Microporous and Mesoporous Materials最新文献

γ-Aminobutyric acid-promoted crystallization of Beta zeolite and its application for direct amination of isobutene with ammonia

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-17 DOI: 10.1016/j.micromeso.2025.113648

Yijun Zhong , Dongpu Zhao , Weifeng Chu , Fucun Chen , Jie An , Yanan Wang , Wanling Shen , Shenglin Liu , Longya Xu

Beta zeolite is a significant catalyst used in petroleum refining and fine chemical course. We report a novel way to considerably shorten the crystallization time of Beta zeolite by adding γ-aminobutyric acid (GABA) as a ‘promoter’. The synthesis parameters are systematically investigated to unveil the promotion effect of GABA on Beta zeolite synthesis via a range of characterization skills, such as XRD, SEM, TEM, TG-DTG, NH₃-TPD, Py-IR and NMR. The results demonstrate that under hydrothermal synthesis at 140 °C (initial Si/Al₂ = 43), the addition of GABA has been shown to result in a significant reduction in crystallization time, from 130 h to 18 h, while concurrently enhancing product yield from 51.7 % to 76.1 %. The resulting Si/Al₂ ratio increases from 22.6 to 33.1, suggesting that GABA regulates aluminum incorporation kinetics during zeolite nucleation. GABA can break the hydration layer round TEA⁺ and aluminosilicate, and consequently, the formation of 5Rs structure and the nucleation process are accelerated. Meanwhile, the Hoffmann decomposition of TEAOH is inhibited as well. In comparison with the conventionally synthesized counterpart, the fast-synthesized Beta zeolite possessing high product yield and high Si/Al₂ ratio, exhibits comparable or even better catalytic performance in the direct amination of isobutene (i-C₄H₈) with ammonia (NH₃), due to its relatively high concentration of weak acid site.

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引用次数: 0

Two-stage crystallisation of the MFI zeolite: kinetic control for efficient catalyst development

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-17 DOI: 10.1016/j.micromeso.2025.113649

Vladimir S. Pavlov , Daniil V. Bruter , Andrey V. Efimov , Andrey G. Popov , Irina I. Ivanova , Vladimir L. Zholobenko

A detailed investigation of the MFI zeolite crystallisation mechanism in an alkaline synthetic gel system has been carried out using XRD, SEM, nitrogen adsorption, ammonia TPD, elemental analysis, NMR and FTIR spectroscopy. During the first stage of the synthesis, a highly crystalline zeolite is formed via solid hydrogel transformation mechanism, while for a prolonged synthesis, a second stage of crystallisation is clearly distinguished. The zeolite yield and its Si/Al ratio increase during the second stage, whereas the number of defect sites and the mesopore volume decrease. The second stage leads to increased diffusion limitations owing to the blockage of the transport mesopores and to shortened catalyst lifetime in the MTH and butenes oligomerisation processes as well as to a lower activity in toluene alkylation with methanol. Identification of the second stage of crystallisation potentially allows for fine tuning of the zeolite catalytic properties by varying the crystallisation time.

我们使用 XRD、SEM、氮吸附、氨 TPD、元素分析、核磁共振和傅立叶变换红外光谱对碱性合成凝胶体系中的 MFI 沸石结晶机理进行了详细研究。在合成的第一阶段，通过固体水凝胶转化机制形成了高度结晶的沸石，而在长时间的合成过程中，第二阶段的结晶过程非常明显。在第二阶段，沸石的产量及其硅/铝比率都会增加，而缺陷点的数量和中孔体积则会减少。第二阶段导致传输介孔堵塞，增加了扩散限制，缩短了 MTH 和丁烯低聚过程的催化剂寿命，降低了甲苯与甲醇烷基化的活性。通过对第二阶段结晶的鉴定，可以通过改变结晶时间对沸石的催化特性进行微调。

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引用次数: 0

Facile fabrication of hierarchical SAPO-34 zeolite with enhanced MTO catalytic performance

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-17 DOI: 10.1016/j.micromeso.2025.113647

Weijiong Dai, Zongqiang Liu, Jing Zhao, Yan Wang, Jiajun Zheng, Ruifeng Li

SAPO-34 zeolites with excellent selectivity towards to light olefins and highly catalytic stability are highly desirable. In this work, SAPO-34 zeolite (SAPO-34-S-F) featuring both significantly reduced crystal dimension and a hierarchical structure was synthesized for the first time through a seed-assisted strategy employing cost-effective triethylamine (TEA) as the only organic structure-directing agent (OSDA) in the NH₄F-containing medium. The resulting SAPO-34 zeolite demonstrated exceptional catalytic performance in methanol-to-olefin (MTO) reaction, exhibiting a substantially increased catalytic lifetime of 525 min as well as an impressive light olefin selectivity of up to 83.7 %. These results significantly outperform those of conventional SAPO-34 zeolite with larger crystal dimension synthesized using TEA as OSDA, and SAPO-34 zeolite with similar crystal dimension synthesized without fluoride addition. Thermogravimetric analysis (TGA) of the spent catalysts revealed that SAPO-34-S-F possesses enhanced coke tolerance. Furthermore, in situ UV/Vis studies of the organic intermediates generated on zeolites during MTO reaction provided additional evidence for the excellent catalytic activity and stability of the SAPO-34-S-F sample. These findings offer important insights for the rational development of stable and high-efficiency SAPO-34 zeolite for MTO reaction.

{"title":"Facile fabrication of hierarchical SAPO-34 zeolite with enhanced MTO catalytic performance","authors":"Weijiong Dai, Zongqiang Liu, Jing Zhao, Yan Wang, Jiajun Zheng, Ruifeng Li","doi":"10.1016/j.micromeso.2025.113647","DOIUrl":"10.1016/j.micromeso.2025.113647","url":null,"abstract":"<div><div>SAPO-34 zeolites with excellent selectivity towards to light olefins and highly catalytic stability are highly desirable. In this work, SAPO-34 zeolite (SAPO-34-S-F) featuring both significantly reduced crystal dimension and a hierarchical structure was synthesized for the first time through a seed-assisted strategy employing cost-effective triethylamine (TEA) as the only organic structure-directing agent (OSDA) in the NH<sub>4</sub>F-containing medium. The resulting SAPO-34 zeolite demonstrated exceptional catalytic performance in methanol-to-olefin (MTO) reaction, exhibiting a substantially increased catalytic lifetime of 525 min as well as an impressive light olefin selectivity of up to 83.7 %. These results significantly outperform those of conventional SAPO-34 zeolite with larger crystal dimension synthesized using TEA as OSDA, and SAPO-34 zeolite with similar crystal dimension synthesized without fluoride addition. Thermogravimetric analysis (TGA) of the spent catalysts revealed that SAPO-34-S-F possesses enhanced coke tolerance. Furthermore, in situ UV/Vis studies of the organic intermediates generated on zeolites during MTO reaction provided additional evidence for the excellent catalytic activity and stability of the SAPO-34-S-F sample. These findings offer important insights for the rational development of stable and high-efficiency SAPO-34 zeolite for MTO reaction.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113647"},"PeriodicalIF":4.8,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143850460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A rapid microwave-assisted solvothermal La3+ ion exchange of NaA zeolite membranes for enhanced performance of ethanol dehydration

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-16 DOI: 10.1016/j.micromeso.2025.113645

Wenbin Zhao , Jinhuai Hua , Yi Cao , Rui Yao , Yanshuo Li

A microwave-assisted solvothermal method was developed to achieve La³⁺ exchange in NaA zeolite membranes for enhanced ethanol dehydration via pervaporation. Traditional ion-exchange processes are time-consuming and risk structural degradation, whereas the proposed approach utilizes alcohol-based solvents under microwave irradiation to accelerate ion exchange while preserving membrane integrity. By optimizing solvent selection (isopropanol) and La³⁺ concentration (0.04–0.05 mol L⁻¹), the modified La-LTA membrane exhibited simultaneous improvements in water flux (up to 12.78 % increase) and separation factor (up to 227 % enhancement), particularly in low-water-content systems. Characterization via SEM, XRD, and XPS confirmed retained crystallinity and successful La³⁺ incorporation (35.42 % exchange degree). The method's universality was validated by exchanging other ions (Li⁺, Cu²⁺, Nd³⁺), with Li-LTA and Nd-LTA membranes also showing dual performance enhancements. This work provides an energy-efficient, scalable strategy to tailor zeolite membranes for industrial dehydration applications.

研究人员开发了一种微波辅助溶热法，以实现 NaA 沸石膜中的 La3+ 交换，从而通过渗透蒸发增强乙醇脱水。传统的离子交换过程耗时且有结构退化的风险，而所提出的方法是在微波辐照下利用醇基溶剂加速离子交换，同时保持膜的完整性。通过优化溶剂选择（异丙醇）和 La3+ 浓度（0.04-0.05 mol L-1），改良后的 La-LTA 膜同时提高了水通量（最高提高 12.78%）和分离因子（最高提高 227%），尤其是在低水含量系统中。通过 SEM、XRD 和 XPS 进行的表征证实了结晶度的保持和 La3+ 的成功加入（交换度为 35.42%）。通过交换其他离子（Li+、Cu2+、Nd3+）验证了该方法的通用性，Li-LTA 和 Nd-LTA 膜也显示出双重性能提升。这项工作为工业脱水应用提供了一种节能、可扩展的沸石膜定制策略。

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引用次数: 0

Adsorption separation of propylene/propane by pressure induced flexible porous MOF

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-16 DOI: 10.1016/j.micromeso.2025.113644

Huiping Chen , Meiling Li , Dongxu Gu , Guang Che

The separation of C₃H₆ from C₃H₈ represents a significant yet challenging industrial task. Utilizing adsorption separation technology based on porous materials emerges as an energy-saving and cost-effective strategy. In this study, we investigate a flexible porous MOF, HNU-49, as a promising adsorbent for the efficient separation of C₃H₆ and C₃H₈ within the temperature range of 288–308 K. Due to its adaptable microporous structure, HNU-49 displays a distinct guest-dependent pressure-induced gate-opening effect, facilitating the effective separation of propylene and propane. Experimental studies, including adsorption isotherms and transient breakthrough experiments, were conducted to evaluate the separation performance of HNU-49, and cyclic experiments were performed to assess its structural stability. At a temperature of 298 K and a pressure of 0.2 bar, HNU-49 exhibits an IAST selectivity of 5.13 for C₃H₆/C₃H₈. The findings indicate that flexible MOFs with guest-dependent pressure-induced gate-opening effects hold potential applications in selective gas adsorption and separation. Moreover, these stable materials demonstrate good regenerability, making them advantageous for practical applications.

{"title":"Adsorption separation of propylene/propane by pressure induced flexible porous MOF","authors":"Huiping Chen , Meiling Li , Dongxu Gu , Guang Che","doi":"10.1016/j.micromeso.2025.113644","DOIUrl":"10.1016/j.micromeso.2025.113644","url":null,"abstract":"<div><div>The separation of C<sub>3</sub>H<sub>6</sub> from C<sub>3</sub>H<sub>8</sub> represents a significant yet challenging industrial task. Utilizing adsorption separation technology based on porous materials emerges as an energy-saving and cost-effective strategy. In this study, we investigate a flexible porous MOF, HNU-49, as a promising adsorbent for the efficient separation of C<sub>3</sub>H<sub>6</sub> and C<sub>3</sub>H<sub>8</sub> within the temperature range of 288–308 K. Due to its adaptable microporous structure, HNU-49 displays a distinct guest-dependent pressure-induced gate-opening effect, facilitating the effective separation of propylene and propane. Experimental studies, including adsorption isotherms and transient breakthrough experiments, were conducted to evaluate the separation performance of HNU-49, and cyclic experiments were performed to assess its structural stability. At a temperature of 298 K and a pressure of 0.2 bar, HNU-49 exhibits an IAST selectivity of 5.13 for C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub>. The findings indicate that flexible MOFs with guest-dependent pressure-induced gate-opening effects hold potential applications in selective gas adsorption and separation. Moreover, these stable materials demonstrate good regenerability, making them advantageous for practical applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"393 ","pages":"Article 113644"},"PeriodicalIF":4.8,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhancement of the olefin selectivity over ZnSAPO-34 zeolite toward methanol-to-olefins conversion and its mechanistic interpretation ZnSAPO-34 沸石对甲醇-烯烃转化的烯烃选择性增强及其机理解释

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-12 DOI: 10.1016/j.micromeso.2025.113632

Chang Wang , Lei Zhang , Jiahui Yang , Jun Yu , Xue Shao , Lina Zhang , Runze Liu , Weiping Zhu , Weili Dai

The SAPO-34 zeolite serves as a crucial catalyst in the methanol-to-olefins (MTO) conversion to produce ethylene and propylene, yet suffering from the unsatisfied trade-off between long catalyst lifetime and high light olefins selectivity. Herein, we report a stable and efficient hierarchical ZnSAPO-34 zeolite prepared via hydrothermal method, which is featured with the successful introduction of Zn species into SAPO-34 framework. Impressively, the ZnSAPO-34 catalyst achieves a significantly enhanced ethylene selectivity of 60 % without obviously sacrificing catalyst lifetime. A combination study including online mass spectrometer (MS), ¹³C MAS NMR and in situ UV–visible (UV–vis) spectroscopy demonstrates that Zn species facilitate the initial generation of carbonyl species accompanied by the formation of hydrocarbon pool species, thus boosting the ethylene selectivity via the aromatic-based cycle. Meanwhile, the one-step introduction of Zn species leads to smaller crystal size and increases mesoporous in zeolite, enhancing the diffusion capacity of the ZnSAPO-34 sample, which accounts for the almost unchanged catalyst lifetime. The mechanistic interpretation provides a novel perspective to optimize zeolite catalysts by one-step introducing heteroatom, which shows potential applications in industrial MTO production.

{"title":"Enhancement of the olefin selectivity over ZnSAPO-34 zeolite toward methanol-to-olefins conversion and its mechanistic interpretation","authors":"Chang Wang , Lei Zhang , Jiahui Yang , Jun Yu , Xue Shao , Lina Zhang , Runze Liu , Weiping Zhu , Weili Dai","doi":"10.1016/j.micromeso.2025.113632","DOIUrl":"10.1016/j.micromeso.2025.113632","url":null,"abstract":"<div><div>The SAPO-34 zeolite serves as a crucial catalyst in the methanol-to-olefins (MTO) conversion to produce ethylene and propylene, yet suffering from the unsatisfied trade-off between long catalyst lifetime and high light olefins selectivity. Herein, we report a stable and efficient hierarchical ZnSAPO-34 zeolite prepared via hydrothermal method, which is featured with the successful introduction of Zn species into SAPO-34 framework. Impressively, the ZnSAPO-34 catalyst achieves a significantly enhanced ethylene selectivity of 60 % without obviously sacrificing catalyst lifetime. A combination study including online mass spectrometer (MS), <sup>13</sup>C MAS NMR and <em>in situ</em> UV–visible (UV–vis) spectroscopy demonstrates that Zn species facilitate the initial generation of carbonyl species accompanied by the formation of hydrocarbon pool species, thus boosting the ethylene selectivity via the aromatic-based cycle. Meanwhile, the one-step introduction of Zn species leads to smaller crystal size and increases mesoporous in zeolite, enhancing the diffusion capacity of the ZnSAPO-34 sample, which accounts for the almost unchanged catalyst lifetime. The mechanistic interpretation provides a novel perspective to optimize zeolite catalysts by one-step introducing heteroatom, which shows potential applications in industrial MTO production.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113632"},"PeriodicalIF":4.8,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Effective elimination of Congo red dye from tannery wastewater using Fe-pillared bentonite: Synthesis, adsorption isotherm, kinetics, and optimization via Box-Behnken design

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-12 DOI: 10.1016/j.micromeso.2025.113641

Soukaina El Abbadi , Hajar El Moustansiri , Mohamed Douma , Abdelmjid Bouazizi , Mounia Baidou , Abdelaziz Elgamouz , Najib Tijani

Untreated tannery wastewater with a high concentration of Congo Red (CR) dye can harm the ecosystem and public health. Therefore, Iron-pillared bentonite (Fe-PB) was synthesized and evaluated for its ability to remove CR dye from tannery wastewater. The effect of OH⁻/Fe³⁺ molar ratio within the range of 1.2–2.4 on the physico-chemical properties of Fe-PBs was examined. The solids obtained were characterized by XRF, XRD, BET, and SEM analyses, which confirmed that the pillaring process was successful. The adsorption process was optimized using response surface methodology combined with the Box-Behnken design (RSM-BBD). For both raw bentonite (RB) and Fe-PB_2.0 clays, the optimized conditions were found at 0.03 g adsorbent mass, pH solution 2, 45 °C temperature, and 115 min contact time. The maximum adsorption capacity of CR reached 95.72 mg/g for RB and 175.75 mg/g for Fe-PB_2.0, due to an increase in specific surface area, from 78 m²/g for RB to 190 m²/g for Fe-PB_2.0. The pseudo-second-order kinetic and Freundlich models indicated a better fit with the adsorption data. Moreover, five adsorption-desorption cycles were used in regeneration studies, and the removal rate of Fe-PB_2.0 varied from 98 to 86 %, indicating the material's great potential for reuse. Before and after the adsorption experiments, several physicochemical characteristics of the tannery wastewater were examined, including pH, conductivity, turbidity, BOD₅, COD, and CR content. The study highlights the potential of the pillared bentonite clay as a cost-effective adsorbent for treating tannery wastewater and indicates the effectiveness of the RSM-BBD approach for modeling and optimization.

{"title":"Effective elimination of Congo red dye from tannery wastewater using Fe-pillared bentonite: Synthesis, adsorption isotherm, kinetics, and optimization via Box-Behnken design","authors":"Soukaina El Abbadi , Hajar El Moustansiri , Mohamed Douma , Abdelmjid Bouazizi , Mounia Baidou , Abdelaziz Elgamouz , Najib Tijani","doi":"10.1016/j.micromeso.2025.113641","DOIUrl":"10.1016/j.micromeso.2025.113641","url":null,"abstract":"<div><div>Untreated tannery wastewater with a high concentration of Congo Red (CR) dye can harm the ecosystem and public health. Therefore, Iron-pillared bentonite (Fe-PB) was synthesized and evaluated for its ability to remove CR dye from tannery wastewater. The effect of OH<sup>−</sup>/Fe<sup>3+</sup> molar ratio within the range of 1.2–2.4 on the physico-chemical properties of Fe-PBs was examined. The solids obtained were characterized by XRF, XRD, BET, and SEM analyses, which confirmed that the pillaring process was successful. The adsorption process was optimized using response surface methodology combined with the Box-Behnken design (RSM-BBD). For both raw bentonite (RB) and Fe-PB<sub>2.0</sub> clays, the optimized conditions were found at 0.03 g adsorbent mass, pH solution 2, 45 °C temperature, and 115 min contact time. The maximum adsorption capacity of CR reached 95.72 mg/g for RB and 175.75 mg/g for Fe-PB<sub>2.0</sub>, due to an increase in specific surface area, from 78 m<sup>2</sup>/g for RB to 190 m<sup>2</sup>/g for Fe-PB<sub>2.0</sub>. The pseudo-second-order kinetic and Freundlich models indicated a better fit with the adsorption data. Moreover, five adsorption-desorption cycles were used in regeneration studies, and the removal rate of Fe-PB<sub>2.0</sub> varied from 98 to 86 %, indicating the material's great potential for reuse. Before and after the adsorption experiments, several physicochemical characteristics of the tannery wastewater were examined, including pH, conductivity, turbidity, BOD<sub>5</sub>, COD, and CR content. The study highlights the potential of the pillared bentonite clay as a cost-effective adsorbent for treating tannery wastewater and indicates the effectiveness of the RSM-BBD approach for modeling and optimization.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113641"},"PeriodicalIF":4.8,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143839022","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","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 Hg(II) from aqueous solutions on β-zeolite: Theoretical-experimental proposal for the surface interaction mechanism and the formation of metal complexes

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-12 DOI: 10.1016/j.micromeso.2025.113642

Lisette Ruiz-Bravo , Kevin Granados-Tavera , Gloria Cárdenas-Jirón

A β-zeolite (Zβ) was synthesized and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic absorption spectroscopy, nitrogen adsorption-desorption isotherms, thermogravimetric analysis (TG-DTA), and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The material exhibited a Si/Al ratio of 23.3, a BET surface area of 619 m²/g, and a predominantly microporous structure. The adsorption of Hg(II) onto Zβ was rapid, reaching equilibrium within 40 min. Kinetic analysis best fitted the pseudo-second order model, indicating chemisorption on active sites, while the Freundlich isotherm suggested multilayer adsorption on heterogeneous surfaces. ATR-FTIR analysis suggests the involvement of silanol groups in the adsorption mechanism. After Hg(II) adsorption, the intensity of the hydroxyl (-OH) band at 3370 cm⁻¹ decreased significantly, indicating interaction with the metal ions. Theoretical calculations further elucidated the adsorption mechanism, showing the formation of inner and outer sphere complexes. The inner sphere complex involved direct coordination between Hg(II) and silanol groups, while the outer sphere complex was stabilized by hydrogen bonding. The calculated reaction energies (−0.6 and −2.1 eV) supported the thermodynamic feasibility of these interactions. Density functional theory (DFT) and Ab initio molecular dynamics (AIMD) simulations revealed a significant bandgap reduction upon mercury adsorption, confirming strong electronic interactions. These findings highlight the efficiency of Zβ for Hg(II) removal, particularly at low concentrations. The combined experimental and theoretical approach provides valuable insights into the adsorption process, contributing to the design of advanced materials for heavy metal remediation.

{"title":"Adsorption of Hg(II) from aqueous solutions on β-zeolite: Theoretical-experimental proposal for the surface interaction mechanism and the formation of metal complexes","authors":"Lisette Ruiz-Bravo , Kevin Granados-Tavera , Gloria Cárdenas-Jirón","doi":"10.1016/j.micromeso.2025.113642","DOIUrl":"10.1016/j.micromeso.2025.113642","url":null,"abstract":"<div><div>A β-zeolite (<strong>Zβ</strong>) was synthesized and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic absorption spectroscopy, nitrogen adsorption-desorption isotherms, thermogravimetric analysis (TG-DTA), and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The material exhibited a Si/Al ratio of 23.3, a BET surface area of 619 m<sup>2</sup>/g, and a predominantly microporous structure. The adsorption of Hg(II) onto <strong>Zβ</strong> was rapid, reaching equilibrium within 40 min. Kinetic analysis best fitted the pseudo-second order model, indicating chemisorption on active sites, while the Freundlich isotherm suggested multilayer adsorption on heterogeneous surfaces. ATR-FTIR analysis suggests the involvement of silanol groups in the adsorption mechanism. After Hg(II) adsorption, the intensity of the hydroxyl (-OH) band at 3370 cm<sup>−1</sup> decreased significantly, indicating interaction with the metal ions. Theoretical calculations further elucidated the adsorption mechanism, showing the formation of inner and outer sphere complexes. The inner sphere complex involved direct coordination between Hg(II) and silanol groups, while the outer sphere complex was stabilized by hydrogen bonding. The calculated reaction energies (−0.6 and −2.1 eV) supported the thermodynamic feasibility of these interactions. Density functional theory (DFT) and Ab initio molecular dynamics (AIMD) simulations revealed a significant bandgap reduction upon mercury adsorption, confirming strong electronic interactions. These findings highlight the efficiency of <strong>Zβ</strong> for Hg(II) removal, particularly at low concentrations. The combined experimental and theoretical approach provides valuable insights into the adsorption process, contributing to the design of advanced materials for heavy metal remediation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113642"},"PeriodicalIF":4.8,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143848100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Selective hydrogenation of dienes to olefins and sulfur removal from model FCC gasoline over Ni-Mo sulfide catalyst supported on MCM-41 type silica

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-09 DOI: 10.1016/j.micromeso.2025.113631

Sijing Dai , M.Yu. Talanova , A.A. Samarov , S.P. Verevkin , M.V. Poliakov , E.A. Karakhanov , A.P. Glotov , A.V. Vutolkina

The transformation of 2,5-dimethyl-hexadiene-2,4 and benzothiophene over mesoporous MCM-41 silica supported Ni-Mo sulfide catalyst was estimated. The physico-chemical properties of support and catalyst were evaluated by XRD, low-temperature N₂ adsorption, TEM, EDX mapping and XPS analysis. The catalyst reveals the sulfide particles with 5.4 nm in length and 3.5 stacks supported on MCM-41 silica having hexagonal porous arrangement with 2.5 nm in diameter. The effective content of Mo in MoS₂ was 48.3 wt%. According to thermodynamic calculations, the equilibrium mixture contains 2,5-dimethylhexane (82 %) and n-octane (18 %). For catalytic tests, at 260–340 °C for 1–2 h selectivity to olefins reaches 85–90 %, whereas 100 % benzothiophene conversion to ethylbenzene was achieved at 300–340 °C for 6–10 h. n-Octane was detected as the product of skeletal isomerization of 2,5-dimethyl-hexadiene-1,5. For model FCC gasoline, the optimal conditions providing effective sulfur removal and selective hydrogenation were defined as 300–320 °C and 2–4 h under 3–5 MPa hydrogen pressure. The reusability of the catalyst was evaluated using model feed containing BT and C₈H₁₄ with molar ratio of 2:1 under 5 MPa hydrogen pressure at 320 °C for 2 h without any pre-treatment or regeneration of the catalyst before the next reaction run. In was established that HDS/HYDO selectivity increases with reaction run, which is due to the conversion of C₈H₁₄ decrease more significant as compared to that for BT, whereas conversion and product distribution maintain unchanged from 5 reaction run, indicating that the catalyst is running-in. For the spent NiMoS/MCM-41 catalyst the effective content of Mo in MoS₂ phase reaches 42.8 wt%, whereas that for Ni in NiS and NiMoS phase was 1.7 wt% and 0.7 wt%, respectively, which is compared to those values for the fresh sample.

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引用次数: 0

Direct synthesis of sulfonic acid functionalized zirconium metal-organic framework

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-04-08 DOI: 10.1016/j.micromeso.2025.113639

Ananya Chari , Toyoto Sato , Sofiia Bercha , John Senith Ravishan Fernando , Agnieszka Anna Gorzkowska-Sobas , Wakshum Mekonnen Tucho , Olena Zavorotynska , Sachin Maruti Chavan

This study successfully develops a direct synthesis protocol for sulfonic acid functionalized four carbons (C4) based Zr-Metal-Organic Frameworks (MOFs), resulting in the formation of two MOFs one with a defective UiO-type and a new structure named as UiS-1 (Universitetet i Stavanger). The new phase is formed in presence of modulators and at the excess linker to metal ratio (L:M) of 4:1. The synthesis with 40 equivalences of acetic acid and L:M ratio of 4:1 exhibits a similar pH, highlighting the role of H⁺ and, consequently pH of the reaction. The tuning of pH plays a crucial role in determining the formation of these distinct MOF structures, emphasizing the importance of precise control over synthetic conditions. The ZrSSA MOF (without modulator) aligns with the well-known UiO-type MOF, while UiS-1-40AA forms UiS-1 structure. UiS-1 is a tetragonal structure, previously unreported, is further elucidated in this research. This UiS-1 structure is characterized by lattice parameters a = b = 13.5233(4) Å, c = 16.3543(9) Å and angles α = β = γ = 90°. The UiS-1 structure is characterized using in-situ techniques and compositional analysis to assess, its properties and structural integrity, additional methods employed to verify the physical, chemical, and mechanical stability of UiS-1. These analyses demonstrate that UiS-1 maintains its structural integrity under various conditions, making sulfosuccinic acid a robust building block for designing of MOFs. Furthermore, the study explores the potential applications of the synthesized MOFs in gas adsorption. The adsorption capabilities of the MOFs were tested using CO₂, H₂O, and NH₃ gases, showcasing the material's efficiency and selectivity in capturing these molecules. The CO₂ adsorption results indicate that the functionalized Zr-MOFs, particularly ZrSSA and UiS-1-40AA shows 1.79 mmol g⁻¹ (7.88 wt%), and 1.46 mmol g⁻¹ (6.42 wt%), respectively at 1 bar and 273 K. This high CO₂ uptake per m² could be attributed to the high number of functional groups present in the structures.

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引用次数: 0