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Control of phosphorus release from sediment by multiple applications of lanthanum-modified palygorskite in the presence of suspended particulate matter input 在存在悬浮颗粒物输入的情况下,镧改性坡缕石的多种应用控制沉积物中磷的释放
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-01 Epub Date: 2025-11-27 DOI: 10.1016/j.clay.2025.108063
Chunyu Tian, Jianwei Lin, Yanhui Zhan
This study explored the performance and underlying mechanisms of multiple applications of lanthanum-modified palygorskite (LMP) for mitigating phosphorus (P) release from sediment to the overlying water under the condition of suspended particulate matter (SPM) input, with a further analysis of the impact of LMP dosing frequency on the control efficiency. The findings revealed that LMP possessed a strong phosphate adsorption capacity in water (maximum adsorption capacity at pH 7: 22.5 mg/g), with significantly higher lanthanum utilization efficiency than pure lanthanum hydroxide (LH) and commercial lanthanum-modified bentonite (LMB). Multiple applications of LMP effectively inhibited the release of sediment-derived P to the overlying water under SPM input conditions, with superior control efficiency compared to multiple applications of LMB. Average reduction efficiencies of SRP in the overlying water of 72.8 %, 76.2 %, and 76.5 % were achieved with six, eleven, and thirty-one applications of LMP, respectively. These multiple LMP applications also effectively suppressed internal P release from the upper sediment layer into the pore water, achieving higher control efficiency than LMB. Even with LMP application, the release of sedimentary P to the pore water continued through mechanisms involving iron-reducing bacteria (IRB)-driven dissimilatory Fe(III) reduction and chemical Fe(III) reduction mediated by sulfate-reducing bacteria (SRB)-driven sulfate reduction products. However, LMP effectively eliminated soluble reactive phosphorus (SRP) in the pore water through two pathways: adsorbing pore water SRP, and inactivating diffusive gradients in thin films (DGT)-labile P and mobile P in the upper sediment. This dual-pathway action constitutes the key mechanism by which multiple LMP applications control the release of sediment-derived P to the overlying water under SPM input conditions. Additionally, the frequency of LMP dosing in the multiple additions affected its efficacy in controlling sediment P release. Overall, multiple applications of LMP represent a highly promising method for controlling sediment P release in the presence of SPM inputs.
本研究探讨了在悬浮颗粒物(SPM)输入条件下,镧改性坡缕石(LMP)多种应用对沉积物上覆水体磷释放的抑制作用及其机制,并进一步分析了LMP投加频率对控制效果的影响。结果表明,LMP在水中具有较强的磷酸盐吸附能力(pH = 7时吸附量最大,为22.5 mg/g),镧的利用率明显高于纯氢氧化镧(LH)和工业镧改性膨润土(LMB)。在SPM输入条件下,多次施用LMP有效地抑制了沉积物源磷向上覆水体的释放,与多次施用LMB相比,控制效率更高。在LMP的6次、11次和31次应用中,SRP在上覆水中的平均还原效率分别达到72.8%、76.2%和76.5%。这些多重LMP应用也有效地抑制了上层沉积物向孔隙水中的内部磷释放,达到了比LMB更高的控制效果。即使使用了LMP,沉积态磷仍通过铁还原细菌(IRB)驱动的异构化Fe(III)还原和硫酸盐还原细菌(SRB)驱动的硫酸盐还原产物介导的化学Fe(III)还原机制继续向孔隙水中释放。然而,LMP通过吸附孔隙水中的可溶性活性磷(SRP)和使上层沉积物中薄膜(DGT)-不稳定P和流动P的扩散梯度失活两种途径有效地消除了孔隙水中的可溶性活性磷(SRP)。这种双途径作用构成了多个LMP应用在SPM输入条件下控制沉积物源磷向上覆水体释放的关键机制。此外,在多次添加中,LMP的添加频率影响其控制沉积物P释放的效果。总的来说,LMP的多种应用代表了在SPM输入存在的情况下控制沉积物P释放的一种非常有前途的方法。
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引用次数: 0
Clay-polymer composite adsorbents for in situ uranium remediation in groundwater: Adsorption mechanism, reusability, and field-scale performance estimation 用于地下水铀原位修复的粘土-聚合物复合吸附剂:吸附机制、可重复使用性和现场规模性能评估
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-01 Epub Date: 2025-11-22 DOI: 10.1016/j.clay.2025.108043
Subeen Kim , Sanghee Park , Donghye Heo , Jimin Mun , Minhee Lee , Minjune Yang
This study presents the development and evaluation of a montmorillonite–polysulfone sorbent (MPS) designed for the remediation of uranium-contaminated groundwater. The composite was synthesized by embedding montmorillonite (MMT) into a polysulfone (PSF) matrix to combine the high adsorption capacity of layered silicates with the mechanical stability of synthetic polymers. Batch experiments were conducted to investigate the effects of MMT content, pH, contact time, and uranium (U) concentration on adsorption behavior. Optimal performance was achieved with 4 wt% MMT, showing >99 % adsorption efficiency at pH 7.0. Kinetic data were best described by the pseudo-first-order model (R2 = 0.969), while the Elovich model captured late-stage adsorption behavior, suggesting a two-phase mechanism involving rapid physisorption followed by slower chemisorption. Isotherm analysis indicated that both Langmuir and Freundlich models fitted the data well, with a maximum adsorption capacity of 453.7 μg/g. SEM-EDS characterization confirmed U penetration into both surface and internal pore structures of MPS. Reusability tests demonstrated sustained adsorption (≥95 %) and desorption (≥93 %) efficiencies over ten cycles using 0.1 M HNO₃. In continuous-flow permeable reactive barrier (PRB) system, MPS maintained U removal efficiencies >95 % over 34 pore volumes, with minimal breakthrough. Field-scale modeling suggests that an MPS-based PRB can treat 3.27 × 104 m3 of groundwater over 7 yr with ten regeneration cycles. These findings highlight the structural robustness and practical applicability of MPS for in situ U remediation under realistic hydrogeological conditions.
研究了一种用于铀污染地下水修复的蒙脱石-聚砜吸附剂(MPS)的研制与评价。将蒙脱土(MMT)包埋在聚砜(PSF)基体中,结合层状硅酸盐的高吸附能力和合成聚合物的机械稳定性,合成了该复合材料。通过批量实验考察了MMT含量、pH、接触时间和铀浓度对吸附行为的影响。4 wt% MMT的吸附效果最佳,在pH 7.0时的吸附效率为99 %。拟一阶模型(R2 = 0.969)最能描述动力学数据,而Elovich模型捕获了后期吸附行为,表明两相吸附机制包括快速物理吸附和缓慢化学吸附。等温线分析表明,Langmuir和Freundlich模型拟合较好,最大吸附量为453.7 μg/g。SEM-EDS表征证实了U在MPS表面和内部孔隙结构中均有渗透。可重用性测试表明,使用0.1 M HNO₃,在10个循环中,持续的吸附(≥95 %)和解吸(≥93 %)效率。在连续渗流反应性屏障(PRB)体系中,MPS在34个孔隙体积内保持了95% %的U去除效率,并且几乎没有突破。现场尺度模拟表明,基于mps的PRB在7 年的10个再生周期内可以处理3.27 × 104 m3的地下水。这些发现突出了MPS的结构稳健性和在现实水文地质条件下的原位U修复的实用性。
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引用次数: 0
Metakaolin-based single-step engineered geopolymer composites: Design and performance characterization 基于偏高岭土的单步工程地聚合物复合材料:设计和性能表征
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-01 Epub Date: 2025-11-24 DOI: 10.1016/j.clay.2025.108055
Fei Wang , Long Liang , Yao Ding , Xinjian Sun , Jingming Cai , Neven Ukrainczyk , Kequan Yu
Conventional one-part engineered geopolymer composite (EGC) facilitates the mixing process of EGC. However, this “one-part” only refers to the matrix of EGC, the reinforcing fiber as the second step should be separately added during mixing. In this study, through a careful multi-component design to regulate matrix rheology and fiber dispersion, we pioneer the development of a single-step metakaolin-based EGC, which requires only a single mixing step of adding water to achieve exceptional tensile performance, without dry pre-mixing process. This one-part EGC exhibits a density of approximately 1100 kg/m3 and a compressive strength of up to 40 MPa, outperforming conventional “one-part” geopolymers with similar densities. Remarkably, with only 0.5 % fiber volume fraction, about 1/4 of that in conventional EGC, the proposed single-step EGC achieves a high tensile strain capacity of 6 %. Further, the 28-day dry shrinkage remains below 300 με, setting a new benchmark for the lowest dry shrinkage in geopolymers (400–1000 με) and even rivaling ordinary concrete with similar strength grades. The current findings can address the production process shortcoming of conventional fiber-reinforced composite compared to ordinary concrete and facilitate the practical application of EGC.
传统的单组分工程地聚合物复合材料(EGC)有利于EGC的混合过程。但是,这里的“一部分”仅指EGC的基体,作为第二步的增强纤维应在混合时单独添加。在这项研究中,通过精心的多组分设计来调节基体流变和纤维分散,我们率先开发了一种基于偏高岭土的单步EGC,它只需要一个混合步骤,即加水就可以达到优异的拉伸性能,而不需要干燥的预混合过程。这种单组分EGC的密度约为1100 kg/m3,抗压强度高达40 MPa,优于类似密度的传统“单组分”地聚合物。值得注意的是,当纤维体积分数仅为0.5%,约为常规EGC的1/4时,单步EGC的拉伸应变容量达到6%。此外,28天干收缩率保持在300 με以下,为地聚合物中最低干收缩率(400-1000 με)设定了新的基准,甚至可以与类似强度等级的普通混凝土相媲美。本研究结果可以解决传统纤维增强复合材料相对于普通混凝土的生产工艺缺陷,促进纤维增强复合材料的实际应用。
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引用次数: 0
Swelling pressure response of Bentonil-WRK bentonite under thermal cycling up to 150°C 膨润土- wrk膨润土在150℃热循环下的膨胀压力响应
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-01 Epub Date: 2025-11-21 DOI: 10.1016/j.clay.2025.108046
Deuk-Hwan Lee , Seok Yoon , Minhyeong Lee , Seeun Chang , Changsoo Lee , Dong-Keun Cho , Gi-Jun Lee
This study investigates the thermal effects on the swelling pressure response of compacted Bentonil-WRK (Ca-type) bentonite. Swelling pressure tests were conducted under saturated conditions at dry densities ranging from 1.40 to 1.62 g/cm3 using a high-temperature load cell system capable of operation up to 160°C. To simulate repository thermal environments, the specimens were subjected to two controlled thermal cycles between 30°C and 150°C. Results revealed a temperature-dependent response, characterized by a gradual decrease in swelling pressure during heating. While the absolute pressure reduction was larger at higher dry densities, the swelling pressure normalized by its value at 30°C showed a more pronounced decrease at lower densities, indicating that the lower-density specimens exhibited greater relative thermal sensitivity. During the heating–cooling cycles, all specimens exhibited thermal hysteresis, characterized by partial recovery of swelling pressure upon cooling, whereas the magnitude of hysteresis was markedly reduced in the second thermal cycle. The swelling pressure did not reach equilibrium at temperatures above 90°C during the first heating stage and only at 150°C in the second heating stage. Although higher dry density specimens exhibited larger absolute pressure reductions, their smaller relative decreases indicate enhanced thermal stability, suggesting that such compaction levels are favorable for ensuring long-term barrier performance under repository-relevant thermal loads.
研究了热效应对压实膨润土- wrk (ca型)膨润土膨胀压力响应的影响。膨胀压力测试是在干密度为1.40至1.62 g/cm3的饱和条件下进行的,使用的是能够在160°C下工作的高温称重传感器系统。为了模拟储存库的热环境,在30°C和150°C之间进行了两个受控的热循环。结果揭示了温度依赖的响应,其特征是在加热过程中膨胀压力逐渐降低。干密度高时,绝对压力降低幅度较大,30℃时膨胀压力归一化后,低密度时膨胀压力降低幅度更大,说明低密度试样表现出更大的相对热敏性。在加热-冷却循环过程中,所有试样都表现出热滞后现象,其特征是冷却后膨胀压力部分恢复,而在第二次热循环过程中,热滞后的幅度明显减小。在第一次加热阶段,膨胀压力在温度高于90℃时未达到平衡,在第二次加热阶段,膨胀压力仅在温度高于150℃时达到平衡。尽管干密度高的样品表现出更大的绝对压力降低,但其较小的相对降低表明热稳定性增强,这表明这种压实水平有利于在与库相关的热负荷下确保长期屏障性能。
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引用次数: 0
Preparation of composite material sodium dodecyl sulfonate/2-methylimidazole zinc MOF/ palygorskite and its high- efficiency adsorption for tetracycline 十二烷基磺酸钠/2-甲基咪唑锌复合材料的制备及其对四环素的高效吸附
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-01 Epub Date: 2025-11-18 DOI: 10.1016/j.clay.2025.108057
Xin Li , Wen Chen , Jin-Long Jiang , Xia-ping Zhu , Ping Zhao
In this study, a one pot self-assembly strategy was adopted in aqueous solution to prepare a new material of sodium dodecyl sulfonate/2-methylimidazole zinc MOF/palygorskite (SDS/ZIF-8/PAL, abbreviated as SZP) with certain mesopores and high adsorption capacity for tetracycline. The material was prepared using surfactants such as sodium dodecyl sulfonate (SDS), Zn(NO3)2·6H2O, 2-methylimidazole (2-MI) (maintaining 2-MI: Zn2+ = 10: 1), and palygorskite (PAL), and was environmentally friendly in both preparation and application. The saturated adsorption capacity of SZP was 914 mg/g at pH 7.0, temperature 298 K, adsorption time 180 min and ionic strength 0.01 mol/L, which was much higher than that of unmodified PAL and TC adsorption materials in other reports. X-ray photoelectron spectroscopy (XPS) analysis showed that SZP mainly removes TC through hydrogen bonding and coordination. Furthermore, SZP had good adsorption selectivity for TC, and the interference of dissolved organic substances, coexisting inorganic anions, cations and antibiotics with high detection rate in environmental water was small. And the removal rate was still above 90 % after five times of reuse. When SZP was applied to adsorb TC simulated water samples with different environmental water as the background, the concentration was 2.5 times of the highest concentration (20 mg/L) in actual aquaculture water, and the removal rate was up to 97 %. It showed that SZP can not only remove all TC from environmental water, but also its adsorption capacity far exceeds the pollution capacity, which indicated that SZP has potential application value in removing TC from environmental water.
本研究在水溶液中采用一锅自组装策略,制备了一种具有一定介孔且对四环素具有较高吸附能力的十二烷基磺酸钠/2-甲基咪唑锌MOF/坡高岭土新材料(SDS/ZIF-8/PAL,简称SZP)。该材料采用十二烷基磺酸钠(SDS)、Zn(NO3)2·6H2O、2-甲基咪唑(2- mi)(维持2- mi: Zn2+ = 10:1)和坡面石(PAL)等表面活性剂制备,制备和应用均具有环保性。在pH 7.0、温度298 K、吸附时间180 min、离子强度0.01 mol/L条件下,SZP的饱和吸附容量为914 mg/g,远高于其他报道的未改性PAL和TC吸附材料。x射线光电子能谱(XPS)分析表明,SZP主要通过氢键和配位去除TC。SZP对TC具有良好的吸附选择性,对环境水体中溶解有机物、共存的无机阴离子、阳离子和高检出率的抗生素干扰小。重复使用5次后,去除率仍在90%以上。应用SZP吸附不同环境水为背景的TC模拟水样时,浓度为实际养殖水中最高浓度(20 mg/L)的2.5倍,去除率可达97%。结果表明,SZP不仅可以去除环境水中的全部TC,而且其吸附量远远超过污染能力,这表明SZP在去除环境水中TC方面具有潜在的应用价值。
{"title":"Preparation of composite material sodium dodecyl sulfonate/2-methylimidazole zinc MOF/ palygorskite and its high- efficiency adsorption for tetracycline","authors":"Xin Li ,&nbsp;Wen Chen ,&nbsp;Jin-Long Jiang ,&nbsp;Xia-ping Zhu ,&nbsp;Ping Zhao","doi":"10.1016/j.clay.2025.108057","DOIUrl":"10.1016/j.clay.2025.108057","url":null,"abstract":"<div><div>In this study, a one pot self-assembly strategy was adopted in aqueous solution to prepare a new material of sodium dodecyl sulfonate/2-methylimidazole zinc MOF/palygorskite (SDS/ZIF-8/PAL, abbreviated as SZP) with certain mesopores and high adsorption capacity for tetracycline. The material was prepared using surfactants such as sodium dodecyl sulfonate (SDS), Zn(NO<sub>3</sub>)<sub>2</sub>·6H<sub>2</sub>O, 2-methylimidazole (2-MI) (maintaining 2-MI: Zn<sup>2+</sup> = 10: 1), and palygorskite (PAL), and was environmentally friendly in both preparation and application. The saturated adsorption capacity of SZP was 914 mg/g at pH 7.0, temperature 298 K, adsorption time 180 min and ionic strength 0.01 mol/L, which was much higher than that of unmodified PAL and TC adsorption materials in other reports. X-ray photoelectron spectroscopy (XPS) analysis showed that SZP mainly removes TC through hydrogen bonding and coordination. Furthermore, SZP had good adsorption selectivity for TC, and the interference of dissolved organic substances, coexisting inorganic anions, cations and antibiotics with high detection rate in environmental water was small. And the removal rate was still above 90 % after five times of reuse. When SZP was applied to adsorb TC simulated water samples with different environmental water as the background, the concentration was 2.5 times of the highest concentration (20 mg/L) in actual aquaculture water, and the removal rate was up to 97 %. It showed that SZP can not only remove all TC from environmental water, but also its adsorption capacity far exceeds the pollution capacity, which indicated that SZP has potential application value in removing TC from environmental water.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108057"},"PeriodicalIF":5.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576383","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 of Na-montmorillonite in the presence of dissolved gas molecules 钠蒙脱土在溶解气体分子存在下的溶胀
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-01 Epub Date: 2025-11-18 DOI: 10.1016/j.clay.2025.108058
Jerry Peprah Owusu , Konstantinos Karalis , Nikolaos I. Prasianakis , Alessio Ferrari , Sergey V. Churakov
Various dissolved gases, such as CO2, H2, and CH4, may be present in the near-field geological repository due to metal corrosion or the degradation of organic waste. However, the influence of dissolved gases on the swelling behavior of bentonites, commonly used as backfill material, is still poorly understood. In this study, classical molecular dynamics simulations are conducted to investigate the swelling behavior of Na-Mt as a function of compaction and the presence of dissolved gas. The simulations revealed that the presence of gas molecules increases the swelling pressure of Na-Mt and can be quantitatively explained by Henry’s law, which describes the increase in the gas solubility with pressure. The magnitude of the effect is gas-specific, depending on the dry density of clay and the gas concentration in the external reservoir. Accordingly, a general equation describing the enhanced swelling pressure due to gas solubility is proposed. A detailed analysis of structural transformations in the clay interlayer provided a model-based explanation for the discrepancy between the experimentally measured swelling curves and the simulated curves at high compaction levels. These findings contribute to a better understanding of the fundamental mechanisms underlying the swelling behavior of clays used as barrier material in deep geological disposal.
由于金属腐蚀或有机废物的降解,近场地质储存库中可能存在各种溶解气体,如CO2、H2和CH4。然而,溶解气体对膨润土膨胀行为的影响,通常被用作回填材料,仍然知之甚少。在这项研究中,经典分子动力学模拟研究了Na-Mt的膨胀行为作为压实和溶解气体存在的函数。模拟结果表明,气体分子的存在增加了Na-Mt的溶胀压力,这可以用Henry定律来定量解释,Henry定律描述了气体溶解度随压力的增加。这种影响的大小取决于粘土的干密度和外部储层中的气体浓度,是特定于气体的。据此,提出了描述气体溶解度引起的膨胀压力增大的一般方程。通过对粘土夹层结构变化的详细分析,为高压实水平下实验测量膨胀曲线与模拟曲线之间的差异提供了基于模型的解释。这些发现有助于更好地理解深层地质处置中作为屏障材料的粘土膨胀行为的基本机制。
{"title":"Swelling of Na-montmorillonite in the presence of dissolved gas molecules","authors":"Jerry Peprah Owusu ,&nbsp;Konstantinos Karalis ,&nbsp;Nikolaos I. Prasianakis ,&nbsp;Alessio Ferrari ,&nbsp;Sergey V. Churakov","doi":"10.1016/j.clay.2025.108058","DOIUrl":"10.1016/j.clay.2025.108058","url":null,"abstract":"<div><div>Various dissolved gases, such as CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, and CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>, may be present in the near-field geological repository due to metal corrosion or the degradation of organic waste. However, the influence of dissolved gases on the swelling behavior of bentonites, commonly used as backfill material, is still poorly understood. In this study, classical molecular dynamics simulations are conducted to investigate the swelling behavior of Na-Mt as a function of compaction and the presence of dissolved gas. The simulations revealed that the presence of gas molecules increases the swelling pressure of Na-Mt and can be quantitatively explained by Henry’s law, which describes the increase in the gas solubility with pressure. The magnitude of the effect is gas-specific, depending on the dry density of clay and the gas concentration in the external reservoir. Accordingly, a general equation describing the enhanced swelling pressure due to gas solubility is proposed. A detailed analysis of structural transformations in the clay interlayer provided a model-based explanation for the discrepancy between the experimentally measured swelling curves and the simulated curves at high compaction levels. These findings contribute to a better understanding of the fundamental mechanisms underlying the swelling behavior of clays used as barrier material in deep geological disposal.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108058"},"PeriodicalIF":5.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576382","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
Efficient Zn2+ transport and stable electrolyte/electrode interface achieved in acid-modified palygorskite-based quasi-solid-state electrolyte for high-performance zinc-ion batteries 高性能锌离子电池用酸修饰坡高岭土基准固态电解质实现了高效的Zn2+输运和稳定的电解质/电极界面
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-01 Epub Date: 2025-10-21 DOI: 10.1016/j.clay.2025.108015
Zhuo Zhang , Jingyi Zeng , Ming Liu , Bing Xue
The parasitic reactions induced by free water molecules in the electrolyte of aqueous zinc-ion batteries severely disrupt the stability of the electrolyte/electrode interface, significantly affecting the application performance of the batteries. To mitigate the adverse effects of free water molecules in the electrolyte of aqueous zinc-ion batteries, this paper utilized acid-treated palygorskite as the matrix and prepared a palygorskite-based quasi-solid-state electrolyte by adsorbing liquid electrolyte. This approach reduced the reactivity of water molecules in the electrolyte while enhancing the conductivity of zinc ions. The acid treatment with hydrochloric acid achieved fine-tuning of the palygorskite structure, increasing the number of surface -OH groups and enhancing the specific surface area of palygorskite to 199.16 m2 g−1. The plastic limit-liquid limit test results of the palygorskite-salt-water system showed that acid treatment improved the plastic limit (52.6 %) and liquid limit (68.4 %) of palygorskite, confirming that acid treatment could enhance the electrolyte adsorption capacity of palygorskite. Furthermore, acid treatment reduced the Zeta potential of palygorskite (−38.25 mV), strengthening the electrostatic attraction field of palygorskite in the palygorskite-salt-water system. This significantly improved the “relay-style” transmission efficiency of zinc ions in the palygorskite diffusion layer, promoting uniform deposition of zinc ions and inhibiting the growth of zinc dendrites. Simultaneously, it effectively suppressed the transmission of sulfate ions in this diffusion layer, thereby inhibiting the occurrence of side reactions and stabilizing the electrolyte/electrode interface. Based on the unique effect of acid treatment on the microstructure adjustment of palygorskite, the quasi-solid-state electrolyte prepared from acid-treated palygorskite exhibited an ionic conductivity of 20.84 mS cm−1 and an ionic transference number of 0.87. The Zn//Zn symmetric cell assembled with this quasi-solid-state electrolyte demonstrated stable cycling for 3000 h at a current density of 0.2 mA cm−2, with a polarization voltage less than 40 mV. The assembled Zn//MnO2 full cell exhibited an initial discharge specific capacity of 240.57 mAh g−1 at a current density of 0.33 A g−1, and the average coulombic efficiency after 500 cycles was approximately 100 %.
含水锌离子电池电解质中游离水分子诱导的寄生反应严重破坏了电解质/电极界面的稳定性,严重影响电池的应用性能。为了减轻水基锌离子电池电解液中游离水分子的不利影响,本文以酸处理的坡栅土为基体,通过吸附液态电解液制备了坡栅土基准固态电解液。这种方法降低了电解质中水分子的反应性,同时增强了锌离子的导电性。盐酸酸处理实现了坡纹石结构的微调,增加了表面-OH基团的数量,使坡纹石的比表面积达到199.16 m2 g−1。坡缕石-盐-水体系的塑液限试验结果表明,酸处理提高了坡缕石的塑液限(52.6%)和液限(68.4%),证实酸处理可以提高坡缕石对电解质的吸附能力。此外,酸处理降低了坡面石的Zeta电位(- 38.25 mV),增强了坡面石在坡面石-盐-水体系中的静电吸引力。这显著提高了锌离子在坡纹石扩散层中的“继电器式”传输效率,促进了锌离子的均匀沉积,抑制了锌枝晶的生长。同时,它有效地抑制了硫酸盐离子在该扩散层中的传递,从而抑制了副反应的发生,稳定了电解质/电极界面。基于酸处理对坡壁石微观结构调整的独特作用,由酸处理的坡壁石制备的准固态电解质的离子电导率为20.84 mS cm−1,离子转移数为0.87。在0.2 mA cm−2电流密度、极化电压小于40 mV的条件下,用该准固态电解质组装的Zn//Zn对称电池可稳定循环3000 h。该电池在0.33 ag−1电流密度下的初始放电比容量为240.57 mAh g−1,循环500次后的平均库仑效率约为100%。
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引用次数: 0
Construction of superhydrophobic CoZnAl-LDH coating on anodized aluminum surfaces to enhance corrosion and wear resistance 在阳极氧化铝表面制备超疏水CoZnAl-LDH涂层以提高其耐蚀性和耐磨性
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-01 Epub Date: 2025-10-28 DOI: 10.1016/j.clay.2025.108025
Guixiang Wang , Qizi Wu , Maomao Guo , Shilong Zhang , Qiuyan Luo , Hao Yu , Xuyan Guo , Fuqiu Ma , Haining Feng , Ruizhi Wu , Boris Krit
In this study, a novel CoZnAl-LDH coating was synthesized in-situ on anodized aluminum through a hydrothermal method without introducing trivalent metal salts. Subsequently, a vanadate-intercalated LDH-VS coating was fabricated via ion exchange and hexadecyltrimethoxysilane (HDTMS) self-assembly, which integrated long-term corrosion resistance, friction reduction, and superhydrophobicity into a single coating. The morphology and structure of the coatings were investigated using SEM, EDS, XRD, FT-IR, and XPS. The coating performance was evaluated through scratch tests, contact angle, electrochemical, and friction wear tests. The results demonstrated that the contact angle of the LDH-VS increased from 26° to 154° and remained above 120° even after prolonged immersion, exhibiting outstanding self-cleaning and antifouling properties. After 28 days of immersion in 3.5 wt% NaCl solution, the corrosion current density of LDH-VS decreased by four orders of magnitude to 8.09 × 10−9 A·cm−2 compared to bare aluminum alloy and the microstructure remained intact, indicating excellent long-term corrosion resistance. Friction tests confirmed the superior friction reduction of the modified coating, with the average friction coefficient of LDH-VS decreasing to 0.28, significantly lower than that of the aluminum alloy. Scratch tests also verified the coating's excellent adhesion strength. This study provides new insights into the development and application of LDH in superhydrophobicity, long-term corrosion protection, and wear resistance.
本研究在不引入三价金属盐的情况下,通过水热法在阳极氧化铝上原位合成了一种新型的CoZnAl-LDH涂层。随后,通过离子交换和十六烷基三甲氧基硅烷(HDTMS)自组装制备了钒酸盐插层的LDH-VS涂层,该涂层集长期耐腐蚀、减少摩擦和超疏水性于一体。采用SEM、EDS、XRD、FT-IR和XPS对涂层的形貌和结构进行了表征。通过划痕试验、接触角试验、电化学试验和摩擦磨损试验对涂层性能进行了评价。结果表明,LDH-VS的接触角从26°增加到154°,即使长时间浸泡也保持在120°以上,具有出色的自清洁和防污性能。在3.5 wt% NaCl溶液中浸泡28天后,LDH-VS的腐蚀电流密度为8.09 × 10−9 A·cm−2,比裸铝合金降低了4个数量级,且组织保持完整,具有良好的长期耐蚀性。摩擦试验证实,改性涂层具有较好的减摩性能,LDH-VS的平均摩擦系数降至0.28,明显低于铝合金。划痕试验也验证了涂层优异的附着力。本研究为LDH在超疏水性、长效防腐、耐磨性等方面的开发与应用提供了新的思路。
{"title":"Construction of superhydrophobic CoZnAl-LDH coating on anodized aluminum surfaces to enhance corrosion and wear resistance","authors":"Guixiang Wang ,&nbsp;Qizi Wu ,&nbsp;Maomao Guo ,&nbsp;Shilong Zhang ,&nbsp;Qiuyan Luo ,&nbsp;Hao Yu ,&nbsp;Xuyan Guo ,&nbsp;Fuqiu Ma ,&nbsp;Haining Feng ,&nbsp;Ruizhi Wu ,&nbsp;Boris Krit","doi":"10.1016/j.clay.2025.108025","DOIUrl":"10.1016/j.clay.2025.108025","url":null,"abstract":"<div><div>In this study, a novel CoZnAl-LDH coating was synthesized in-situ on anodized aluminum through a hydrothermal method without introducing trivalent metal salts. Subsequently, a vanadate-intercalated LDH-VS coating was fabricated via ion exchange and hexadecyltrimethoxysilane (HDTMS) self-assembly, which integrated long-term corrosion resistance, friction reduction, and superhydrophobicity into a single coating. The morphology and structure of the coatings were investigated using SEM, EDS, XRD, FT-IR, and XPS. The coating performance was evaluated through scratch tests, contact angle, electrochemical, and friction wear tests. The results demonstrated that the contact angle of the LDH-VS increased from 26° to 154° and remained above 120° even after prolonged immersion, exhibiting outstanding self-cleaning and antifouling properties. After 28 days of immersion in 3.5 wt% NaCl solution, the corrosion current density of LDH-VS decreased by four orders of magnitude to 8.09 × 10<sup>−9</sup> A·cm<sup>−2</sup> compared to bare aluminum alloy and the microstructure remained intact, indicating excellent long-term corrosion resistance. Friction tests confirmed the superior friction reduction of the modified coating, with the average friction coefficient of LDH-VS decreasing to 0.28, significantly lower than that of the aluminum alloy. Scratch tests also verified the coating's excellent adhesion strength. This study provides new insights into the development and application of LDH in superhydrophobicity, long-term corrosion protection, and wear resistance.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108025"},"PeriodicalIF":5.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414419","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
Steel-bentonite interaction at elevated temperatures 高温下钢-膨润土相互作用
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-01 Epub Date: 2025-10-21 DOI: 10.1016/j.clay.2025.108011
Šárka Šachlová , Vlastislav Kašpar , Michaela Matulová , Petr Bezdička , Zbyněk Veselka , Petr Večerník
The long-term durability of carbon steel, proposed as the outer layer of waste disposal packages in the Czech deep geological repository concept, is influenced by anaerobic conditions, elevated temperatures, irradiation, bentonite composition and water content. These factors were examined in a small-scale laboratory experiment within the European Joint Programme on Radioactive Waste Management, project CONtainer CORrosion under Disposal conditions (EURAD CONCORD). Carbon steel coupons were embedded in compacted (1600 kg⋅m-3) bentonite of Ca/Mg-type (BCV) and reference bentonite of Na-type (MX-80), subjected to water saturation under a pressure of 5 MPa, heated to 90 °C and 150 °C, and irradiated with a 60Co source at 0.4 Gy·h−1 for 6 to 18 months.
Corrosion rates were primarily affected by temperature and saturation level. Similar rates were observed for both bentonites at 150 °C over 18 months, while lower rates were recorded for MX-80 at 90 °C and at ambient temperature. Irradiation had a negligible effect. Corrosion product composition strongly depended on temperature. At 90 °C, Fe-Ca‑carbonates formed in both bentonites, along with Fe-Ca(Mn-Mg)‑carbonates in BCV. At 150 °C, Fe-Si-O-rich layers and Fe-oxides developed, probably linked to the dissolution of amorphous silica and its incorporation into alteration products.
Elevated temperatures altered the mineralogy and chemistry of the bentonite. Changes included shifts in smectite basal spacing, enrichment with Fex+ and Mn2+, and modifications to exchangeable cation composition, including reduced Mg2+ content. Increased SO₄2− and Cl concentrations in bentonite water leachates, particularly in BCV at 90 °C and MX-80 at 150 °C, partially correlated with higher corrosion rates. These results highlight the interconnected influence of temperature, bentonite type, and chemical interactions on carbon steel corrosion in repository-relevant environments.
在捷克深部地质处置库概念中,作为废物处置包外层的碳钢的长期耐久性受到厌氧条件、高温、辐照、膨润土成分和含水量的影响。这些因素在欧洲放射性废物管理联合方案处置条件下容器腐蚀项目(EURAD CONCORD)范围内进行了小规模实验室试验。将碳钢片埋于压实的(1600 kg⋅m-3) Ca/ mg型膨润土(BCV)和参考型na型膨润土(MX-80)中,在5 MPa压力下进行水饱和,加热至90℃和150℃,用60Co源以0.4 Gy·h−1照射6 ~ 18个月。腐蚀速率主要受温度和饱和度的影响。两种膨润土在150°C下的18个月内的速率相似,而MX-80在90°C和环境温度下的速率较低。辐照的影响可以忽略不计。腐蚀产物的组成与温度有很大关系。在90°C时,两种膨润土中都形成了Fe-Ca - carbonates, BCV中也形成了Fe-Ca(Mn-Mg) carbonates。在150℃时,fe - si -o富层和fe -氧化物形成,可能与无定形二氧化硅的溶解及其掺入蚀变产物有关。高温改变了膨润土的矿物学和化学性质。变化包括蒙脱石基间距的变化,Fex+和Mn2+的富集,以及交换阳离子组成的改变,包括Mg2+含量的降低。膨润土水浸出液中硫酸铵2−和氯−浓度的增加,特别是在90°C的BCV和150°C的MX-80中,部分与较高的腐蚀速率相关。这些结果强调了温度、膨润土类型和化学相互作用对储存库相关环境中碳钢腐蚀的相互影响。
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引用次数: 0
Injection moulded biodegradable hydroxyapatite–kaolin geopolymer scaffolds with enhanced mechanical strength, biocompatibility, and antibacterial activity for bone regeneration 注射成型可生物降解羟基磷灰石-高岭土聚合物支架,具有增强的机械强度、生物相容性和抗菌活性,用于骨再生
IF 5.8 2区 地球科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-01 Epub Date: 2025-11-19 DOI: 10.1016/j.clay.2025.108051
Zaid Kareem , Ersan Eyiler
This study explored the synthesis and optimization of biodegradable scaffolds composed of bovine-derived hydroxyapatite (HA) and uncalcined kaolin, specifically formulated for extrusion-based injection moulding. The mixture contained geopolymeric solids (kaolin and silica sand, GP) activated with varying concentrations of sodium hydroxide (NaOH) to form a paste compatible with low-temperature curing processes. Characterizations included X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy- energy dispersive X-ray spectroscopy (SEM-EDS), the specific surface area and porosity analysis, and mechanical testing, alongside evaluations of biodegradability, cytotoxicity, and antimicrobial activity. Results demonstrated that a composition of 15 % GP and 1.5 % NaOH achieved an optimal balance of mechanical strength (7 MPa), porosity (55 %), Young's modulus (5.6 GPa), and acceptable biocompatibility. The materials also exhibited effective antimicrobial activity, with the strongest inhibition observed against Staphylococcus aureus (31 mm zone at 1000 μg/mL) and the weakest against Pseudomonas aeruginosa (7 mm at 125 μg/mL). In addition, they demonstrated a suitable degradation behavior over 21 days in both phosphate buffer solution (PBS) and simulated body fluid (SBF) media. The cytotoxicity results showed a dose-dependent cytotoxic response; however, all tested concentrations maintained cell viability above 70 %, suggesting moderate biocompatibility. These findings suggested promising applications in bone tissue engineering, particularly for trabecular bone regeneration.
本研究探索了由牛源羟基磷灰石(HA)和未煅烧高岭土组成的生物可降解支架的合成和优化,该支架专门用于挤压注射成型。该混合物含有地聚合物固体(高岭土和硅砂,GP),用不同浓度的氢氧化钠(NaOH)活化,形成适合低温固化工艺的膏体。表征包括x射线衍射(XRD),傅里叶变换红外(FTIR)光谱,场发射扫描电子显微镜-能量色散x射线光谱(SEM-EDS),比表面积和孔隙度分析,力学测试,以及生物降解性,细胞毒性和抗菌活性的评估。结果表明,15% GP和1.5% NaOH的组合物在机械强度(7 MPa)、孔隙度(55%)、杨氏模量(5.6 GPa)和可接受的生物相容性方面达到了最佳平衡。该材料对金黄色葡萄球菌的抑制作用最强(在1000 μg/mL时为31 mm),对铜绿假单胞菌的抑制作用最弱(在125 μg/mL时为7 mm)。此外,在磷酸盐缓冲溶液(PBS)和模拟体液(SBF)介质中,它们在21天内都表现出合适的降解行为。细胞毒性结果显示剂量依赖性细胞毒性反应;然而,所有测试浓度均使细胞活力保持在70%以上,表明生物相容性中等。这些发现表明在骨组织工程,特别是骨小梁再生方面有很好的应用前景。
{"title":"Injection moulded biodegradable hydroxyapatite–kaolin geopolymer scaffolds with enhanced mechanical strength, biocompatibility, and antibacterial activity for bone regeneration","authors":"Zaid Kareem ,&nbsp;Ersan Eyiler","doi":"10.1016/j.clay.2025.108051","DOIUrl":"10.1016/j.clay.2025.108051","url":null,"abstract":"<div><div>This study explored the synthesis and optimization of biodegradable scaffolds composed of bovine-derived hydroxyapatite (HA) and uncalcined kaolin, specifically formulated for extrusion-based injection moulding. The mixture contained geopolymeric solids (kaolin and silica sand, GP) activated with varying concentrations of sodium hydroxide (NaOH) to form a paste compatible with low-temperature curing processes. Characterizations included X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy- energy dispersive X-ray spectroscopy (SEM-EDS), the specific surface area and porosity analysis, and mechanical testing, alongside evaluations of biodegradability, cytotoxicity, and antimicrobial activity. Results demonstrated that a composition of 15 % GP and 1.5 % NaOH achieved an optimal balance of mechanical strength (7 MPa), porosity (55 %), Young's modulus (5.6 GPa), and acceptable biocompatibility. The materials also exhibited effective antimicrobial activity, with the strongest inhibition observed against <em>Staphylococcus aureus</em> (31 mm zone at 1000 μg/mL) and the weakest against <em>Pseudomonas aeruginosa</em> (7 mm at 125 μg/mL). In addition, they demonstrated a suitable degradation behavior over 21 days in both phosphate buffer solution (PBS) and simulated body fluid (SBF) media. The cytotoxicity results showed a dose-dependent cytotoxic response; however, all tested concentrations maintained cell viability above 70 %, suggesting moderate biocompatibility. These findings suggested promising applications in bone tissue engineering, particularly for trabecular bone regeneration.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108051"},"PeriodicalIF":5.8,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576433","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
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Applied Clay Science
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