Applied Clay Science最新文献_第8页

Oxalate-derived NiO@NiAl-layered double hydroxide core-shell material for supercapacitors

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-28 DOI: 10.1016/j.clay.2025.107715

Hong-Li Yue, Hong-Yan Zeng, Wei Yan, Chao-Wei Luo, Zi-Feng Tian, Kai-Wen Xu

NiO as an appealing electrode material has been used for supercapacitors due to its high theoretical capacity and easy availability, but intrinsically low electrical conductivity and insufficient redox active sites restrict its further applications. In this work, a novel oxalate-derived NiO@NiAl-layered double hydroxide (LDH) with 3D core-shell structure (denoted as NiO_OA@LDH) was prepared via hydrothermal calcination method, where the oxalate-derived porous C-doping NiO (NiO_OA) grown on nickel foam (NF) was constructed using NiC₂O₄ as a sacrificial template and carbon source. The deposition of the ultrathin NiAl-LDH nanosheets on the NiO_OA was conducive to forming robust adhesion between the core and the shell, which promoted effective electron/ion transfer and structure stability. Benefiting from the unique 3D core-shell structure and complementary compositional features, the NiO_OA@LDH gave a high specific charge of 1347.0C g⁻¹ at 1 A g⁻¹, prominent rate performance (68.5 % retention at 15 A g⁻¹) and cycle stability (91.1 % retention at 5 A g⁻¹ after 5000 cycles). Furthermore, the as-assembled NiO_OA@LDH//activated carbon (AC) device achieved a high energy density of 45.6 Wh kg⁻¹ at a power density of 557.8 W kg⁻¹ and an outstanding cycle stability (93.1 % retention at 5 A g⁻¹ after 10,000 cycles).

{"title":"Oxalate-derived NiO@NiAl-layered double hydroxide core-shell material for supercapacitors","authors":"Hong-Li Yue, Hong-Yan Zeng, Wei Yan, Chao-Wei Luo, Zi-Feng Tian, Kai-Wen Xu","doi":"10.1016/j.clay.2025.107715","DOIUrl":"10.1016/j.clay.2025.107715","url":null,"abstract":"<div><div>NiO as an appealing electrode material has been used for supercapacitors due to its high theoretical capacity and easy availability, but intrinsically low electrical conductivity and insufficient redox active sites restrict its further applications. In this work, a novel oxalate-derived NiO@NiAl-layered double hydroxide (LDH) with 3D core-shell structure (denoted as NiO<sub>OA</sub>@LDH) was prepared via hydrothermal calcination method, where the oxalate-derived porous C-doping NiO (NiO<sub>OA</sub>) grown on nickel foam (NF) was constructed using NiC<sub>2</sub>O<sub>4</sub> as a sacrificial template and carbon source. The deposition of the ultrathin NiAl-LDH nanosheets on the NiO<sub>OA</sub> was conducive to forming robust adhesion between the core and the shell, which promoted effective electron/ion transfer and structure stability. Benefiting from the unique 3D core-shell structure and complementary compositional features, the NiO<sub>OA</sub>@LDH gave a high specific charge of 1347.0C g<sup>−1</sup> at 1 A g<sup>−1</sup>, prominent rate performance (68.5 % retention at 15 A g<sup>−1</sup>) and cycle stability (91.1 % retention at 5 A g<sup>−1</sup> after 5000 cycles). Furthermore, the as-assembled NiO<sub>OA</sub>@LDH//activated carbon (AC) device achieved a high energy density of 45.6 Wh kg<sup>−1</sup> at a power density of 557.8 W kg<sup>−1</sup> and an outstanding cycle stability (93.1 % retention at 5 A g<sup>−1</sup> after 10,000 cycles).</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"267 ","pages":"Article 107715"},"PeriodicalIF":5.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143101108","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

Instant formation of AlN whiskers and monocrystalline silicon with the separation of silicon and aluminum elements from 7 Å halloysite during thermite reduction

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-27 DOI: 10.1016/j.clay.2025.107711

Jing Zhang , Hao Zhang , Leibo Ji , Mingyi Huang , Qinfu Liu , JiaXing Li , XiaoYu Ding , Xi Xu

Natural halloysite have attracted great attention owing to their unique hollow tube and strong adsorption capacity. Nevertheless, the straightforward utilization of halloysite without further processing cannot fully discover its potential will lead to the waste of resources. In this study, an environmentally friendly method for the simultaneous separation of silica and aluminum from natural 7 Å halloysite via the aluminum thermal reduction method upon 700 °C under the system of aluminum powder and NaCl in N₂ atmosphere was developed, concurrently occurs with the structural transformation from the raw hollow tubular halloysite to AIN whiskers and monocrystalline silicon droplet tips was observed. The formation of AlN whiskers can be concluded as three steps: (1) the reduction of Si⁴⁺ in SiO tetrahedron into Si⁰ atoms; (2) the separation of silicon and aluminum in the 1:1 meta-halloysite layer and the Si⁰ atoms transportation to the end of whisker rod to form the monocrystalline silicon microsphere; (3) the formation of AlN whiskers by the replacement of the remaining oxygen atoms in the aluminum‑oxygen octahedra. This in-situ replacement of oxygen atoms by nitrogen atoms in the AlO octahedron of tubular meta-halloysite plays a pivotal role in decreasing the reaction temperature. This work provides a novel idea and opens up a new technical route to prepare aluminum nitride and monocrystalline silicon with green efficiency and low cost.

{"title":"Instant formation of AlN whiskers and monocrystalline silicon with the separation of silicon and aluminum elements from 7 Å halloysite during thermite reduction","authors":"Jing Zhang , Hao Zhang , Leibo Ji , Mingyi Huang , Qinfu Liu , JiaXing Li , XiaoYu Ding , Xi Xu","doi":"10.1016/j.clay.2025.107711","DOIUrl":"10.1016/j.clay.2025.107711","url":null,"abstract":"<div><div>Natural halloysite have attracted great attention owing to their unique hollow tube and strong adsorption capacity. Nevertheless, the straightforward utilization of halloysite without further processing cannot fully discover its potential will lead to the waste of resources. In this study, an environmentally friendly method for the simultaneous separation of silica and aluminum from natural 7 Å halloysite via the aluminum thermal reduction method upon 700 °C under the system of aluminum powder and NaCl in N<sub>2</sub> atmosphere was developed, concurrently occurs with the structural transformation from the raw hollow tubular halloysite to AIN whiskers and monocrystalline silicon droplet tips was observed. The formation of AlN whiskers can be concluded as three steps: (1) the reduction of Si<sup>4+</sup> in Si<img>O tetrahedron into Si<sup>0</sup> atoms; (2) the separation of silicon and aluminum in the 1:1 meta-halloysite layer and the Si<sup>0</sup> atoms transportation to the end of whisker rod to form the monocrystalline silicon microsphere; (3) the formation of AlN whiskers by the replacement of the remaining oxygen atoms in the aluminum‑oxygen octahedra. This in-situ replacement of oxygen atoms by nitrogen atoms in the Al<img>O octahedron of tubular meta-halloysite plays a pivotal role in decreasing the reaction temperature. This work provides a novel idea and opens up a new technical route to prepare aluminum nitride and monocrystalline silicon with green efficiency and low cost.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"267 ","pages":"Article 107711"},"PeriodicalIF":5.3,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143101104","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

Montmorillonite-enhanced micro- and nanocomposites for targeted and controlled oral drug delivery systems

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-25 DOI: 10.1016/j.clay.2025.107713

Zhenping Xiao , Xuemin Gu , Ji Huang , Liangzhe Liu , Siying Yuan , Peng Jiang , Yangrong Zhang , Yingshan Zhao , Shijie Wei , Qi Tao , Dongzhi Hou

Oral drug delivery systems (ODDSs) offer numerous advantages, such as convenient administration, high patient adherence, and cost-effectiveness. However, challenges like enzyme barriers and first-pass metabolism limit their effectiveness, and traditional methods often lack features for controlled release and targeted delivery, tending to cause severe systemic toxic side effects. Recent advancements in drug delivery have introduced alternative delivery vehicles. Montmorillonite (Mt), an FDA-approved biocompatible nanomaterial, stands out due to its high specific surface area, ideal adsorption capacity and cation exchange properties. This review explores preparation, modification, and application of Mt-based micro- and nanocomposites (MNCs) for ODDSs. Drugs encapsulated in Mt-based MNCs are shielded from the gastrointestinal environment, facilitating delayed and targeted drug release and enhancing drug bioavailability. The paper provides insights into the rational selection of Mt-based MNCs for advanced ODDSs, highlighting their potential to overcome limitations of traditional drug delivery systems.

{"title":"Montmorillonite-enhanced micro- and nanocomposites for targeted and controlled oral drug delivery systems","authors":"Zhenping Xiao , Xuemin Gu , Ji Huang , Liangzhe Liu , Siying Yuan , Peng Jiang , Yangrong Zhang , Yingshan Zhao , Shijie Wei , Qi Tao , Dongzhi Hou","doi":"10.1016/j.clay.2025.107713","DOIUrl":"10.1016/j.clay.2025.107713","url":null,"abstract":"<div><div>Oral drug delivery systems (ODDSs) offer numerous advantages, such as convenient administration, high patient adherence, and cost-effectiveness. However, challenges like enzyme barriers and first-pass metabolism limit their effectiveness, and traditional methods often lack features for controlled release and targeted delivery, tending to cause severe systemic toxic side effects. Recent advancements in drug delivery have introduced alternative delivery vehicles. Montmorillonite (Mt), an FDA-approved biocompatible nanomaterial, stands out due to its high specific surface area, ideal adsorption capacity and cation exchange properties. This review explores preparation, modification, and application of Mt-based micro- and nanocomposites (MNCs) for ODDSs. Drugs encapsulated in Mt-based MNCs are shielded from the gastrointestinal environment, facilitating delayed and targeted drug release and enhancing drug bioavailability. The paper provides insights into the rational selection of Mt-based MNCs for advanced ODDSs, highlighting their potential to overcome limitations of traditional drug delivery systems.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"267 ","pages":"Article 107713"},"PeriodicalIF":5.3,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143101105","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

Photoinduced cooling effect of water-retentive composite of TiO2 and saponite

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-24 DOI: 10.1016/j.clay.2025.107712

Yosuke Kageshima , Koharu Yagawa , Katsuya Teshima , Hiromasa Nishikiori

TiO₂ coating of a building envelope is expected to contribute to the mitigation of the heat-island effect because of the photoinduced cooling effect. However, the limited water adsorbability and retentivity of the TiO₂ thin film can require successive sprinkling of water onto a building to achieve the sufficient cooling effect. In this study, a thin film consisting of a mixture of TiO₂ and saponite was prepared through a sol–gel method. The high water retentivity of saponite was found to enhance the photoinduced cooling effect of the TiO₂-based thin film. The photoinduced temporal change in the water adsorbability and retentivity of the highly hydrophilic composite was successfully monitored by using a hydrophilic xanthene dye adsorbed onto the coating as a probe. The effect of environmental humidity on the photoinduced cooling effect was also investigated. We found that higher humidity in the surrounding environment triggered stronger photoinduced cooling effects of the composite film. Especially during summer in Japan, when humidity is high, the TiO₂–saponite composite film did not require intentional water sprinkling to achieve cooling effects.

{"title":"Photoinduced cooling effect of water-retentive composite of TiO2 and saponite","authors":"Yosuke Kageshima , Koharu Yagawa , Katsuya Teshima , Hiromasa Nishikiori","doi":"10.1016/j.clay.2025.107712","DOIUrl":"10.1016/j.clay.2025.107712","url":null,"abstract":"<div><div>TiO<sub>2</sub> coating of a building envelope is expected to contribute to the mitigation of the heat-island effect because of the photoinduced cooling effect. However, the limited water adsorbability and retentivity of the TiO<sub>2</sub> thin film can require successive sprinkling of water onto a building to achieve the sufficient cooling effect. In this study, a thin film consisting of a mixture of TiO<sub>2</sub> and saponite was prepared through a sol–gel method. The high water retentivity of saponite was found to enhance the photoinduced cooling effect of the TiO<sub>2</sub>-based thin film. The photoinduced temporal change in the water adsorbability and retentivity of the highly hydrophilic composite was successfully monitored by using a hydrophilic xanthene dye adsorbed onto the coating as a probe. The effect of environmental humidity on the photoinduced cooling effect was also investigated. We found that higher humidity in the surrounding environment triggered stronger photoinduced cooling effects of the composite film. Especially during summer in Japan, when humidity is high, the TiO<sub>2</sub>–saponite composite film did not require intentional water sprinkling to achieve cooling effects.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"267 ","pages":"Article 107712"},"PeriodicalIF":5.3,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143101106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Kaolinite to smectite transformation: A crystal chemistry study by analytical electron microscopy

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-24 DOI: 10.1016/j.clay.2025.107710

Emilia García-Romero , Eva Manchado , Mercedes Suárez

Kaolinite and smectite coexist in variable proportions along the Tamame de Sayago deposit in Zamora, Spain, suggesting a close genetic relationship. Kaolinite is formed through the weathering of the Variscan granite, while smectite is subsequently derived from kaolinite through a superimposed hydrothermal process that contributes to Si and Mg content. The transformation of smectites into kaolinite has been widely investigated, however, the reverse transformation of kaolinite into smectite is rarely documented. In this study, a group of representative samples from the deposit were studied via analytical electron microscopy and high-resolution transmission electron microscopy to determine the crystal chemistry of particles and explain the genetic relationship between the two clay minerals. The results showed that the crystal chemistry of particles varied, both among the particles of a sample and at different points within single particles. Chemical composition varied progressively from compositions of kaolinite to kaolinite/smectite and ultimately montmorillonite, with most particles displaying intermediate compositions. SiO₂ and MgO contents increased progressively from kaolinite to montmorillonite through intermediate compositions. The morphologies and compositions of particles suggest the predominance of a solid-state transformation of kaolinite to smectite via interstratified kaolinite-smectite in areas less affected by hydrothermal fluids. Point analyses revealed the existence of domains with different compositions within single pseudohexagonal particles, suggesting the existence of areas with different degrees of transformation in single particles. In areas closer to faults, through which Si and Mg could circulate, dissolution-crystallisation was likely the main process responsible for smectite neoformation. Occasionally, epitaxial smectite growth was observed along the edges of kaolinite crystals. The simultaneous operation but different intensities of three processes solid-state transformation, epitaxy, and dissolution-precipitation generated particles with a complex crystal chemistry related to the existence of interstratified phases.

{"title":"Kaolinite to smectite transformation: A crystal chemistry study by analytical electron microscopy","authors":"Emilia García-Romero , Eva Manchado , Mercedes Suárez","doi":"10.1016/j.clay.2025.107710","DOIUrl":"10.1016/j.clay.2025.107710","url":null,"abstract":"<div><div>Kaolinite and smectite coexist in variable proportions along the Tamame de Sayago deposit in Zamora, Spain, suggesting a close genetic relationship. Kaolinite is formed through the weathering of the Variscan granite, while smectite is subsequently derived from kaolinite through a superimposed hydrothermal process that contributes to Si and Mg content. The transformation of smectites into kaolinite has been widely investigated, however, the reverse transformation of kaolinite into smectite is rarely documented. In this study, a group of representative samples from the deposit were studied via analytical electron microscopy and high-resolution transmission electron microscopy to determine the crystal chemistry of particles and explain the genetic relationship between the two clay minerals. The results showed that the crystal chemistry of particles varied, both among the particles of a sample and at different points within single particles. Chemical composition varied progressively from compositions of kaolinite to kaolinite/smectite and ultimately montmorillonite, with most particles displaying intermediate compositions. SiO<sub>2</sub> and MgO contents increased progressively from kaolinite to montmorillonite through intermediate compositions. The morphologies and compositions of particles suggest the predominance of a solid-state transformation of kaolinite to smectite via interstratified kaolinite-smectite in areas less affected by hydrothermal fluids. Point analyses revealed the existence of domains with different compositions within single pseudohexagonal particles, suggesting the existence of areas with different degrees of transformation in single particles. In areas closer to faults, through which Si and Mg could circulate, dissolution-crystallisation was likely the main process responsible for smectite neoformation. Occasionally, epitaxial smectite growth was observed along the edges of kaolinite crystals. The simultaneous operation but different intensities of three processes solid-state transformation, epitaxy, and dissolution-precipitation generated particles with a complex crystal chemistry related to the existence of interstratified phases.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"267 ","pages":"Article 107710"},"PeriodicalIF":5.3,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143101109","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

Hydrocalumite and hydrocalumite-type compounds: A special type of layered double hydroxides

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-20 DOI: 10.1016/j.clay.2025.107707

Alejandro Jiménez , Raquel Trujillano , Antonio Gil , Vicente Rives , Miguel Ángel Vicente

An exhaustive bibliographical review of one of the most peculiar Layered Double Hydroxides, LDH, namely hydrocalumite and hydrocalumite–type compounds, has been carried out. The main differences that make hydrocalumite a special and interesting LDH are described, as well as the main methods of synthesis. A comprehensive comparison is also made with respect to MgAl–carbonate hydrotalcite with a Mg/Al molar ratio of 2. Thermal behavior of hydrocalumite is also different than that of other LDH, leading to the formation of attractive Mixed Metallic Oxides, MMO. Thus, the applications of hydrocalumite, hydrocalumite–type compounds and the derived MMO in environmental remediation and heterogeneous catalysis and photocatalysis are presented. Hydrocalumite, contrary to hydrotalcite, is not currently commercialized on an industrial scale, probably because its preparation is more complicated. Considering the excellent properties of hydrocalumite and the price, abundance and biocompatibility of its components, the scaling of its production should be a key challenge to take advantage in its industrial application.

{"title":"Hydrocalumite and hydrocalumite-type compounds: A special type of layered double hydroxides","authors":"Alejandro Jiménez , Raquel Trujillano , Antonio Gil , Vicente Rives , Miguel Ángel Vicente","doi":"10.1016/j.clay.2025.107707","DOIUrl":"10.1016/j.clay.2025.107707","url":null,"abstract":"<div><div>An exhaustive bibliographical review of one of the most peculiar Layered Double Hydroxides, LDH, namely hydrocalumite and hydrocalumite–type compounds, has been carried out. The main differences that make hydrocalumite a special and interesting LDH are described, as well as the main methods of synthesis. A comprehensive comparison is also made with respect to MgAl–carbonate hydrotalcite with a Mg/Al molar ratio of 2. Thermal behavior of hydrocalumite is also different than that of other LDH, leading to the formation of attractive Mixed Metallic Oxides, MMO. Thus, the applications of hydrocalumite, hydrocalumite–type compounds and the derived MMO in environmental remediation and heterogeneous catalysis and photocatalysis are presented. Hydrocalumite, contrary to hydrotalcite, is not currently commercialized on an industrial scale, probably because its preparation is more complicated. Considering the excellent properties of hydrocalumite and the price, abundance and biocompatibility of its components, the scaling of its production should be a key challenge to take advantage in its industrial application.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"267 ","pages":"Article 107707"},"PeriodicalIF":5.3,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143101107","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

Multi-functional nanoarchitectonics of allophane via addition reactions with acrylonitrile through C-O bond formation

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-16 DOI: 10.1016/j.clay.2025.107706

Qingcheng Zhang, Qingbin Xie, Mohammad Fahimizadeh, Meiqing Chen, Yuchen Diao, Weisen Cai, Peng Yuan

Organic functional groups, such as the cyano group (-CN), were introduced onto the Allophane (Allo) surface through addition reactions to achieve precise control over Allo surface properties. Polyacrylonitrile (PAN), Allo and surface-treated Allo were characterized using FT-IR, XRD, XPS and ²⁷Al NMR techniques. It was found that an additional reaction occurs between Allo and acrylonitrile (AN), forming a C-O covalent bond between the unsaturated carbon‑carbon bonds (C=C) of AN and the aluminum hydroxyl groups (Al-OH) on the Allo surface. This reaction constructs an (Al)O-C(C) structure, rearranging the electron density in the aluminum‑oxygen octahedral units, thereby affecting the short-range quasi-crystalline structure within Allo. Concurrently, -CN groups were attached to the Allo surface, while alkenes such as acrylic acid and sodium acrylate introduced organic functional groups like -COOH and -CONH₂ onto the Allo surface. This approach provides a new method for grafting functional groups onto the Allo surface and a novel strategy to modify the surface properties of Allo to obtain multifunctional, high-performance Allo nanocomposite materials.

{"title":"Multi-functional nanoarchitectonics of allophane via addition reactions with acrylonitrile through C-O bond formation","authors":"Qingcheng Zhang, Qingbin Xie, Mohammad Fahimizadeh, Meiqing Chen, Yuchen Diao, Weisen Cai, Peng Yuan","doi":"10.1016/j.clay.2025.107706","DOIUrl":"10.1016/j.clay.2025.107706","url":null,"abstract":"<div><div>Organic functional groups, such as the cyano group (-CN), were introduced onto the Allophane (Allo) surface through addition reactions to achieve precise control over Allo surface properties. Polyacrylonitrile (PAN), Allo and surface-treated Allo were characterized using FT-IR, XRD, XPS and <sup>27</sup>Al NMR techniques. It was found that an additional reaction occurs between Allo and acrylonitrile (AN), forming a C-O covalent bond between the unsaturated carbon‑carbon bonds (C=C) of AN and the aluminum hydroxyl groups (Al-OH) on the Allo surface. This reaction constructs an (Al)O-C(C) structure, rearranging the electron density in the aluminum‑oxygen octahedral units, thereby affecting the short-range quasi-crystalline structure within Allo. Concurrently, -CN groups were attached to the Allo surface, while alkenes such as acrylic acid and sodium acrylate introduced organic functional groups like -COOH and -CONH<sub>2</sub> onto the Allo surface. This approach provides a new method for grafting functional groups onto the Allo surface and a novel strategy to modify the surface properties of Allo to obtain multifunctional, high-performance Allo nanocomposite materials.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"266 ","pages":"Article 107706"},"PeriodicalIF":5.3,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143137571","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

Surfactant mediated intercalation of a hydrophobic drug into layered double hydroxides: Probing the structural features by the photophysical behaviour of piroxicam

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-16 DOI: 10.1016/j.clay.2025.107708

Nawal Fodil Cherif , François Réveret , Anthony Barros , Vagner Roberto Magri , Fabrice Leroux , Damien Boyer , Vera Regina Leopoldo Constantino , Christine Taviot-Guého

Piroxicam (PIR), a hydrophobic drug with ionisable properties, can adopt various prototropic forms and conformations, which make its structural and dynamic properties highly dependent on its environment. In this study, PIR was, for the first time, incorporated into Zn²⁺/Al³⁺ layered double hydroxides using a surfactant-mediated intercalation method (Zn₂Al-DS_@%PIR), which first involved the encapsulation of PIR within dodecyl sulfate (DS) micelles. A comprehensive investigation of the DS-PIR assembly within the interlayer space of the LDH is proposed, particularly emphasizing the utilization of the optical properties of PIR as a structural probe. The structural and chemical properties of the Zn₂Al-DS_@%PIR samples prepared with different PIR contents (0.16, 0.90 and 2.06 wt%) were assessed by X-ray diffraction, Fourier transform infrared (FTIR) and thermal analysis. By exploiting PIR's photochemical properties in both solid-state and solution, it was gained deeper insights into PIR molecular arrangement within the LDH interlayer space. FTIR results showed the stabilization of the ZZZ conformation form for intercalated PIR, while thermal analyses revealed an improved thermal stability of PIR of 80 °C for the sample with a maximum PIR loading content of 2.06 wt%. Interestingly, fluorescence results clearly confirmed the intercalation of PIR in LDH, both as global neutral and anionic forms, and allowed to infer their location in the interlayer space. A protective effect against photodegradation was also observed. This work can contribute to advancements in the challenging intercalation of other hydrophobic drugs.

{"title":"Surfactant mediated intercalation of a hydrophobic drug into layered double hydroxides: Probing the structural features by the photophysical behaviour of piroxicam","authors":"Nawal Fodil Cherif , François Réveret , Anthony Barros , Vagner Roberto Magri , Fabrice Leroux , Damien Boyer , Vera Regina Leopoldo Constantino , Christine Taviot-Guého","doi":"10.1016/j.clay.2025.107708","DOIUrl":"10.1016/j.clay.2025.107708","url":null,"abstract":"<div><div>Piroxicam (PIR), a hydrophobic drug with ionisable properties, can adopt various prototropic forms and conformations, which make its structural and dynamic properties highly dependent on its environment. In this study, PIR was, for the first time, incorporated into Zn<sup>2+</sup>/Al<sup>3+</sup> layered double hydroxides using a surfactant-mediated intercalation method (Zn<sub>2</sub>Al-DS<sub>@%PIR</sub>), which first involved the encapsulation of PIR within dodecyl sulfate (DS) micelles. A comprehensive investigation of the DS-PIR assembly within the interlayer space of the LDH is proposed, particularly emphasizing the utilization of the optical properties of PIR as a structural probe. The structural and chemical properties of the Zn<sub>2</sub>Al-DS<sub>@%PIR</sub> samples prepared with different PIR contents (0.16, 0.90 and 2.06 wt%) were assessed by X-ray diffraction, Fourier transform infrared (FTIR) and thermal analysis. By exploiting PIR's photochemical properties in both solid-state and solution, it was gained deeper insights into PIR molecular arrangement within the LDH interlayer space. FTIR results showed the stabilization of the ZZZ conformation form for intercalated PIR, while thermal analyses revealed an improved thermal stability of PIR of 80 °C for the sample with a maximum PIR loading content of 2.06 wt%. Interestingly, fluorescence results clearly confirmed the intercalation of PIR in LDH, both as global neutral and anionic forms, and allowed to infer their location in the interlayer space. A protective effect against photodegradation was also observed. This work can contribute to advancements in the challenging intercalation of other hydrophobic drugs.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"266 ","pages":"Article 107708"},"PeriodicalIF":5.3,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143137572","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

Mechanochemical activation of non-conventional precursors for use as suplementary cementitious materials

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-10 DOI: 10.1016/j.clay.2025.107705

A. Seco , M.A. Martín-Antunes , S. Espuelas , A. Fernández , E. Prieto

This work analyzes the effect of Mechanochemical Activation (MA) of a Commercial low-grade kaolinite and low-grade illite, a feldspar, a diatomite and a clayey soil (non-commercial) as supplementary cementitious materials. Milling was conducted at different times for up to 360 min. MA decreased the particles size and increased the specific surface area except for low-grade illite. However, prolonged milling produced agglomeration in feldspar, diatomite and clayey soil. MA partially reduced diffractogram peaks and modified the dehydroxylation losses of mass in the thermogravimetric tests. MA's effect over the solubility of SiO₂ and Al₂O₃ was not conclusive, with differences among aluminosilicate minerals and with no relationships with their physical parameters or chemical structures. Feldspar was the only one not to show Strength Activity Index (SAI) increases due to MA. Low-grade illite, feldspar and diatomite combinations surpassed 75 % on the SAI. No clear relationships were observed between the combinations SAI and their physical parameters, chemical structure or SiO₂ and Al₂O₃ availability.

{"title":"Mechanochemical activation of non-conventional precursors for use as suplementary cementitious materials","authors":"A. Seco , M.A. Martín-Antunes , S. Espuelas , A. Fernández , E. Prieto","doi":"10.1016/j.clay.2025.107705","DOIUrl":"10.1016/j.clay.2025.107705","url":null,"abstract":"<div><div>This work analyzes the effect of Mechanochemical Activation (MA) of a Commercial low-grade kaolinite and low-grade illite, a feldspar, a diatomite and a clayey soil (non-commercial) as supplementary cementitious materials. Milling was conducted at different times for up to 360 min. MA decreased the particles size and increased the specific surface area except for low-grade illite. However, prolonged milling produced agglomeration in feldspar, diatomite and clayey soil. MA partially reduced diffractogram peaks and modified the dehydroxylation losses of mass in the thermogravimetric tests. MA's effect over the solubility of SiO<sub>2</sub> and Al<sub>2</sub>O<sub>3</sub> was not conclusive, with differences among aluminosilicate minerals and with no relationships with their physical parameters or chemical structures. Feldspar was the only one not to show Strength Activity Index (SAI) increases due to MA. Low-grade illite, feldspar and diatomite combinations surpassed 75 % on the SAI. No clear relationships were observed between the combinations SAI and their physical parameters, chemical structure or SiO<sub>2</sub> and Al<sub>2</sub>O<sub>3</sub> availability.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"266 ","pages":"Article 107705"},"PeriodicalIF":5.3,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143137570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Combined effect of 2D nature and structural glass behaviour and true magnetic contribution to the low-temperature heat capacity of layered double hydroxides

IF 5.3 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-01-09 DOI: 10.1016/j.clay.2024.107695

V. Tkáč , Yu.G. Pashkevich , E.L. Fertman , R. Tarasenko , E. Čižmár , A. Feher , A.V. Fedorchenko , C.S. Neves , D.E.L. Vieira , A.N. Salak

Heat capacity of cobalt-aluminium and magnesium-aluminium layered double hydroxides (LDH) with the divalent-to-trivalent cations ratio (n) of 2 and 3, and intercalated with NO₃⁻, CO₃²⁻ and OH⁻, was measured as a function of temperature between 2 and 100 K. Magnetic contribution to the heat capacity (C_mag) of Co_nAl LDH was extracted from comparison of the C(T) dependences with the respective reduced dependences of their non-magnetic counterparts, Mg_nAl LDH. At the lowest measured temperatures, the magnetic contribution to the heat capacity (C_mag) of Co-containing LDH was found to be almost two orders of magnitude bigger than their lattice contribution. In a zero magnetic field, the low-temperature C_mag of Co₂Al LDH was measured to be proportional to T^2.6, while for Co₃Al LDH, C_mag ∼ T² was observed. An application of an external magnetic field was revealed to converge these dependences to C_mag ∼ T³ in compounds with both n = 2 and 3. However, the conversion in Co₂Al LDH occurred at lower values of external magnetic field (50 kOe) than that in Co₃Al LDH (90 kOe).

It was revealed from the C(T) behaviour of the non-magnetic LDH at the lowest measured temperatures that they possess the features typical for both a 2D solid and a structural glass. The reduced C(T)/T³ heat capacity of Mg_nAl LDH intercalated with nitrate was found to demonstrate a so-called boson peak, which is a manifestation of a glassy state. The observed low-temperature structural glassy state in LDH was associated with the disorder of the intercalated species.

{"title":"Combined effect of 2D nature and structural glass behaviour and true magnetic contribution to the low-temperature heat capacity of layered double hydroxides","authors":"V. Tkáč , Yu.G. Pashkevich , E.L. Fertman , R. Tarasenko , E. Čižmár , A. Feher , A.V. Fedorchenko , C.S. Neves , D.E.L. Vieira , A.N. Salak","doi":"10.1016/j.clay.2024.107695","DOIUrl":"10.1016/j.clay.2024.107695","url":null,"abstract":"<div><div>Heat capacity of cobalt-aluminium and magnesium-aluminium layered double hydroxides (LDH) with the divalent-to-trivalent cations ratio (<em>n</em>) of 2 and 3, and intercalated with NO<sub>3</sub><sup>−</sup>, CO<sub>3</sub><sup>2−</sup> and OH<sup>−</sup>, was measured as a function of temperature between 2 and 100 K. Magnetic contribution to the heat capacity (<em>C</em><sub>mag</sub>) of Co<sub><em>n</em></sub>Al LDH was extracted from comparison of the <em>C</em>(<em>T</em>) dependences with the respective reduced dependences of their non-magnetic counterparts, Mg<sub><em>n</em></sub>Al LDH. At the lowest measured temperatures, the magnetic contribution to the heat capacity (<em>C</em><sub>mag</sub>) of Co-containing LDH was found to be almost two orders of magnitude bigger than their lattice contribution. In a zero magnetic field, the low-temperature <em>C</em><sub>mag</sub> of Co<sub>2</sub>Al LDH was measured to be proportional to <em>T</em><sup>2.6</sup>, while for Co<sub>3</sub>Al LDH, <em>C</em><sub>mag</sub> ∼ <em>T</em><sup>2</sup> was observed. An application of an external magnetic field was revealed to converge these dependences to <em>C</em><sub>mag</sub> ∼ <em>T</em><sup>3</sup> in compounds with both <em>n</em> = 2 and 3. However, the conversion in Co<sub>2</sub>Al LDH occurred at lower values of external magnetic field (50 kOe) than that in Co<sub>3</sub>Al LDH (90 kOe).</div><div>It was revealed from the <em>C</em>(<em>T</em>) behaviour of the non-magnetic LDH at the lowest measured temperatures that they possess the features typical for both a 2D solid and a structural glass. The reduced <em>C</em>(<em>T</em>)/<em>T</em><sup>3</sup> heat capacity of Mg<sub><em>n</em></sub>Al LDH intercalated with nitrate was found to demonstrate a so-called boson peak, which is a manifestation of a glassy state. The observed low-temperature structural glassy state in LDH was associated with the disorder of the intercalated species.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"266 ","pages":"Article 107695"},"PeriodicalIF":5.3,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143137596","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0