This work investigated the formation conditions of cronstedtite, the most Fe-rich serpentine, using a steel autoclave lined with Teflon at 90 °C, over 167 days, allowing for in situ monitoring of pH, T and P, as well as for gas sampling. From a starting mineralogical mixture composed of quartz and metal iron, cronstedtite crystallized in association with, magnetite, akaganeite, ferrihydrite and amorphous silica. This mineralogical association was not observed in previous syntheses and it is likely related to the experimental conditions of this study. These conditions also affected the composition and structure (polytypic sequence and crystallinity degree) of cronstedtite, which are accurately characterized for the first time. Experimental data and thermodynamic modelling indicate that this Fe-serpentine formed under neutral conditions, -62 < logfO2 < −59, and redox potential ranging from −0.46 to −0.41 Volts. During the experiment, H2 was generated by iron oxidation in presence of water, explaining the increase of pressure in the autoclave until 6.8 bar at 90 °C. The total amount of H2 generated was of 0.23 mol. The results of this study are useful to improve the understanding of cronstedtite formation in natural and anthropic environments. They also showed that formation conditions of cronstedtite seem to be compatible with those needed for hydrogenotrophic life, as previously supposed by other works.
这项研究利用一个内衬特氟隆的钢制高压釜，在 90 ° C 的温度下，历时 167 天，研究了最富含铁的蛇纹石--川长石的形成条件，从而对 pH 值、T 值和 P 值以及气体采样进行了现场监测。在由石英和金属铁组成的初始矿物混合物中，铁石棉与磁铁矿、赤铁矿、铁水合物和无定形二氧化硅结晶在一起。这种矿物关联在以前的合成中没有观察到，可能与本研究的实验条件有关。这些条件还影响了芒硝的组成和结构（多晶序列和结晶度），并首次对其进行了精确表征。实验数据和热力学模型表明，这种铁蛇纹石是在-62 < logfO2 < -59的中性条件和-0.46至-0.41伏的氧化还原电位下形成的。在实验过程中，铁在水中氧化产生了 H2，这也是高压釜中的压力在 90 °C 时上升到 6.8 巴的原因。产生的 H2 总量为 0.23 摩尔。这项研究的结果有助于人们更好地了解自然和人为环境中铜闪石的形成。研究结果还表明，芒硝的形成条件似乎与之前其他研究推测的养氢生命所需的条件相符。
{"title":"Cronstedtite: H2 generation and new constraints on its formation conditions","authors":"Isabella Pignatelli , Enrico Mugnaioli , Régine Mosser-Ruck , Mustapha Abdelmoula , Jérôme Sterpenich","doi":"10.1016/j.clay.2024.107627","DOIUrl":"10.1016/j.clay.2024.107627","url":null,"abstract":"<div><div>This work investigated the formation conditions of cronstedtite, the most Fe-rich serpentine, using a steel autoclave lined with Teflon at 90 °C, over 167 days, allowing for in situ monitoring of pH, T and P, as well as for gas sampling. From a starting mineralogical mixture composed of quartz and metal iron, cronstedtite crystallized in association with, magnetite, akaganeite, ferrihydrite and amorphous silica. This mineralogical association was not observed in previous syntheses and it is likely related to the experimental conditions of this study. These conditions also affected the composition and structure (polytypic sequence and crystallinity degree) of cronstedtite, which are accurately characterized for the first time. Experimental data and thermodynamic modelling indicate that this Fe-serpentine formed under neutral conditions, -62 < log<em>f</em>O<sub>2</sub> < −59, and redox potential ranging from −0.46 to −0.41 Volts. During the experiment, H<sub>2</sub> was generated by iron oxidation in presence of water, explaining the increase of pressure in the autoclave until 6.8 bar at 90 °C. The total amount of H<sub>2</sub> generated was of 0.23 mol. The results of this study are useful to improve the understanding of cronstedtite formation in natural and anthropic environments. They also showed that formation conditions of cronstedtite seem to be compatible with those needed for hydrogenotrophic life, as previously supposed by other works.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107627"},"PeriodicalIF":5.3,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651125","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}
Pub Date : 2024-11-08DOI: 10.1016/j.clay.2024.107589
Kairui Tian, Xiangyu Chen, Xinyuan Zhou, Yuqian Xu, Mingxian Liu
Tea, as one of the three major beverages in the world, has antioxidant, anti-cancer, inhibitory inflammation, immune regulation, diabetes prevention, antibacterial and other effects. In this study, black tea and FeCl3·6H2O were chelated to functionally modify the outer surface of halloysite clay nanotube (Hal). A new nanomaterial with excellent photothermal properties, tea nanoparticles@Hal, was successfully synthesized. Tea nanoparticles@Hal powder can raise to 225.8 °C in 25 s, and the corresponding solution can raise to 50.5 °C in 8 min with a photothermal efficiency of 77.3 %. The tea nanoparticles@Hal was assembled on the polyurethane (PU) sponges by simply soaking to prepare conductive sensor. The flexible sensor shows a fast response time (132.8 ms) and a long service time (400 cycles), which have wide range of applications. The resistance changes with the pressure is in a regular functional relationship, and the sensor can measure the weight of objects with high accuracy. In addition, the sensor can stably monitor various physiological activities of the human body. When finger is bent, the sensor can produce the difference output signals. The prepared tea nanoparticles@Hal/PU sensor has broad prospects in fields such as human-computer interaction and medical detection.
{"title":"Tea nanoparticles modified halloysite clay coated polyurethane sponge as multifunctional sensors","authors":"Kairui Tian, Xiangyu Chen, Xinyuan Zhou, Yuqian Xu, Mingxian Liu","doi":"10.1016/j.clay.2024.107589","DOIUrl":"10.1016/j.clay.2024.107589","url":null,"abstract":"<div><div>Tea, as one of the three major beverages in the world, has antioxidant, anti-cancer, inhibitory inflammation, immune regulation, diabetes prevention, antibacterial and other effects. In this study, black tea and FeCl<sub>3</sub>·6H<sub>2</sub>O were chelated to functionally modify the outer surface of halloysite clay nanotube (Hal). A new nanomaterial with excellent photothermal properties, tea nanoparticles@Hal, was successfully synthesized. Tea nanoparticles@Hal powder can raise to 225.8 °C in 25 s, and the corresponding solution can raise to 50.5 °C in 8 min with a photothermal efficiency of 77.3 %. The tea nanoparticles@Hal was assembled on the polyurethane (PU) sponges by simply soaking to prepare conductive sensor. The flexible sensor shows a fast response time (132.8 ms) and a long service time (400 cycles), which have wide range of applications. The resistance changes with the pressure is in a regular functional relationship, and the sensor can measure the weight of objects with high accuracy. In addition, the sensor can stably monitor various physiological activities of the human body. When finger is bent, the sensor can produce the difference output signals. The prepared tea nanoparticles@Hal/PU sensor has broad prospects in fields such as human-computer interaction and medical detection.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107589"},"PeriodicalIF":5.3,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651127","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}
Pub Date : 2024-11-06DOI: 10.1016/j.clay.2024.107622
Marcus Vinicius do Prado , Vinicius Lima , Larissa Oliveira , Eduardo J. Nassar , Liziane Marçal , Emerson Henrique de Faria , Miguel Angel Vicente , Raquel Trujillano , Leticia Santamaría , Antonio Gil , Sophia Korili , Katia Jorge Ciuffi
The rising global demand for hydrogen peroxide, recognized for its eco–friendly properties, underscores the need for greener synthesis methods. Traditional production processes pose environmental risks, while direct synthesis faces challenges like water formation, explosion hazards, and stability issues, limiting industrial application. On the other hand, Bisphenol A (BPA), an endocrine disruptor widely used in plastics, presents significant environmental and health concerns due to its potential leaching into food and water. The present work introduces efficient and selective photocatalysts aimed at sustainable hydrogen peroxide synthesis and BPA degradation. Both processes were enhanced by the synergistic properties of Fe2O3–TiO2 nanoparticles dispersed within a kaolinite matrix. The Fe2O3–TiO2 photocatalysts, characterized by photoluminescence spectroscopy and X–ray diffraction, showed reduced emission upon iron incorporation and anatase presence on the kaolinite surface. The photocatalytic activity was evaluated through hydroxylation of terephthalic acid, revealing a 127 μmol/L min hydroxylation rate for the KaFeTi400 sample. BPA degradation studies indicated optimal performance in acidic conditions, achieving 96 % removal in 2 h and 98 % in 4 h, with the addition of H2O2 enhancing efficiency. Further, the photocatalyst facilitated benzyl alcohol oxidation to benzaldehyde, demonstrating a H2O2 production rate of 120 μmol. These findings highlight the multifunctional capabilities and environmental benefits of the photocatalyst, underscoring its potential for sustainable hydrogen peroxide synthesis and broader applications in environmental remediation. The catalysts address the pressing challenges associated with hydrogen peroxide synthesis and pollutant removal, particularly in the context of sustainability and environmental impact.
双氧水具有环保特性，全球对双氧水的需求不断增长，这凸显了对更环保合成方法的需求。传统的生产工艺存在环境风险，而直接合成则面临着水形成、爆炸危险和稳定性问题等挑战，从而限制了工业应用。另一方面，双酚 A（BPA）是一种广泛应用于塑料中的内分泌干扰物，由于可能会渗入食物和水中，因此引起了严重的环境和健康问题。本研究介绍了高效且具有选择性的光催化剂，旨在实现可持续的过氧化氢合成和双酚 A 降解。分散在高岭石基质中的 Fe2O3-TiO2 纳米粒子的协同特性增强了这两个过程。通过光致发光光谱和 X 射线衍射对 Fe2O3-TiO2 光催化剂进行了表征，结果表明，在高岭石表面掺入铁和锐钛矿后，发射率降低。通过对对苯二甲酸的羟基化来评估光催化活性，结果显示 KaFeTi400 样品的羟基化率为 127 μmol/L min。双酚 A 降解研究表明，该催化剂在酸性条件下具有最佳性能，2 小时内的去除率达到 96%，4 小时内达到 98%，加入 H2O2 可提高效率。此外，这种光催化剂还能促进苯甲醇氧化成苯甲醛，其 H2O2 生成率为 120 μmol。这些发现凸显了光催化剂的多功能性和环境效益，强调了它在可持续过氧化氢合成和更广泛的环境修复应用方面的潜力。这些催化剂解决了与过氧化氢合成和污染物去除相关的紧迫挑战，特别是在可持续发展和环境影响方面。
{"title":"Multifunctional nanocomposites based on kaolinite/titania/iron applied to hydrogen peroxide production and bisphenol–A removal","authors":"Marcus Vinicius do Prado , Vinicius Lima , Larissa Oliveira , Eduardo J. Nassar , Liziane Marçal , Emerson Henrique de Faria , Miguel Angel Vicente , Raquel Trujillano , Leticia Santamaría , Antonio Gil , Sophia Korili , Katia Jorge Ciuffi","doi":"10.1016/j.clay.2024.107622","DOIUrl":"10.1016/j.clay.2024.107622","url":null,"abstract":"<div><div>The rising global demand for hydrogen peroxide, recognized for its eco–friendly properties, underscores the need for greener synthesis methods. Traditional production processes pose environmental risks, while direct synthesis faces challenges like water formation, explosion hazards, and stability issues, limiting industrial application. On the other hand, Bisphenol A (BPA), an endocrine disruptor widely used in plastics, presents significant environmental and health concerns due to its potential leaching into food and water. The present work introduces efficient and selective photocatalysts aimed at sustainable hydrogen peroxide synthesis and BPA degradation. Both processes were enhanced by the synergistic properties of Fe<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> nanoparticles dispersed within a kaolinite matrix. The Fe<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> photocatalysts, characterized by photoluminescence spectroscopy and X–ray diffraction, showed reduced emission upon iron incorporation and anatase presence on the kaolinite surface. The photocatalytic activity was evaluated through hydroxylation of terephthalic acid, revealing a 127 μmol/L min hydroxylation rate for the <em>KaFeTi400</em> sample. BPA degradation studies indicated optimal performance in acidic conditions, achieving 96 % removal in 2 h and 98 % in 4 h, with the addition of H<sub>2</sub>O<sub>2</sub> enhancing efficiency. Further, the photocatalyst facilitated benzyl alcohol oxidation to benzaldehyde, demonstrating a H<sub>2</sub>O<sub>2</sub> production rate of 120 μmol. These findings highlight the multifunctional capabilities and environmental benefits of the photocatalyst, underscoring its potential for sustainable hydrogen peroxide synthesis and broader applications in environmental remediation. The catalysts address the pressing challenges associated with hydrogen peroxide synthesis and pollutant removal, particularly in the context of sustainability and environmental impact.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107622"},"PeriodicalIF":5.3,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593190","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}
Pub Date : 2024-11-06DOI: 10.1016/j.clay.2024.107626
Ceren Özcan Diker, Osman Duman, Sibel Tunç
Fabrication of functional colored water-repellent surfaces is very important for many industrial applications. Here, various colorful surface coating materials having water repellent property, chemical, thermal and UV light resistance and self-cleaning property were prepared using activated halloysite nanotube loaded with dye (A-Hal/dye), different alkoxysilanes (methyltriethoxysilane (MTES), octyltriethoxysilane (OTES) and hexadecyltrimethoxysilane (HDTMS)), and tetraethoxysilane and their coatings were performed on various substrates to determine the effect of alkyl chain length of alkoxysilane compound used in the coating formulation on the surface properties of colorful surfaces. Characterization studies of the synthesized surfaces or coated materials were performed using electron microscopy (TEM and SEM), SEM-mapping, FTIR, XRD, XPS and thermal gravimetic analysis techniques. Water contact angle (WCA) of glass surfaces coated with A-Hal/MB/MTES, A-Hal/MB/OTES and A-Hal/MB/HDTMS materials was found to be 148.0, 156.2 and 159.3°, respectively. The use of an alkoxysilane compound with long functional alkyl chain group in the coating formulation improved the water-repellent property of surface, while it slightly weakened the mechanical stability of the colorful surface. Polydimethylsiloxane (PDMS) coating, which were applied on colorful surfaces, improved the mechanical, thermal, chemical and environmental stability of coating, but decreased the water-repellent property of coated colorful surfaces. Fabricated coating materials having different colors were successfully used to coat various substrates such as glass, filter paper, wood, and cotton fabric. The results of this study show that A-Hal/dye/HDTMS coating materials prepared here are of a great potential in the fabrication of functional surface coatings.
{"title":"Design and characterization of multicolor water-repellent coatings: Impact of alkyl chain length on surface properties","authors":"Ceren Özcan Diker, Osman Duman, Sibel Tunç","doi":"10.1016/j.clay.2024.107626","DOIUrl":"10.1016/j.clay.2024.107626","url":null,"abstract":"<div><div>Fabrication of functional colored water-repellent surfaces is very important for many industrial applications. Here, various colorful surface coating materials having water repellent property, chemical, thermal and UV light resistance and self-cleaning property were prepared using activated halloysite nanotube loaded with dye (A-Hal/dye), different alkoxysilanes (methyltriethoxysilane (MTES), octyltriethoxysilane (OTES) and hexadecyltrimethoxysilane (HDTMS)), and tetraethoxysilane and their coatings were performed on various substrates to determine the effect of alkyl chain length of alkoxysilane compound used in the coating formulation on the surface properties of colorful surfaces. Characterization studies of the synthesized surfaces or coated materials were performed using electron microscopy (TEM and SEM), SEM-mapping, FTIR, XRD, XPS and thermal gravimetic analysis techniques. Water contact angle (WCA) of glass surfaces coated with A-Hal/MB/MTES, A-Hal/MB/OTES and A-Hal/MB/HDTMS materials was found to be 148.0, 156.2 and 159.3°, respectively. The use of an alkoxysilane compound with long functional alkyl chain group in the coating formulation improved the water-repellent property of surface, while it slightly weakened the mechanical stability of the colorful surface. Polydimethylsiloxane (PDMS) coating, which were applied on colorful surfaces, improved the mechanical, thermal, chemical and environmental stability of coating, but decreased the water-repellent property of coated colorful surfaces. Fabricated coating materials having different colors were successfully used to coat various substrates such as glass, filter paper, wood, and cotton fabric. The results of this study show that A-Hal/dye/HDTMS coating materials prepared here are of a great potential in the fabrication of functional surface coatings.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107626"},"PeriodicalIF":5.3,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593191","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}
Pub Date : 2024-11-05DOI: 10.1016/j.clay.2024.107625
Shixiang Zuo , Min Sun , Weifeng Gong , Tongtong Tang , Xuhua Ye , Wenjie Liu , Ngie Hing Wong , Rong Xu , Guihua Chen , Chao Yao , Haoguan Gui , Xiazhang Li
Layered double hydroxides (LDH) are regarded as an outstanding adsorbent with the ability to capture CO2. Nevertheless, the stacking and curling of CoAl-LDH significantly impact the CO2 adsorption performance. In this study, CoAl-LDH were synthesized on a rigid palygorskite (Pal) framework to form a hierarchical CoAl-LDH/Pal composite, which effectively reduced the original particle size of CoAl-LDH and addressed the drawbacks. Subsequently, polyethylene imine (PEI) was impregnated onto the surface of CoAl-LDH/Pal to fabricate PEI/CoAl-LDH/Pal adsorbent, further improving the CO2 capture performance. Finally, the mechanism of CO2 adsorption was also elaborated. The PEI/CoAl-LDH/Pal demonstrated a higher equilibrium adsorption capacity and a longer breakthrough time for CO2 capture, with the adsorption capacity reaching 158.8 mg/g and increasing by 8 times compared to that of CoAl-LDH/Pal. Herein, CO2 was adsorbed on the surface of PEI/CoAl-LDH/Pal in the forms of bicarbonate and amino carboxylate. Additionally, PEI/CoAl-LDH/Pal exhibited excellent regeneration performance and maintained the adsorption capacity over 9 cycles, which is anticipated to be a promising candidate for CO2 capture.
{"title":"Preparation of amino-functionalized CoAl-LDH/palygorskite hierarchical composites for CO2 capture","authors":"Shixiang Zuo , Min Sun , Weifeng Gong , Tongtong Tang , Xuhua Ye , Wenjie Liu , Ngie Hing Wong , Rong Xu , Guihua Chen , Chao Yao , Haoguan Gui , Xiazhang Li","doi":"10.1016/j.clay.2024.107625","DOIUrl":"10.1016/j.clay.2024.107625","url":null,"abstract":"<div><div>Layered double hydroxides (LDH) are regarded as an outstanding adsorbent with the ability to capture CO<sub>2</sub>. Nevertheless, the stacking and curling of CoAl-LDH significantly impact the CO<sub>2</sub> adsorption performance. In this study, CoAl-LDH were synthesized on a rigid palygorskite (Pal) framework to form a hierarchical CoAl-LDH/Pal composite, which effectively reduced the original particle size of CoAl-LDH and addressed the drawbacks. Subsequently, polyethylene imine (PEI) was impregnated onto the surface of CoAl-LDH/Pal to fabricate PEI/CoAl-LDH/Pal adsorbent, further improving the CO<sub>2</sub> capture performance. Finally, the mechanism of CO<sub>2</sub> adsorption was also elaborated. The PEI/CoAl-LDH/Pal demonstrated a higher equilibrium adsorption capacity and a longer breakthrough time for CO<sub>2</sub> capture, with the adsorption capacity reaching 158.8 mg/g and increasing by 8 times compared to that of CoAl-LDH/Pal. Herein, CO<sub>2</sub> was adsorbed on the surface of PEI/CoAl-LDH/Pal in the forms of bicarbonate and amino carboxylate. Additionally, PEI/CoAl-LDH/Pal exhibited excellent regeneration performance and maintained the adsorption capacity over 9 cycles, which is anticipated to be a promising candidate for CO<sub>2</sub> capture.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107625"},"PeriodicalIF":5.3,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142586269","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}
Pub Date : 2024-11-05DOI: 10.1016/j.clay.2024.107623
Fengyuan Wang, Min Yang, Yuchun Yang, Yanling Tian
With the escalating market demand for lithium, the development and efficient utilization of lithium resources have become crucial. This study introduced a method for leaching lithium from raw clay-type lithium ores using a composite sulfuric acid oxalic acid system. The experimental results revealed that the optimal conditions for the leaching process included roasting temperature of 600 °C, sulfuric acid concentration of 0.8 mol/L, liquid-solid ratio of 5 mL/g, leaching temperature of 90 °C, leaching duration of 90 min, and oxalic acid dosage of 2 g. Under these conditions, the leaching efficiency of lithium reached 93.45 %. The structural changes during the lithium leaching process and leaching mechanism were analyzed by XRD, SEM, TOF-SIMS. It was found that the minerals after mixed-acid leaching showed a loose morphology, a decrease in the average particle size, and a significant increase in the specific surface area as well as the pore volume, leading to improved lithium leaching efficiency. Furthermore, the mechanism underlying the mixed-acid leaching of lithium from clay-type lithium ores was explored. According to this mechanism, sulfuric acid first dissociated H+, which disrupted the mineral structure, allowing further destruction by oxalic acid. During this process, Li+ was continuously replaced by H+ and reacted with C2O42− dissociated from oxalic acid to form water-soluble Li2C2O4.
{"title":"Synergistic leaching of lithium from clay-type lithium ore using sulfuric acid and oxalic acid","authors":"Fengyuan Wang, Min Yang, Yuchun Yang, Yanling Tian","doi":"10.1016/j.clay.2024.107623","DOIUrl":"10.1016/j.clay.2024.107623","url":null,"abstract":"<div><div>With the escalating market demand for lithium, the development and efficient utilization of lithium resources have become crucial. This study introduced a method for leaching lithium from raw clay-type lithium ores using a composite sulfuric acid oxalic acid system. The experimental results revealed that the optimal conditions for the leaching process included roasting temperature of 600 °C, sulfuric acid concentration of 0.8 mol/L, liquid-solid ratio of 5 mL/g, leaching temperature of 90 °C, leaching duration of 90 min, and oxalic acid dosage of 2 g. Under these conditions, the leaching efficiency of lithium reached 93.45 %. The structural changes during the lithium leaching process and leaching mechanism were analyzed by XRD, SEM, TOF-SIMS. It was found that the minerals after mixed-acid leaching showed a loose morphology, a decrease in the average particle size, and a significant increase in the specific surface area as well as the pore volume, leading to improved lithium leaching efficiency. Furthermore, the mechanism underlying the mixed-acid leaching of lithium from clay-type lithium ores was explored. According to this mechanism, sulfuric acid first dissociated H<sup>+</sup>, which disrupted the mineral structure, allowing further destruction by oxalic acid. During this process, Li<sup>+</sup> was continuously replaced by H<sup>+</sup> and reacted with C<sub>2</sub>O<sub>4</sub><sup>2−</sup> dissociated from oxalic acid to form water-soluble Li<sub>2</sub>C<sub>2</sub>O<sub>4</sub>.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107623"},"PeriodicalIF":5.3,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142592520","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}
Layered double hydroxides (LDH) have gained considerable attention for their potential application in agriculture, serving as a slow-release source of essential nutrients for plants. This study aimed to investigate the effects of Mg-Al-LDH materials (with M2+/M3+ ratios of 2:1 and 3:1) intercalated with phosphate, both with and without the presence of two plant growth-promoting rhizobacteria (PGPR) strains, on maize growth and the uptake of phosphorus (P), magnesium (Mg), and manganese (Mn). The LDH materials were synthesized, and their properties were assessed by X-ray diffraction (XRD) patterns, Fourier-transform infrared (FT-IR) spectra, and elemental analysis. In an in vitro experiment, the P solubilization capacity of five PGPR strains was evaluated, and the two most effective strains (Bacillus anthracis: B1 & Pseudomonas sp.: B2) were selected for the subsequent pot trials (greenhouse). In the pot experiment, the effectiveness of these two bacterial strains was evaluated in relation to the availability of P for maize plants from specific quantities of Mg-Al-LDH-P (2:1) and Mg-Al-LDH-P (3:1) materials amended in 500 g of soil, providing P concentrations of 0, 50, and 100 mg kg−1. A treatment of triple superphosphate (TSP) was also included as a fast-release P source (50 mg P kg−1). Irrespective of the type of LDH used, the application of LDHs significantly increased the shoot and root biomass of maize plants; the LDH effect was similar or even higher than that of the TSP, driven by the LDH type and P content. The application of LDHs and TSP resulted in higher shoot P concentration in maize plants compared to the untreated control. Inoculation with both bacterial strains increased the shoot P concentration of maize plants in the absence of any P treatments. Moreover, both bacterial strains increased the shoot P concentration of plants in LDH 2:1 (100 mg P kg−1) and TSP treatments, indicating synergistic interactions between PGPR and LDH 2:1 and TSP (while no synergism was found between PGPR and other LDH treatments). Without any LDH/TSP application, only the B1 strain increased the shoot and root biomass of plants compared to the non-inoculated control. In terms of shoot biomass, no synergistic effects were observed in any PGPR-LDH combinations compared to the individual application of PGPR and LDH, which could possibly be due to the short growth period (40 days) of plants. Overall, this study suggests that LDH (2,1) and LDH (3,1) can effectively serve as a P source for enhancing plant growth under P deficiency conditions. Furthermore, the results underscore the potential of PGPR strains to release P from P-containing LDH compounds, which could vary based on the molar ratios of metal cations in LDHs.
层状双氢氧化物（LDH）因其在农业中的潜在应用而备受关注，它是植物必需营养元素的缓释源。本研究旨在探讨磷酸盐插层的 Mg-Al-LDH 材料（M2+/M3+比例为 2:1 和 3:1）在含有或不含有两种植物生长促进根瘤菌（PGPR）菌株的情况下，对玉米生长以及磷（P）、镁（Mg）和锰（Mn）吸收的影响。合成了 LDH 材料，并通过 X 射线衍射（XRD）图谱、傅立叶变换红外光谱（FT-IR）和元素分析评估了它们的特性。在体外实验中，对五种 PGPR 菌株的 P 溶解能力进行了评估，并挑选出两种最有效的菌株（炭疽芽孢杆菌：B1 & ；假单胞菌：B2）用于随后的盆栽试验（温室）。在盆栽试验中，这两种细菌菌株的功效与玉米植株从特定数量的 Mg-Al-LDH-P（2:1）和 Mg-Al-LDH-P（3:1）材料中获取钾的情况有关，这两种材料分别添加在 500 克土壤中，提供的钾浓度分别为 0、50 和 100 毫克/千克。此外，还加入了三重过磷酸钙（TSP）作为快速释放钾源（50 毫克 P kg-1）。无论使用哪种 LDH，施用 LDHs 都能显著增加玉米植株的芽和根的生物量；受 LDH 类型和 P 含量的影响，LDH 的效果与 TSP 相似，甚至更高。与未处理的对照组相比，施用 LDHs 和 TSP 可提高玉米植株嫩枝的 P 浓度。在没有任何 P 处理的情况下，接种这两种细菌菌株会增加玉米植株的芽 P 浓度。此外，在 LDH 2:1 （100 毫克 P kg-1）和 TSP 处理中，两种细菌菌株都能提高植株的芽 P 浓度，这表明 PGPR 与 LDH 2:1 和 TSP 之间存在协同作用（而 PGPR 与其他 LDH 处理之间没有协同作用）。在不施用任何 LDH/TSP 的情况下，与未接种对照相比，只有 B1 菌株能增加植物的芽和根的生物量。就嫩枝生物量而言，与单独施用 PGPR 和 LDH 相比，任何 PGPR-LDH 组合都未观察到协同效应，这可能是由于植物的生长期较短（40 天）。总之，这项研究表明，LDH（2,1）和 LDH（3,1）可以有效地作为缺钾条件下促进植物生长的钾源。此外，研究结果还强调了 PGPR 菌株从含 P 的 LDH 化合物中释放 P 的潜力，这可能会根据 LDH 中金属阳离子的摩尔比而有所不同。
{"title":"Maximizing the efficiency of layered double hydroxides as a slow-release phosphate fertilizer: A study on the impact of plant growth-promoting rhizobacteria","authors":"Amir Hassanzadeh , Mohsen Hamidpour , Payman Abbaszadeh Dahaji , Abdolreza Akhgar , Khalil Kariman","doi":"10.1016/j.clay.2024.107620","DOIUrl":"10.1016/j.clay.2024.107620","url":null,"abstract":"<div><div>Layered double hydroxides (LDH) have gained considerable attention for their potential application in agriculture, serving as a slow-release source of essential nutrients for plants. This study aimed to investigate the effects of Mg-Al-LDH materials (with M<sup>2+</sup>/M<sup>3+</sup> ratios of 2:1 and 3:1) intercalated with phosphate, both with and without the presence of two plant growth-promoting rhizobacteria (PGPR) strains, on maize growth and the uptake of phosphorus (P), magnesium (Mg), and manganese (Mn). The LDH materials were synthesized, and their properties were assessed by X-ray diffraction (XRD) patterns, Fourier-transform infrared (FT-IR) spectra, and elemental analysis. In an in vitro experiment, the P solubilization capacity of five PGPR strains was evaluated, and the two most effective strains (<em>Bacillus anthracis</em>: B1 & <em>Pseudomonas</em> sp.: B2) were selected for the subsequent pot trials (greenhouse). In the pot experiment, the effectiveness of these two bacterial strains was evaluated in relation to the availability of P for maize plants from specific quantities of Mg-Al-LDH-P (2:1) and Mg-Al-LDH-P (3:1) materials amended in 500 g of soil, providing P concentrations of 0, 50, and 100 mg kg<sup>−1</sup>. A treatment of triple superphosphate (TSP) was also included as a fast-release P source (50 mg P kg<sup>−1</sup>). Irrespective of the type of LDH used, the application of LDHs significantly increased the shoot and root biomass of maize plants; the LDH effect was similar or even higher than that of the TSP, driven by the LDH type and P content. The application of LDHs and TSP resulted in higher shoot P concentration in maize plants compared to the untreated control. Inoculation with both bacterial strains increased the shoot P concentration of maize plants in the absence of any P treatments. Moreover, both bacterial strains increased the shoot P concentration of plants in LDH 2:1 (100 mg P kg<sup>−1</sup>) and TSP treatments, indicating synergistic interactions between PGPR and LDH 2:1 and TSP (while no synergism was found between PGPR and other LDH treatments). Without any LDH/TSP application, only the B1 strain increased the shoot and root biomass of plants compared to the non-inoculated control. In terms of shoot biomass, no synergistic effects were observed in any PGPR-LDH combinations compared to the individual application of PGPR and LDH, which could possibly be due to the short growth period (40 days) of plants. Overall, this study suggests that LDH (2,1) and LDH (3,1) can effectively serve as a P source for enhancing plant growth under P deficiency conditions. Furthermore, the results underscore the potential of PGPR strains to release P from P-containing LDH compounds, which could vary based on the molar ratios of metal cations in LDHs.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107620"},"PeriodicalIF":5.3,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142578315","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}
Pub Date : 2024-10-31DOI: 10.1016/j.clay.2024.107609
Ting Xiong, Bowen Zheng, Keding Li, Lin Zhang, Shuai Zhang
In this task, a novel montmorillonite composite (CMH) was successfully prepared by surfactant modifying with cetyltrimethylammonium bromide (CTAB) and compounding with hydroxyapatite (HAP). In contrast to nature montmorillonite (MMT), CMH showed better U(VI) adsorption properties (R > 99 %) in a wide adsorbent dose range (0.2 to 1.0 mg/L) with the initial U(VI) concentration of 10 mg/L at pH = 5.0 and T = 298 K. The adsorption capacity of CMH for U(VI) reached 678.6 mg/g, which was much higher than most of reported clay-based adsorbents, suggesting that the adsorption performances of CMH were at the upper-middle level among clay-based adsorbents. In addition, CMH also performed good recoverability with the adsorption efficiency of 96.2 % after five cycles and could still maintain relatively high U(VI) adsorption capacity even during complex water system, which was expected to be used for adsorbing U(VI) from various water environment. In terms of the differences in morphology, structure and composition between MMT and CMH, the excellent U(VI) adsorption performances of CMH could be explained by the rougher surface, larger interlayer spacing and more pores and functional groups, thus providing more binding sites. The adsorption mechanism involved electrostatic interaction, ion exchange and complexation. This job supplied a novel opinion for the explore of low cost and highly efficient adsorbent synthesis for U(VI) adsorption.
{"title":"Adsorption behaviors of U(VI) in aqueous solution by cetyltrimethylammonium bromide modified montmorillonite-hydroxyapatite composite adsorbent","authors":"Ting Xiong, Bowen Zheng, Keding Li, Lin Zhang, Shuai Zhang","doi":"10.1016/j.clay.2024.107609","DOIUrl":"10.1016/j.clay.2024.107609","url":null,"abstract":"<div><div>In this task, a novel montmorillonite composite (CMH) was successfully prepared by surfactant modifying with cetyltrimethylammonium bromide (CTAB) and compounding with hydroxyapatite (HAP). In contrast to nature montmorillonite (MMT), CMH showed better U(VI) adsorption properties (<em>R</em> > 99 %) in a wide adsorbent dose range (0.2 to 1.0 mg/L) with the initial U(VI) concentration of 10 mg/L at pH = 5.0 and <em>T</em> = 298 K. The adsorption capacity of CMH for U(VI) reached 678.6 mg/g, which was much higher than most of reported clay-based adsorbents, suggesting that the adsorption performances of CMH were at the upper-middle level among clay-based adsorbents. In addition, CMH also performed good recoverability with the adsorption efficiency of 96.2 % after five cycles and could still maintain relatively high U(VI) adsorption capacity even during complex water system, which was expected to be used for adsorbing U(VI) from various water environment. In terms of the differences in morphology, structure and composition between MMT and CMH, the excellent U(VI) adsorption performances of CMH could be explained by the rougher surface, larger interlayer spacing and more pores and functional groups, thus providing more binding sites. The adsorption mechanism involved electrostatic interaction, ion exchange and complexation. This job supplied a novel opinion for the explore of low cost and highly efficient adsorbent synthesis for U(VI) adsorption.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107609"},"PeriodicalIF":5.3,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552242","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}
Pub Date : 2024-10-30DOI: 10.1016/j.clay.2024.107621
Rongpeng Yu , Qinya Huang , Zhiwei Ding , Yiran Li , Chaoyang Li , Zhanchao Liu , Yan Liu
Considering the effect of secondary metabolites on quercetin (QC) separation and purification in plants, herein, four types of hydrophilic deep eutectic solvents (DESs) composed by organic acids and glycosyl-, quaternary ammonium- or alcohol-based hydrogen bond acceptors were designed and modified on the palygoskite (Pal) surface to improve the selectivity of QC via dispersive solid-phase extraction (D-SPE). The selectivity study followed the following order: Pal- [Choline chloride (ChCl)] [Levulinic acid (Lev)] > Pal- [Glycerol (Gly)] [L-Proline (Pro)] > Pal- [Glucose (Glu)] [D-lactic acid (Lac)] > Pal- [Benzyl triethyl ammonium chloride (BTBAC)] [D-lactic acid (Lac)]. Based on the single-factor method, Response surface methodology (RSM) by using a Box-Behnken design (BBD) was applied to assess the mutual interactions and effects between the three factors and the optimized preparation conditions. The optimal nanoparticles (Pal- [ChCl] [Lev]) showed the best adsorption capacity for QC (29.81 mg/g) in the mixture of methanol and phosphate buffered solution (PBS) and high selectivity which was 1.95 times and 2.12 times that of luteolin and rutin hydrate, respectively. Mechanism exploration indicated that Pal-DESs selectively adsorbed QC via electrostatic interaction, π-π stacking and hydrogen bonds. Furthermore, the screened DES of ([ChCl] [Lev]) could act on QC aqueous solution to improve its solubility and stability during preservation. The proposed QC separation strategy centered on the guiding role of DESs in selective adsorption. Additional alternatives for the synthesis of high-efficiency and hydrophilic functional adsorbents for flavonoids were made available by this green DESs regulation concept.
{"title":"Design of deep eutectic solvents modified palygorskite for selective recognition, mechanism study and stable preservation of quercetin","authors":"Rongpeng Yu , Qinya Huang , Zhiwei Ding , Yiran Li , Chaoyang Li , Zhanchao Liu , Yan Liu","doi":"10.1016/j.clay.2024.107621","DOIUrl":"10.1016/j.clay.2024.107621","url":null,"abstract":"<div><div>Considering the effect of secondary metabolites on quercetin (QC) separation and purification in plants, herein, four types of hydrophilic deep eutectic solvents (DESs) composed by organic acids and glycosyl-, quaternary ammonium- or alcohol-based hydrogen bond acceptors were designed and modified on the palygoskite (Pal) surface to improve the selectivity of QC via dispersive solid-phase extraction (D-SPE). The selectivity study followed the following order: Pal- [Choline chloride (ChCl)] [Levulinic acid (Lev)] > Pal- [Glycerol (Gly)] [L-Proline (Pro)] > Pal- [Glucose (Glu)] [D-lactic acid (Lac)] > Pal- [Benzyl triethyl ammonium chloride (BTBAC)] [D-lactic acid (Lac)]. Based on the single-factor method, Response surface methodology (RSM) by using a Box-Behnken design (BBD) was applied to assess the mutual interactions and effects between the three factors and the optimized preparation conditions. The optimal nanoparticles (Pal- [ChCl] [Lev]) showed the best adsorption capacity for QC (29.81 mg/g) in the mixture of methanol and phosphate buffered solution (PBS) and high selectivity which was 1.95 times and 2.12 times that of luteolin and rutin hydrate, respectively. Mechanism exploration indicated that Pal-DESs selectively adsorbed QC via electrostatic interaction, π-π stacking and hydrogen bonds. Furthermore, the screened DES of ([ChCl] [Lev]) could act on QC aqueous solution to improve its solubility and stability during preservation. The proposed QC separation strategy centered on the guiding role of DESs in selective adsorption. Additional alternatives for the synthesis of high-efficiency and hydrophilic functional adsorbents for flavonoids were made available by this green DESs regulation concept.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107621"},"PeriodicalIF":5.3,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552248","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}
Pub Date : 2024-10-30DOI: 10.1016/j.clay.2024.107619
Fengya Ran , Meng He , Shiyong Sun , Rui Lv , Sen Lin , Ke Wang , Yevgeny Aleksandrovich Golubev , Olga Borisovna Kotova , Elena Leonidovna Kotova
Zeolite products synthesized from mineral materials are receiving widespread attention, while there are few reports on the introduction of heteroatom metals from minerals into zeolites. Herein, the effects of different silicon sources, hydrothermal reaction time and the amount of template on the crystallisation of Fe-ZSM-5 were investigated. The morphology and structure of ZSM-5 were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), X-ray electron spectroscopy (XPS) and scanning electron microscopy (SEM). The catalysis of 3,3′,5,5′-tetramethylbenzidine (TMB) by Fe-ZSM-5 was then carried out to evaluate its enzyme-like catalytic performance as a type of nanozyme catalyst. The results showed that Fe-ZSM-5 exhibited peroxidase-like activity, oxidizing TMB into a colored substance in the presence of hydrogen peroxide (H2O2). Kinetic analysis implied that, compared with natural horseradish peroxidase (HRP), Fe-ZSM-5 peroxidase mimics exhibit inferior affinity and enzymatic catalytic velocity towards the TMB substrate. However, it exhibited excellent stability under extreme pH, temperature, and ionic strength conditions. This work provides a possible reference for the construction of functional nanozymes using natural mineral resources.
{"title":"Synthesis of Fe-ZSM-5 zeolite from high iron-containing palygorskite with peroxidase-like catalytic performance","authors":"Fengya Ran , Meng He , Shiyong Sun , Rui Lv , Sen Lin , Ke Wang , Yevgeny Aleksandrovich Golubev , Olga Borisovna Kotova , Elena Leonidovna Kotova","doi":"10.1016/j.clay.2024.107619","DOIUrl":"10.1016/j.clay.2024.107619","url":null,"abstract":"<div><div>Zeolite products synthesized from mineral materials are receiving widespread attention, while there are few reports on the introduction of heteroatom metals from minerals into zeolites. Herein, the effects of different silicon sources, hydrothermal reaction time and the amount of template on the crystallisation of Fe-ZSM-5 were investigated. The morphology and structure of ZSM-5 were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), X-ray electron spectroscopy (XPS) and scanning electron microscopy (SEM). The catalysis of 3,3′,5,5′-tetramethylbenzidine (TMB) by Fe-ZSM-5 was then carried out to evaluate its enzyme-like catalytic performance as a type of nanozyme catalyst. The results showed that Fe-ZSM-5 exhibited peroxidase-like activity, oxidizing TMB into a colored substance in the presence of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). Kinetic analysis implied that, compared with natural horseradish peroxidase (HRP), Fe-ZSM-5 peroxidase mimics exhibit inferior affinity and enzymatic catalytic velocity towards the TMB substrate. However, it exhibited excellent stability under extreme pH, temperature, and ionic strength conditions. This work provides a possible reference for the construction of functional nanozymes using natural mineral resources.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"262 ","pages":"Article 107619"},"PeriodicalIF":5.3,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552241","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}
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