficient mechanical strength for easy recovery. Moreover, the composite catalyst demonstrated excellent stability and broad applicability under various conditions, particularly reaching a degradation rate of 99.40% at pH = 9. Electron paramagnetic resonance (EPR) and radical quenching experiments revealed that reactive species, including SO₄•⁻, •OH, ¹O₂, O₂•⁻ and h⁺, collectively contributed to TCH degradation. Recycling experiments further confirmed the satisfactory reusability of the CG-DP catalyst. Nano-CuO catalysts supported on metakaolin-based geopolymer foam provide a simple, eco-friendly method for wastewater treatment.

本研究以聚氨酯泡沫为模板，通过复制模板法制备了高连通孔隙度的偏高岭土聚合物基质。随后，通过直接沉淀法（DP）成功地将纳米cuo沉积在多孔地聚合物（PG）上。采用CuO/地聚合物催化剂（CG）在紫外光照射下活化过氧单硫酸根（PMS）降解盐酸四环素（TCH）。CG-DP催化剂在1 h内的降解效率高达94.80%，同时保持了足够的机械强度，易于回收。此外，复合催化剂在各种条件下都表现出优异的稳定性和广泛的适用性，特别是在pH = 9时，降解率达到99.40%。电子顺磁共振（EPR）和自由基猝灭实验表明，SO4•−、•OH、1O2、O2•−和h+等活性物质共同促进了TCH的降解。回收实验进一步证实了CG-DP催化剂具有良好的可重复使用性。偏高岭土聚合物泡沫支撑的纳米cuo催化剂为废水处理提供了一种简单、环保的方法。

{"title":"CuO-decorated metakaolin-based geopolymer foams for catalytic degradation of tetracycline","authors":"Chengying Bai , Jingwa Gao , Hongxue Chen , Ting Zheng , Xiaodong Wang , Xinyu Li , Hongqiang Li , Paolo Colombo , Bin Wang","doi":"10.1016/j.clay.2026.108126","DOIUrl":"10.1016/j.clay.2026.108126","url":null,"abstract":"<div><div>This study utilized polyurethane foam as a template to prepare a metakaolin-based geopolymer matrix with highly interconnected porosity via the replica template method. Subsequently, nano-CuO was successfully deposited onto the porous geopolymer (PG) through a direct precipitation (DP) method. The resulting CuO/geopolymer catalyst (CG) was employed to activate peroxymonosulfate (PMS) under UV light irradiation for the degradation of tetracycline hydrochloride (TCH). The CG-DP catalyst achieved a degradation efficiency of up to 94.80% within 1 h while maintaining sufficient mechanical strength for easy recovery. Moreover, the composite catalyst demonstrated excellent stability and broad applicability under various conditions, particularly reaching a degradation rate of 99.40% at pH = 9. Electron paramagnetic resonance (EPR) and radical quenching experiments revealed that reactive species, including SO<sub>4</sub>•<sup>−</sup>, •OH, <sup>1</sup>O<sub>2</sub>, O<sub>2</sub>•<sup>−</sup> and h<sup>+</sup>, collectively contributed to TCH degradation. Recycling experiments further confirmed the satisfactory reusability of the CG-DP catalyst. Nano-CuO catalysts supported on metakaolin-based geopolymer foam provide a simple, eco-friendly method for wastewater treatment.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108126"},"PeriodicalIF":5.8,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

MoS2 nanosheets assembly on Sb-SnO2 modified kaolinite nanoflakes for efficient catalytic hydrogenation Sb-SnO2改性高岭石纳米片上MoS2纳米片的高效催化加氢组装

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2026-01-20 DOI: 10.1016/j.clay.2026.108132

Xiaoyu Li , Wenqing Zhang , Kang Peng , Zheng Zhou , Yewei Dou , Jianguo Feng

Molybdenum disulfide (MoS₂) is promising for aqueous-phase catalytic hydrogenation due to its two-dimensional morphology and abundant catalytic active sites, but limited by poor conductivity and hydrophobicity. Herein, a ternary FK/ATO/MoS₂ composite was fabricated by growing MoS₂ nanosheets on an antimony-doped tin oxide (ATO)-modified hydrophilic kaolinite nanoflakes (FK) via simple coprecipitation-hydrothermal method. Evaluated by the aqueous hydrogenation of 4-nitrophenol (4-NP), the optimal composite with 25% Sb doping in ATO and 50% MoS₂ loading (FK/ATO/MoS₂–50%) exhibits remarkably enhanced hydrogenation activities as compared to other catalysts, and the reaction rate constant is 0.0809 min⁻¹, 10 times higher than that of pure MoS₂ (0.0081 min⁻¹). The improved performances are due to the synergistic contributions from the exposed active sites of MoS₂, the conductivity of ATO, the hydrophilicity and dispersion of kaolinite. This work presents an efficient aqueous-phase hydrogenation catalyst and a general design strategy for synergistic “support–mediator–active component” catalytic systems.

二硫化钼（MoS2）由于其二维形态和丰富的催化活性位点，在水相催化加氢中具有广阔的应用前景，但受其导电性和疏水性差的限制。本文通过简单共沉淀法-水热法在掺锑氧化锡（ATO）修饰的亲水性高岭石纳米片（FK）上生长MoS2纳米片，制备了三元FK/ATO/MoS2复合材料。通过对4-硝基苯酚（4-NP）的水加氢评价，结果表明，与其他催化剂相比，在ATO中掺杂25% Sb，负载50% MoS2 （FK/ATO/MoS2 - 50%）的最佳复合材料的加氢活性显著增强，反应速率常数为0.0809 min−1，是纯MoS2 （0.0081 min−1）的10倍。性能的提高是由于MoS2暴露的活性位点、ATO的电导率、高岭石的亲水性和分散性的协同作用。这项工作提出了一种高效的水相加氢催化剂和协同“载体-介质-活性组分”催化系统的一般设计策略。

{"title":"MoS2 nanosheets assembly on Sb-SnO2 modified kaolinite nanoflakes for efficient catalytic hydrogenation","authors":"Xiaoyu Li , Wenqing Zhang , Kang Peng , Zheng Zhou , Yewei Dou , Jianguo Feng","doi":"10.1016/j.clay.2026.108132","DOIUrl":"10.1016/j.clay.2026.108132","url":null,"abstract":"<div><div>Molybdenum disulfide (MoS<sub>2</sub>) is promising for aqueous-phase catalytic hydrogenation due to its two-dimensional morphology and abundant catalytic active sites, but limited by poor conductivity and hydrophobicity. Herein, a ternary FK/ATO/MoS<sub>2</sub> composite was fabricated by growing MoS<sub>2</sub> nanosheets on an antimony-doped tin oxide (ATO)-modified hydrophilic kaolinite nanoflakes (FK) via simple coprecipitation-hydrothermal method. Evaluated by the aqueous hydrogenation of 4-nitrophenol (4-NP), the optimal composite with 25% Sb doping in ATO and 50% MoS<sub>2</sub> loading (FK/ATO/MoS<sub>2</sub>–50%) exhibits remarkably enhanced hydrogenation activities as compared to other catalysts, and the reaction rate constant is 0.0809 min<sup>−1</sup>, 10 times higher than that of pure MoS<sub>2</sub> (0.0081 min<sup>−1</sup>). The improved performances are due to the synergistic contributions from the exposed active sites of MoS<sub>2</sub>, the conductivity of ATO, the hydrophilicity and dispersion of kaolinite. This work presents an efficient aqueous-phase hydrogenation catalyst and a general design strategy for synergistic “support–mediator–active component” catalytic systems.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"284 ","pages":"Article 108132"},"PeriodicalIF":5.8,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0