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Adsorption of Hg(II) from aqueous solutions on β-zeolite: Theoretical-experimental proposal for the surface interaction mechanism and the formation of metal complexes β-沸石对水溶液中汞(II)的吸附:表面相互作用机制和金属配合物形成的理论-实验建议
IF 4.8 3区 材料科学
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
{"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 ,&nbsp;Kevin Granados-Tavera ,&nbsp;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
Effective elimination of Congo red dye from tannery wastewater using Fe-pillared bentonite: Synthesis, adsorption isotherm, kinetics, and optimization via Box-Behnken design 铁柱膨润土有效去除制革废水中的刚果红染料:合成、吸附等温线、动力学和Box-Behnken设计优化
IF 4.8 3区 材料科学
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
{"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 ,&nbsp;Hajar El Moustansiri ,&nbsp;Mohamed Douma ,&nbsp;Abdelmjid Bouazizi ,&nbsp;Mounia Baidou ,&nbsp;Abdelaziz Elgamouz ,&nbsp;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
Selective hydrogenation of dienes to olefins and sulfur removal from model FCC gasoline over Ni-Mo sulfide catalyst supported on MCM-41 type silica MCM-41型二氧化硅负载Ni-Mo硫化物催化剂对模型FCC汽油中二烯选择性加氢制烯烃及脱硫的影响
IF 4.8 3区 材料科学
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
{"title":"Selective hydrogenation of dienes to olefins and sulfur removal from model FCC gasoline over Ni-Mo sulfide catalyst supported on MCM-41 type silica","authors":"Sijing Dai ,&nbsp;M.Yu. Talanova ,&nbsp;A.A. Samarov ,&nbsp;S.P. Verevkin ,&nbsp;M.V. Poliakov ,&nbsp;E.A. Karakhanov ,&nbsp;A.P. Glotov ,&nbsp;A.V. Vutolkina","doi":"10.1016/j.micromeso.2025.113631","DOIUrl":"10.1016/j.micromeso.2025.113631","url":null,"abstract":"<div><div>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 N<sub>2</sub> 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 MoS<sub>2</sub> was 48.3 wt%. According to thermodynamic calculations, the equilibrium mixture contains 2,5-dimethylhexane (82 %) and <em>n</em>-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. <em>n-</em>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 <strong>BT</strong> and <strong>C<sub>8</sub>H<sub>14</sub></strong> 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 <strong>HDS/HYDO</strong> selectivity increases with reaction run, which is due to the conversion of <strong>C<sub>8</sub>H<sub>14</sub></strong> decrease more significant as compared to that for <strong>BT,</strong> 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 MoS<sub>2</sub> 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.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113631"},"PeriodicalIF":4.8,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835062","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
Three-dimensional CMK-8 and CMK-9 ordered mesoporous carbons as potential nanocarriers for cephalexin controlled release 三维CMK-8和CMK-9有序介孔碳作为头孢氨苄控释的潜在纳米载体
IF 4.8 3区 材料科学
Microporous and Mesoporous Materials Pub Date : 2025-04-08 DOI: 10.1016/j.micromeso.2025.113640
Kiara Montiel-Centeno , Deicy Barrera , Fátima García-Villén , César Viseras , Enrique Rodríguez-Castellón , Cristian A. Diaz , Jhonny Villarroel-Rocha , M. Sergio Moreno , Karim Sapag
{"title":"Three-dimensional CMK-8 and CMK-9 ordered mesoporous carbons as potential nanocarriers for cephalexin controlled release","authors":"Kiara Montiel-Centeno ,&nbsp;Deicy Barrera ,&nbsp;Fátima García-Villén ,&nbsp;César Viseras ,&nbsp;Enrique Rodríguez-Castellón ,&nbsp;Cristian A. Diaz ,&nbsp;Jhonny Villarroel-Rocha ,&nbsp;M. Sergio Moreno ,&nbsp;Karim Sapag","doi":"10.1016/j.micromeso.2025.113640","DOIUrl":"10.1016/j.micromeso.2025.113640","url":null,"abstract":"<div><div>Ordered mesoporous carbons with a three-dimensional cubic structure, CMK-8 and CMK-9, were synthesized using the hard-template method and evaluated, for the first time, as drug delivery systems for cephalexin (CFX), a widely used antibiotic in infectious disease therapy. The materials were functionalized with 3-aminopropyltriethoxysilane via graftin<em>g</em> to enhance aqueous dispersion and control drug release. CFX was loaded by adsorption, and its release was studied under simulated oral conditions at acidic (pH 1.2) and intestinal (pH 6.8) environments. Due to its dual mesoporosity and larger surface area, CMK-9 exhibited superior CFX adsorption capacity compared to CMK-8. Both materials facilitated controlled drug release, with CMK-9 achieving the highest release rate (89 %) within 14 h under acidic conditions, whereas pure CFX exhibited a much faster release. Kinetic analysis using the Weibull model indicated a Fickian diffusion mechanism governed by porosity and electrostatic interactions. These findings underscore the potential of ordered mesoporous carbons with cubic structures as promising platforms for controlled antibiotic delivery.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113640"},"PeriodicalIF":4.8,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817061","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
Direct synthesis of sulfonic acid functionalized zirconium metal-organic framework 磺酸功能化金属锆-有机骨架的直接合成
IF 4.8 3区 材料科学
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
{"title":"Direct synthesis of sulfonic acid functionalized zirconium metal-organic framework","authors":"Ananya Chari ,&nbsp;Toyoto Sato ,&nbsp;Sofiia Bercha ,&nbsp;John Senith Ravishan Fernando ,&nbsp;Agnieszka Anna Gorzkowska-Sobas ,&nbsp;Wakshum Mekonnen Tucho ,&nbsp;Olena Zavorotynska ,&nbsp;Sachin Maruti Chavan","doi":"10.1016/j.micromeso.2025.113639","DOIUrl":"10.1016/j.micromeso.2025.113639","url":null,"abstract":"<div><div>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<sup>+</sup> 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 CO<sub>2</sub>, H<sub>2</sub>O, and NH<sub>3</sub> gases, showcasing the material's efficiency and selectivity in capturing these molecules. The CO<sub>2</sub> adsorption results indicate that the functionalized Zr-MOFs, particularly ZrSSA and UiS-1-40AA shows 1.79 mmol g<sup>−1</sup> (7.88 wt%), and 1.46 mmol g<sup>−1</sup> (6.42 wt%), respectively at 1 bar and 273 K. This high CO<sub>2</sub> uptake per m<sup>2</sup> could be attributed to the high number of functional groups present in the structures.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113639"},"PeriodicalIF":4.8,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826413","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
Degradation of quinoline by ozone oxidation using Fe3Ce2/NaY catalyst Fe3Ce2/NaY催化臭氧氧化降解喹啉
IF 4.8 3区 材料科学
Microporous and Mesoporous Materials Pub Date : 2025-04-08 DOI: 10.1016/j.micromeso.2025.113630
Xinyue Li, Gang Li, Runfa He
{"title":"Degradation of quinoline by ozone oxidation using Fe3Ce2/NaY catalyst","authors":"Xinyue Li,&nbsp;Gang Li,&nbsp;Runfa He","doi":"10.1016/j.micromeso.2025.113630","DOIUrl":"10.1016/j.micromeso.2025.113630","url":null,"abstract":"<div><div>Herein, Fe<sub>3</sub>Ce<sub>2</sub>/NaY catalysts for catalyzing the oxidative degradation of quinoline by ozonation were prepared by the impregnation method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The Fe<sub>3</sub>Ce<sub>2</sub>/NaY had high activity for catalyzing ozone oxidation, the quinoline removal efficiency reached 99.14 % in 10 min for the 90 mg/L quinoline solution. Meanwhile, the catalyst had good reusability and the COD removal performance was almost unchanged during four cycles of reaction. In the catalytic ozone oxidation system, the reaction kinetics of quinoline degradation were consistent with a pseudo-first-order reaction. Surface hydroxyl groups facilitated the adsorption and decomposition of O<sub>3</sub>, thus promoting the generation of reactive oxygen species (ROS) and improving the quinoline mineralization efficiency, which played an important role in the catalytic process. The degradation intermediates were also investigated using liquid chromatography-mass spectrometry (LC-MS) and ion chromatography.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113630"},"PeriodicalIF":4.8,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817059","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
Performance and mechanism of zeolite derived from coal gasification coarse slag for adsorbing Ni(II) from wastewater 煤气化粗渣沸石吸附废水中Ni(II)的性能及机理
IF 4.8 3区 材料科学
Microporous and Mesoporous Materials Pub Date : 2025-04-07 DOI: 10.1016/j.micromeso.2025.113627
Yangyang Tang , Linbo Li , Kai Yang , Chao Wang , Pan Yang , Lei Dong , Feiping Zhao , Zhao Fang
{"title":"Performance and mechanism of zeolite derived from coal gasification coarse slag for adsorbing Ni(II) from wastewater","authors":"Yangyang Tang ,&nbsp;Linbo Li ,&nbsp;Kai Yang ,&nbsp;Chao Wang ,&nbsp;Pan Yang ,&nbsp;Lei Dong ,&nbsp;Feiping Zhao ,&nbsp;Zhao Fang","doi":"10.1016/j.micromeso.2025.113627","DOIUrl":"10.1016/j.micromeso.2025.113627","url":null,"abstract":"<div><div>The heavy metal Ni<sup>2+</sup> in water, posing a serious threat to humans and other organisms through food accumulation, can be removed using high-performance zeolites. The study successfully prepared a highly efficient Y-zeolite adsorbent from coal gasification coarse slag (CGCS) via alkali melt-seed induced hydrothermal synthesis, with an average pore diameter of 8.3 nm. The comprehensive characterization and adsorption experiments were conducted on the synthesized Y-zeolite to investigate diverse factors' influence on performance. The removal efficiency of Ni<sup>2+</sup> reached 98.325 % within 20 min and then stabilized at 99.760 % at a dosage of 1 g L<sup>−1</sup>, pH maintained at 7.0, and an initial concentration of Ni<sup>2+</sup> at 100 mg L<sup>−1</sup>. The adsorption process conforms to the Pseudo-second-order kinetic model and Langmuir adsorption isotherm model, with the adsorption capacity of 98.943 mg g<sup>−1</sup> and the theoretical maximum adsorption capacity of 515.500 mg g<sup>−1</sup>. The adsorption mechanism was analyzed by SEM-EDS and FTIR, based on the ion exchange interaction between Ni<sup>2+</sup> and T-O groups. Furthermore, DFT calculations were employed to prove the most stable site for Ni<sup>2+</sup> adsorption on Y-zeolite. The successful adsorption of Ni<sup>2+</sup> on suitable sites located in six-membered rings of SuCage-6mr and Cage-6mr. In conclusion, Y-zeolite showed great potential as an efficient adsorbent for Ni<sup>2+</sup> removal, promoting the comprehensive utilization of solid waste and creating a mutually beneficial outcome.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113627"},"PeriodicalIF":4.8,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817060","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
Tailoring the preparation of USY zeolite with uniform mesoporosity for improved catalytic activity in phenol/isopropanol alkylation 为提高苯酚/异丙醇烷基化的催化活性,定制均匀介孔USY分子筛的制备
IF 4.8 3区 材料科学
Microporous and Mesoporous Materials Pub Date : 2025-04-06 DOI: 10.1016/j.micromeso.2025.113629
C. Molina , A. Abdrassilova , M.I. Ávila , M.M. Alonso-Doncel , J. Cueto , G. Gómez-Pozuelo , L. Briones , J.A. Botas , D.P. Serrano , A. Peral , J.M. Escola
{"title":"Tailoring the preparation of USY zeolite with uniform mesoporosity for improved catalytic activity in phenol/isopropanol alkylation","authors":"C. Molina ,&nbsp;A. Abdrassilova ,&nbsp;M.I. Ávila ,&nbsp;M.M. Alonso-Doncel ,&nbsp;J. Cueto ,&nbsp;G. Gómez-Pozuelo ,&nbsp;L. Briones ,&nbsp;J.A. Botas ,&nbsp;D.P. Serrano ,&nbsp;A. Peral ,&nbsp;J.M. Escola","doi":"10.1016/j.micromeso.2025.113629","DOIUrl":"10.1016/j.micromeso.2025.113629","url":null,"abstract":"<div><div>The preparation of hierarchical USY zeolite, exhibiting uniform mesoporosity and high Si/Al atomic ratio (48–52), has been investigated by means of a surfactant/ammonia post-treatment applied to a commercial USY sample. The procedure involved the use of temperatures within 40–135 °C, a low ammonia concentration solution (0.05 N) and hydrothermal synthesis times of 20 h. When working at 40–80 °C, the obtained USY samples exhibit enhanced intraparticular mesoporosity (324–418 m<sup>2</sup> g<sup>−1</sup>), showing increasingly uniform mesopores around 4.0 nm, while holding a remarkable zeolitic microporosity (413–363 m<sup>2</sup> g<sup>−1</sup>). In contrast, higher temperatures resulted in a steady abatement of crystalline zeolitic domains, with a total collapse of the zeolite structure at 135 °C. These hierarchical USY materials were tested in the alkylation of phenol with isopropanol, wherein one of the obtained products, e.g. 2,6-diisopropylphenol (Propofol), is the most important intravenous anaesthetic in the market. Interestingly, the generation of the uniform mesoporosity in USY samples led to an enhancement of both the phenol conversion and the selectivity towards C-alkylation products. Thus, the sample treated at 60 °C (USY-60) gave rise to the highest selectivity towards C-alkylation products (84 %) and poly-alkylphenols formation (72 %), with an encouraging selectivity towards 2,6-diisopropylphenol (43 %).</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113629"},"PeriodicalIF":4.8,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792112","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
Remarkable catalytic performance of newly synthesized H-SSZ-23 zeolite in methanol to olefin process 新合成的H-SSZ-23沸石在甲醇制烯烃过程中具有显著的催化性能
IF 4.8 3区 材料科学
Microporous and Mesoporous Materials Pub Date : 2025-04-05 DOI: 10.1016/j.micromeso.2025.113628
Elmira Asghari , Reza Alizadeh , Hafez Maghsoudi
{"title":"Remarkable catalytic performance of newly synthesized H-SSZ-23 zeolite in methanol to olefin process","authors":"Elmira Asghari ,&nbsp;Reza Alizadeh ,&nbsp;Hafez Maghsoudi","doi":"10.1016/j.micromeso.2025.113628","DOIUrl":"10.1016/j.micromeso.2025.113628","url":null,"abstract":"<div><div>Methanol-to-olefin technology, designed to produce light olefins from methanol, often encounters issues with rapid catalyst deactivation due to diffusion challenges and coke build-up. The structure of zeolite significantly influences both the distribution of olefin products and the stability of the catalyst. In this research, H-SSZ-23 zeolite synthesized by hydrothermal method in two different OH<sup>−</sup> and F<sup>−</sup> mediums investigated as a novel catalyst in MTO process. Additionally, conventional H-SSZ-13 zeolite was synthesized with the identical conditions to compare the performance of H-SSZ-23 zeolite with the literature. To determine the physicochemical properties of the catalysts, various characterization methods were employed, including XRD, FESEM, ICP, BET-BJH, FTIR, NH3-TPD, and TG/DTG analyses. The methanol conversion and product selectivity of the synthesized zeolites were tested in the MTO reaction at temperatures ranging from 350 to 450 °C, under atmospheric pressure with a methanol weight hourly space velocity (WHSV) of 1.2 h<sup>−1</sup>. The seed-assisted synthesis method yielded pure H-SSZ-23 (STT) and H-SSZ-13 (CHA) zeolite phases with distinct morphologies, textural properties, surface acidity and catalytic performance in the MTO process. Among the findings, the H-SSZ-23 zeolite synthesized in OH<sup>−</sup> medium having 99 % methanol conversion, 70 % light olefins selectivity and about 300 min stability (80 % initial conversion) at 450 °C exhibited best performance with improved stability and reduced coke formation in the MTO process. This superior stability can be attributed to its unique structure with smaller particle size at nanoscale, increased mesopore volume, larger pore diameter and milder acidity compared to H-SSZ-13 (CHA) zeolite.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"392 ","pages":"Article 113628"},"PeriodicalIF":4.8,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143808598","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
Calcination effects on meta-forms of kaolin and halloysite: Role of Al-Si spinel crystallization in zeolite synthesis 煅烧对高岭土和高岭土元形态的影响:铝硅尖晶石结晶在沸石合成中的作用
IF 4.8 3区 材料科学
Microporous and Mesoporous Materials Pub Date : 2025-04-05 DOI: 10.1016/j.micromeso.2025.113626
Pelin Pasabeyoglu , Burcu Akata
{"title":"Calcination effects on meta-forms of kaolin and halloysite: Role of Al-Si spinel crystallization in zeolite synthesis","authors":"Pelin Pasabeyoglu ,&nbsp;Burcu Akata","doi":"10.1016/j.micromeso.2025.113626","DOIUrl":"10.1016/j.micromeso.2025.113626","url":null,"abstract":"<div><div>The role of Al-Si spinel crystallization during high-temperature calcination of kaolin and halloysite was investigated to optimize the direct synthesis of zeolites 4A and 13X without additional silica or structure-directing agents. Differential thermogravimetry (DTG) and in situ synchrotron X-ray diffraction (SR-XRD) tracked dehydroxylation and Al-Si spinel crystallization, revealing complete dehydroxylation at 575 °C for kaolin and 500 °C for halloysite, with spinel crystallization occurring in a range of 900–940 °C for both clays. Calcination promoted the formation of Al-Si spinel and amorphous silica, increasing the Si/Al ratio and enabling control of zeolite composition and porosity. Calcination conditions determined the zeolite type, evolving from pure 4A to a mixture of 4A/13X, and finally pure 13X. The presence of Al-Si spinel in 13X enhanced mesoporosity, introducing voids and channels between micropores and contributing to high BET surface areas (&gt;500 m<sup>2</sup>/g) with a dual micro/mesoporous structure. This study establishes a direct link between calcination parameters and zeolite properties, highlighting Al-Si spinel's role in phase transitions and porosity development. These findings provide valuable insights for optimizing industrial applications such as adsorption and catalysis.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113626"},"PeriodicalIF":4.8,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785569","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
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