Applied Clay Science最新文献_第6页

A novel green approach for the synthesis of binder-free zeolite NaX foams by joint utilization of metakaolin and clinoptilolite as Si-Al precursors 以偏高岭土和斜沸石为硅铝前驱体合成无粘结剂NaX泡沫沸石的绿色新方法

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-11-21 DOI: 10.1016/j.clay.2025.108060

Luowen Xiang , Qiancheng Qiao , Xiumei Qiu , Sen Zhou , Hongquan Wang , Xiaoyan Zhu , Chunjie Yan , Yi Liu

Binder-free zeolite NaX foams were successfully prepared through a novel one-step geopolymer-gels-conversion approach using H₂O₂ solution as a foaming agent. Unlike traditional methods that utilize clay materials combined with expensive chemical SiAl reagents as precursors, metakaolin and natural clinoptilolite (mass ratio = 1:1) were selected as SiAl sources for zeolite NaX synthesis. Zeolite foams were systematically characterized and their CO₂ adsorption performance was evaluated. Crystalline phases in natural clinoptilolite (clinoptilolite, albite, illite and quartz) and impurity phases in metakaolin (anatase and quartz) were found to be partially or completely dissolved during alkaline activation process. The resultant foam products exhibit hierarchical porosity, featuring macropores (∼1–2 mm) and zeolite micropores, with compressive strength of 0.83–2.6 MPa, bulk density of 0.51–0.84 g/cm³, BET surface area of 33.18–188.79 m²/g and CO₂ adsorption capacity of 0.24–1.84 mmol/g (1 bar). Pure phase binder-free zeolite NaX foam with the relatively high crystallinity, suitable compressive strength (1.48 MPa), and high BET surface area (188.79 m²/g) was synthesized at SiO₂/Al₂O₃ molar ratio = 3.4, SiO₂/Na₂O molar ratio = 3.8, NaOH activator concentration = 10 M, crystallization temperature of 80 °C and crystallization time of 24 h. This work presents an innovative perspective on developing clay materials as promising SiAl sources for zeolite synthesis.

以H2O2溶液为发泡剂，通过一种新型的地聚合物-凝胶-一步转化方法，成功制备了无粘结剂的沸石泡沫。与传统方法使用粘土材料结合昂贵的化学SiAl试剂作为前驱体不同，本文选择偏高岭土和天然斜沸石（质量比为1:1）作为SiAl源合成沸石NaX。对沸石泡沫进行了系统表征，并对其CO2吸附性能进行了评价。天然斜发沸石（斜发沸石、钠长石、伊利石和石英）中的结晶相和偏高岭土（锐钛矿和石英）中的杂质相在碱性活化过程中部分或完全溶解。所得泡沫产品孔隙度呈分层状，具有大孔（~ 1 ~ 2 mm）和沸石微孔，抗压强度为0.83 ~ 2.6 MPa，容重为0.51 ~ 0.84 g/cm3， BET表面积为33.18 ~ 188.79 m2/g， CO2吸附量为0.24 ~ 1.84 mmol/g （1 bar）。在SiO2/Al2O3摩尔比为3.4、SiO2/Na2O摩尔比为3.8、NaOH活化剂浓度为10 M、结晶温度为80℃、结晶时间为24 h的条件下，合成了结晶度较高、抗压强度适宜（1.48 MPa）、BET表面积较高（188.79 m2/g）的纯相无粘结剂沸石NaX泡沫。本研究为开发粘土材料作为合成沸石的SiAl源提供了创新的视角。

{"title":"A novel green approach for the synthesis of binder-free zeolite NaX foams by joint utilization of metakaolin and clinoptilolite as Si-Al precursors","authors":"Luowen Xiang , Qiancheng Qiao , Xiumei Qiu , Sen Zhou , Hongquan Wang , Xiaoyan Zhu , Chunjie Yan , Yi Liu","doi":"10.1016/j.clay.2025.108060","DOIUrl":"10.1016/j.clay.2025.108060","url":null,"abstract":"<div><div>Binder-free zeolite NaX foams were successfully prepared through a novel one-step geopolymer-gels-conversion approach using H<sub>2</sub>O<sub>2</sub> solution as a foaming agent. Unlike traditional methods that utilize clay materials combined with expensive chemical Si<img>Al reagents as precursors, metakaolin and natural clinoptilolite (mass ratio = 1:1) were selected as Si<img>Al sources for zeolite NaX synthesis. Zeolite foams were systematically characterized and their CO<sub>2</sub> adsorption performance was evaluated. Crystalline phases in natural clinoptilolite (clinoptilolite, albite, illite and quartz) and impurity phases in metakaolin (anatase and quartz) were found to be partially or completely dissolved during alkaline activation process. The resultant foam products exhibit hierarchical porosity, featuring macropores (∼1–2 mm) and zeolite micropores, with compressive strength of 0.83–2.6 MPa, bulk density of 0.51–0.84 g/cm<sup>3</sup>, BET surface area of 33.18–188.79 m<sup>2</sup>/g and CO<sub>2</sub> adsorption capacity of 0.24–1.84 mmol/g (1 bar). Pure phase binder-free zeolite NaX foam with the relatively high crystallinity, suitable compressive strength (1.48 MPa), and high BET surface area (188.79 m<sup>2</sup>/g) was synthesized at SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> molar ratio = 3.4, SiO<sub>2</sub>/Na<sub>2</sub>O molar ratio = 3.8, NaOH activator concentration = 10 M, crystallization temperature of 80 °C and crystallization time of 24 h. This work presents an innovative perspective on developing clay materials as promising Si<img>Al sources for zeolite synthesis.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"280 ","pages":"Article 108060"},"PeriodicalIF":5.8,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145571116","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 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

Applied Clay Science

Pub 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。

{"title":"Swelling pressure response of Bentonil-WRK bentonite under thermal cycling up to 150°C","authors":"Deuk-Hwan Lee , Seok Yoon , Minhyeong Lee , Seeun Chang , Changsoo Lee , Dong-Keun Cho , Gi-Jun Lee","doi":"10.1016/j.clay.2025.108046","DOIUrl":"10.1016/j.clay.2025.108046","url":null,"abstract":"<div><div>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/cm<sup>3</sup> 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.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"280 ","pages":"Article 108046"},"PeriodicalIF":5.8,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145555248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Adsorption of phospholipids onto layered silicate surface: The case of clinochlore 磷脂在层状硅酸盐表面的吸附：以斜沸石为例

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-11-20 DOI: 10.1016/j.clay.2025.108053

Gianfranco Ulian, Giacomo Trondoli, Francesca Ranellucci, Giovanni Valdrè

The adsorption of phospholipids on clay minerals is an important research topic for both increasing the knowledge of prebiotic chemistry processes and the development of new biotechnological/pharmaceutical applications using natural components. However, atomic-scale information on the intimate relationship between lipids and clays is still missing in the scientific literature. The present work reports a detailed Density Functional Theory investigation of the adsorption of a simple phospholipid molecular model, i.e., 1, 2-divaleroyl-sn-glycero-3-phosphatidic acid (DVPA) and clinochlore, a phyllosilicate presenting an alternate stacking of hydrophobic brucite-like (B) and hydrophilic talc-like (TOT) layers. The results of the simulations, in absence of solvents and considering different surface coverages, showed that both substrates could condense DVPA, albeit with a general preference of the biomolecule for the B surface over the TOT one. Polar contacts were established between the DVPA and the substrates, originating mainly from the – PO₄H₂ group of the phospholipids. The presence of acidic (Al^III/Si^IV substitutions) and basic (Al^III/Mg^II) Brønsted-Lowry sites on the TOT and B layers, respectively, deeply increased the adsorption strength between DVPA and the substrates. The obtained results, encompassing both the molecular conformation on the clinochlore surface and the molecule/substrate binding energy, provided further knowledge on the phospholipid-mineral interactions, which could be very useful to devise innovative applications in biotechnology and environmental fields.

磷脂在粘土矿物上的吸附是一个重要的研究课题，既可以增加对益生元化学过程的了解，也可以利用天然成分开发新的生物技术/制药应用。然而，在科学文献中，关于脂质和粘土之间密切关系的原子尺度信息仍然缺失。本文报道了一种简单磷脂分子模型的详细的密度泛函理论研究，即1,2 -二valeroyl- n-glycero-3-phosphatidic acid （DVPA）和clinocholite，一种呈现疏水水辉石样(B)和亲水滑石样（TOT）层交替堆积的层状硅酸盐。模拟结果表明，在没有溶剂和考虑不同表面覆盖率的情况下，两种底物都可以凝聚DVPA，尽管生物分子一般更倾向于B表面而不是TOT表面。DVPA与底物之间建立了极性接触，主要源于磷脂的- PO4H2基团。在TOT层和B层上分别存在酸性（AlIII/SiIV取代）和碱性（AlIII/MgII） Brønsted-Lowry位点，大大增加了DVPA与底物之间的吸附强度。所获得的结果涵盖了沸石表面的分子构象和分子/底物结合能，为磷脂-矿物相互作用提供了进一步的知识，这可能对生物技术和环境领域的创新应用非常有用。

{"title":"Adsorption of phospholipids onto layered silicate surface: The case of clinochlore","authors":"Gianfranco Ulian, Giacomo Trondoli, Francesca Ranellucci, Giovanni Valdrè","doi":"10.1016/j.clay.2025.108053","DOIUrl":"10.1016/j.clay.2025.108053","url":null,"abstract":"<div><div>The adsorption of phospholipids on clay minerals is an important research topic for both increasing the knowledge of prebiotic chemistry processes and the development of new biotechnological/pharmaceutical applications using natural components. However, atomic-scale information on the intimate relationship between lipids and clays is still missing in the scientific literature. The present work reports a detailed Density Functional Theory investigation of the adsorption of a simple phospholipid molecular model, i.e., 1, 2-divaleroyl-<em>sn</em>-glycero-3-phosphatidic acid (DVPA) and clinochlore, a phyllosilicate presenting an alternate stacking of hydrophobic brucite-like (B) and hydrophilic talc-like (TOT) layers. The results of the simulations, in absence of solvents and considering different surface coverages, showed that both substrates could condense DVPA, albeit with a general preference of the biomolecule for the B surface over the TOT one. Polar contacts were established between the DVPA and the substrates, originating mainly from the – PO<sub>4</sub>H<sub>2</sub> group of the phospholipids. The presence of acidic (Al<sup>III</sup>/Si<sup>IV</sup> substitutions) and basic (Al<sup>III</sup>/Mg<sup>II</sup>) Brønsted-Lowry sites on the TOT and B layers, respectively, deeply increased the adsorption strength between DVPA and the substrates. The obtained results, encompassing both the molecular conformation on the clinochlore surface and the molecule/substrate binding energy, provided further knowledge on the phospholipid-mineral interactions, which could be very useful to devise innovative applications in biotechnology and environmental fields.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108053"},"PeriodicalIF":5.8,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576429","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

Unravelling and characterizing new halloysitic kaolin occurrences from the Barra do Piraí, Rio de Janeiro, southeastern Brazil. 巴西东南部里约热内卢巴拉岛Piraí的新卤石高岭土分布的揭示和特征。

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-11-20 DOI: 10.1016/j.clay.2025.108033

Ernesto Adler Licursi , Luiz Carlos Bertolino , Francisco José da Silva

With the continued advancement of nanotechnology and emergence of new applications, the number of publications directly related to technological uses involving halloysite has shown an exponential growth over the years. However, despite the overall increase, the number of publications dedicated to the geological/mineralogical characterization of halloysite has not expanded proportionally. In this context, new researches focusing on mineral exploration, ore processing, identification of occurrences, and mineralogical/technological characterization should be developed to meet the growing demand of material suitable for novel applications. This study aims to characterize the mineralogy associated with new halloysitic kaolin occurrences in the region of Barra do Piraí and surroundings, state of Rio de Janeiro. X-ray diffraction (XRD) patterns of the raw and < 20 μm fractions were used to identify and quantify the major mineral phases, while the diffraction patterns of the clay fractions enabled the differentiation between kaolinite and halloysite. X-ray fluorescence (XRF) was used not only to quantify the major oxides, but also to validate the quantification by the Rietveld method. Scanning electron microscopy (SEM) was performed to enhance the accuracy of the clay minerals identification. Six out of seven samples contain significant quantities of halloysite, while only one is composed essentially by kaolinite. The results suggest that there is a strong potential for halloysite mineral exploration in this specific region of southeastern Brazil, opening up the possibility of delimiting sufficient volumes compatible with the new demands of emerging applications.

随着纳米技术的不断进步和新应用的出现，与涉及高岭土的技术用途直接相关的出版物数量近年来呈指数级增长。然而，尽管总体上有所增加，但专门研究高岭土地质/矿物学特征的出版物数量并没有按比例增加。在这方面，应发展新的研究，重点是矿物勘探、矿石加工、产地鉴定和矿物学/技术特征，以满足对适合新用途的材料日益增长的需求。本研究旨在描述相关的矿物学新halloysitic高岭土出现在该地区的Barra皮拉伊河以及伊奇洛河环境,里约热内卢状态里约热内卢。原始组分和<； 20 μm组分的x射线衍射（XRD）图谱用于鉴定和定量主要矿物相，而粘土组分的衍射图谱用于区分高岭石和高岭石。x射线荧光（XRF）不仅对主要氧化物进行了定量，而且对Rietveld法的定量进行了验证。利用扫描电子显微镜（SEM）提高粘土矿物鉴定的准确性。七个样品中有六个含有大量的高岭土，而只有一个主要由高岭石组成。结果表明，在巴西东南部的这一特定区域进行高岭土矿物勘探的潜力很大，有可能划定足够的面积，以满足新出现的应用的新需求。

{"title":"Unravelling and characterizing new halloysitic kaolin occurrences from the Barra do Piraí, Rio de Janeiro, southeastern Brazil.","authors":"Ernesto Adler Licursi , Luiz Carlos Bertolino , Francisco José da Silva","doi":"10.1016/j.clay.2025.108033","DOIUrl":"10.1016/j.clay.2025.108033","url":null,"abstract":"<div><div>With the continued advancement of nanotechnology and emergence of new applications, the number of publications directly related to technological uses involving halloysite has shown an exponential growth over the years. However, despite the overall increase, the number of publications dedicated to the geological/mineralogical characterization of halloysite has not expanded proportionally. In this context, new researches focusing on mineral exploration, ore processing, identification of occurrences, and mineralogical/technological characterization should be developed to meet the growing demand of material suitable for novel applications. This study aims to characterize the mineralogy associated with new halloysitic kaolin occurrences in the region of Barra do Piraí and surroundings, state of Rio de Janeiro. X-ray diffraction (XRD) patterns of the raw and < 20 μm fractions were used to identify and quantify the major mineral phases, while the diffraction patterns of the clay fractions enabled the differentiation between kaolinite and halloysite. X-ray fluorescence (XRF) was used not only to quantify the major oxides, but also to validate the quantification by the Rietveld method. Scanning electron microscopy (SEM) was performed to enhance the accuracy of the clay minerals identification. Six out of seven samples contain significant quantities of halloysite, while only one is composed essentially by kaolinite. The results suggest that there is a strong potential for halloysite mineral exploration in this specific region of southeastern Brazil, opening up the possibility of delimiting sufficient volumes compatible with the new demands of emerging applications.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108033"},"PeriodicalIF":5.8,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576432","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

Analysis of the energy and nature of bandgap in layered double hydroxides Mg-Al-X and Zn-Al-X (X= Cl−, OH−, CO32−, or NO3−) 层状双氢氧化物Mg-Al-X和Zn-Al-X （X= Cl−、OH−、CO32−或NO3−）带隙的能量和性质分析

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-11-20 DOI: 10.1016/j.clay.2025.108061

Márcio F. Santos , Pedro Ivo R. Moraes , Sérgio R. Tavares , A.S. Martins , Rodrigo B. Capaz , Fernando Wypych , Alexandre A. Leitão

Photocatalysts are materials activated by sunlight and are therefore in line with so-called “Green Chemistry”. However, ab initio calculations based on Density Functional Theory (DFT) fail to describe the bandgap, which is a fundamental parameter in photocatalysis. Therefore, more sophisticated tools were required to estimate the energy bandgap and construct the band structure of the materials studied. This study expanded the electron’s self-energy in terms of the single particle Green’s function and the screened Coulomb interaction (GW approximation), evaluating how the bandgap behaves when intercalated anions are exchanged and when the ratio M

^{I I}

and M

^{I I I}

cations in the structure of layered double hydroxides (LDH). The calculations demonstrated that the forbidden band in layered double hydroxides can be tuned by varying the composition of the layers, as well as of the intercalated anions. This study suggests that LDH can be designed with finely tuned bandgaps for environmental and economic goals, such as CO

_{2}

photoreduction by sunlight, as well as organic pollutant decomposition.

光催化剂是由阳光激活的材料，因此符合所谓的“绿色化学”。然而，基于密度泛函理论（DFT）的从头计算无法描述光催化的基本参数带隙。因此，需要更复杂的工具来估计所研究材料的能带隙和构建能带结构。本研究从单粒子格林函数和筛选库仑相互作用（GW近似）的角度扩展了电子的自能，评估了层状双氢氧化物（LDH）结构中插入阴离子交换和MII和MIII阳离子比例时带隙的行为。计算表明，层状双氢氧化物中的禁带可以通过改变层的组成以及插入的阴离子来调节。这项研究表明，LDH可以被设计成具有精细调节的带隙，以实现环境和经济目标，如阳光下的二氧化碳光还原，以及有机污染物分解。

{"title":"Analysis of the energy and nature of bandgap in layered double hydroxides Mg-Al-X and Zn-Al-X (X= Cl−, OH−, CO32−, or NO3−)","authors":"Márcio F. Santos , Pedro Ivo R. Moraes , Sérgio R. Tavares , A.S. Martins , Rodrigo B. Capaz , Fernando Wypych , Alexandre A. Leitão","doi":"10.1016/j.clay.2025.108061","DOIUrl":"10.1016/j.clay.2025.108061","url":null,"abstract":"<div><div>Photocatalysts are materials activated by sunlight and are therefore in line with so-called “Green Chemistry”. However, <em>ab initio</em> calculations based on Density Functional Theory (DFT) fail to describe the bandgap, which is a fundamental parameter in photocatalysis. Therefore, more sophisticated tools were required to estimate the energy bandgap and construct the band structure of the materials studied. This study expanded the electron’s self-energy in terms of the single particle Green’s function and the screened Coulomb interaction (GW approximation), evaluating how the bandgap behaves when intercalated anions are exchanged and when the ratio M<span><math><msup><mrow></mrow><mrow><mi>I</mi><mi>I</mi></mrow></msup></math></span> and M<span><math><msup><mrow></mrow><mrow><mi>I</mi><mi>I</mi><mi>I</mi></mrow></msup></math></span> cations in the structure of layered double hydroxides (LDH). The calculations demonstrated that the forbidden band in layered double hydroxides can be tuned by varying the composition of the layers, as well as of the intercalated anions. This study suggests that LDH can be designed with finely tuned bandgaps for environmental and economic goals, such as CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> photoreduction by sunlight, as well as organic pollutant decomposition.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108061"},"PeriodicalIF":5.8,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576430","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

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

Applied Clay Science

Pub 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 , 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":"2025-11-19","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

Reassessment of DLVO theory at sub-nanometric scale: Application to Na-smectite 亚纳米尺度DLVO理论的再评价：在钠蒙脱石上的应用

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-11-19 DOI: 10.1016/j.clay.2025.108049

Julio Gonçalvès , Lucile Rouil , Stéphane Gaboreau , Jean-Charles Robinet , Jean Talandier

The nearly century-old DLVO (Derjaguin, Landau, Verview, and Overbeek) theory decomposes the interaction forces between solid surfaces separated by a fluid into attractive and repulsive components. In its standard version, it applies beyond solid surface separation distances of around 1 nm. For sub-nanometer distances, additional so-called hydration forces were widely invoked to explain the discrepancy between theory and measurements. Alternatively to this semi-empirical approach, either the validity of the theoretical expression for the electrostatic component of the disjoining pressure, or the adaptation of the Boltzmann distribution usually considered in the application of DLVO theory are questioned. Here, it is suggested that the introduction of a hydration component whose parameters cannot be predetermined but are a matter of calibration is unnecessary. Hydration effects, introduced in the calculation of ionic concentrations, directly influence ions distributions and therefore the repulsion of adjacent electric double layers. This effect is thus part of the electrostatic component of the disjoining pressure. An analytical expression extending DLVO theory to small surface separation distances together with a simplified electrical model, both proposed here, enable reproducing data for Na-smectite. Results are also in good agreement with thermodynamic and molecular dynamics calculations. It is confirmed that the discrepancy between theory and observations is mainly due to the underestimation of counterions concentration at the mid-plane identified using an inappropriate electrical model. For ions with radii around 0.1 nm, commonly found in natural media, the standard DLVO expression can still be used, but with mid-plane concentrations calculated using an appropriate electrical model.

近一个世纪的DLVO （Derjaguin, Landau， Verview和Overbeek）理论将被流体分离的固体表面之间的相互作用力分解为吸引和排斥分量。在其标准版本中，它适用于超过约1纳米的固体表面分离距离。对于亚纳米距离，额外的所谓水合力被广泛引用来解释理论和测量之间的差异。与这种半经验方法不同的是，分离压力的静电分量的理论表达式的有效性，或者在DLVO理论应用中通常考虑的玻尔兹曼分布的适应性都受到质疑。在这里，有人建议，引入水化成分，其参数不能预先确定，但是一个校准问题是不必要的。离子浓度计算中引入的水化效应直接影响离子分布，从而影响相邻双电层的斥力。因此，这种效应是分离压力的静电分量的一部分。本文提出了一种将DLVO理论扩展到小表面分离距离的解析表达式，以及一种简化的电模型，可以再现na -蒙脱石的数据。结果与热力学和分子动力学计算结果也很吻合。证实了理论与观测的差异主要是由于使用不适当的电模型对中平面的反离子浓度估计不足。对于通常在自然介质中发现的半径约0.1 nm的离子，仍然可以使用标准DLVO表达，但使用适当的电模型计算平面中间浓度。

{"title":"Reassessment of DLVO theory at sub-nanometric scale: Application to Na-smectite","authors":"Julio Gonçalvès , Lucile Rouil , Stéphane Gaboreau , Jean-Charles Robinet , Jean Talandier","doi":"10.1016/j.clay.2025.108049","DOIUrl":"10.1016/j.clay.2025.108049","url":null,"abstract":"<div><div>The nearly century-old DLVO (Derjaguin, Landau, Verview, and Overbeek) theory decomposes the interaction forces between solid surfaces separated by a fluid into attractive and repulsive components. In its standard version, it applies beyond solid surface separation distances of around 1 nm. For sub-nanometer distances, additional so-called hydration forces were widely invoked to explain the discrepancy between theory and measurements. Alternatively to this semi-empirical approach, either the validity of the theoretical expression for the electrostatic component of the disjoining pressure, or the adaptation of the Boltzmann distribution usually considered in the application of DLVO theory are questioned. Here, it is suggested that the introduction of a hydration component whose parameters cannot be predetermined but are a matter of calibration is unnecessary. Hydration effects, introduced in the calculation of ionic concentrations, directly influence ions distributions and therefore the repulsion of adjacent electric double layers. This effect is thus part of the electrostatic component of the disjoining pressure. An analytical expression extending DLVO theory to small surface separation distances together with a simplified electrical model, both proposed here, enable reproducing data for Na-smectite. Results are also in good agreement with thermodynamic and molecular dynamics calculations. It is confirmed that the discrepancy between theory and observations is mainly due to the underestimation of counterions concentration at the mid-plane identified using an inappropriate electrical model. For ions with radii around 0.1 nm, commonly found in natural media, the standard DLVO expression can still be used, but with mid-plane concentrations calculated using an appropriate electrical model.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108049"},"PeriodicalIF":5.8,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576434","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

Synthesis of well-defined allophane nanospheres 定义良好的allophane纳米球的合成

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-11-19 DOI: 10.1016/j.clay.2025.108056

Pierre Picot, Frédéric Gobeaux, Antoine Thill

Well-defined allophane nanospheres, with internal and external diameters of 3.0 and 3.9 nm, respectively, were successfully synthesized and characterized by cryo-TEM, SAXS, and IR spectroscopy. In addition, we propose a refined structural framework, clarifying the coexistence of open and closed imogolite- local structures, which are commonly grouped together under the term allophane.

成功合成了内径为3.0 nm、外径为3.9 nm、结构清晰的allophane纳米球，并通过低温透射电镜（cro - tem）、SAXS和红外光谱对其进行了表征。此外，我们提出了一个精细的结构框架，阐明了开放和封闭的伊莫长石局部结构共存，它们通常被归为allophane。

引用次数: 0

Thermal assessment of Argentinian waste shales for manufacturing lightweight aggregates 阿根廷废页岩用于制造轻质骨料的热评价

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-11-19 DOI: 10.1016/j.clay.2025.108054

Cecilia Lucía Martinefsky , Anabella Mocciaro , Edgardo Fabián Irassar , Alejandra Tironi

Lightweight aggregates (LWAs) are granular materials with a highly porous interior and an external sintered layer formed during high-temperature processing. The potential of LWAs is significant in construction, as they improve energy efficiency, lightness, and enhance fire resistance. The applications of LWAs have also extended to various fields, including water treatment, adsorption processes, hydroponics, horticulture, green roofs, and other agronomic applications. The aim of this study is to evaluate the suitability of the Argentinian waste shales as a raw material to manufacture LWAs, as a potential solution for its disposal and to add value to this waste. At the same time, it can contribute to expanding the use of waste clays and shales from quarries with illite and chlorite clay minerals. This work includes the thermal transformations of shales using thermogravimetric analysis and hot-stage microscopy. The shales are used as raw material to produce sintered LWAs under two thermal treatment conditions, conventional and rapid heating, and two maximum temperatures, 1150 and 1200 °C. Finally, the mineralogical composition, microstructure, and technological properties of the LWAs are analyzed. The results show that Argentinian waste shales containing illite and chlorite clay minerals can be successfully used for manufacturing LWAs with sintering treatment at 1200 °C. Conventional sintering favours the formation of larger diameter pores, while rapid sintering produces a higher number of smaller pores and improves compressive strength. The selection will depend on the desired technological properties. This study provides a foundation for future research and promotes the industrial production of LWAs in developing countries.

轻质集料（LWAs）是在高温加工过程中形成的具有高度多孔性内部和外部烧结层的颗粒状材料。lwa的潜力在建筑中是重要的，因为它们提高了能源效率，重量轻，并增强了防火性。LWAs的应用也扩展到各个领域，包括水处理、吸附过程、水培、园艺、绿色屋顶和其他农艺应用。本研究的目的是评估阿根廷废页岩作为制造LWAs原材料的适用性，作为其处置的潜在解决方案，并为这种废物增加价值。同时，它还有助于扩大利用来自伊利石和绿泥石粘土矿物采石场的废粘土和页岩。这项工作包括利用热重分析和热级显微镜对页岩进行热转化。以页岩为原料，在常规和快速加热两种热处理条件下，以及1150和1200℃两种最高温度下生产烧结LWAs。最后对LWAs的矿物组成、微观结构和工艺性能进行了分析。结果表明，含伊利石和绿泥石粘土矿物的阿根廷废页岩经1200℃烧结处理后，可成功用于制备LWAs。常规烧结有利于形成直径较大的孔隙，而快速烧结产生更多的小孔隙，提高抗压强度。选择将取决于所需的技术特性。本研究为今后的研究奠定了基础，并促进了发展中国家LWAs的工业化生产。

{"title":"Thermal assessment of Argentinian waste shales for manufacturing lightweight aggregates","authors":"Cecilia Lucía Martinefsky , Anabella Mocciaro , Edgardo Fabián Irassar , Alejandra Tironi","doi":"10.1016/j.clay.2025.108054","DOIUrl":"10.1016/j.clay.2025.108054","url":null,"abstract":"<div><div>Lightweight aggregates (LWAs) are granular materials with a highly porous interior and an external sintered layer formed during high-temperature processing. The potential of LWAs is significant in construction, as they improve energy efficiency, lightness, and enhance fire resistance. The applications of LWAs have also extended to various fields, including water treatment, adsorption processes, hydroponics, horticulture, green roofs, and other agronomic applications. The aim of this study is to evaluate the suitability of the Argentinian waste shales as a raw material to manufacture LWAs, as a potential solution for its disposal and to add value to this waste. At the same time, it can contribute to expanding the use of waste clays and shales from quarries with illite and chlorite clay minerals. This work includes the thermal transformations of shales using thermogravimetric analysis and hot-stage microscopy. The shales are used as raw material to produce sintered LWAs under two thermal treatment conditions, conventional and rapid heating, and two maximum temperatures, 1150 and 1200 °C. Finally, the mineralogical composition, microstructure, and technological properties of the LWAs are analyzed. The results show that Argentinian waste shales containing illite and chlorite clay minerals can be successfully used for manufacturing LWAs with sintering treatment at 1200 °C. Conventional sintering favours the formation of larger diameter pores, while rapid sintering produces a higher number of smaller pores and improves compressive strength. The selection will depend on the desired technological properties. This study provides a foundation for future research and promotes the industrial production of LWAs in developing countries.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"279 ","pages":"Article 108054"},"PeriodicalIF":5.8,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576431","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

Applied Clay Science

Pub 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 CO

_{2}

, H

_{2}

, and CH

_{4}

, 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 , Konstantinos Karalis , Nikolaos I. Prasianakis , Alessio Ferrari , 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":"2025-11-18","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