Microporous and Mesoporous Materials最新文献_第9页

Cationic cellulose nanocrystals assisted synthesis of mesoporous Silicalite-1 zeolites with fewer silanol defects

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-08 DOI: 10.1016/j.micromeso.2024.113448

Run Zou , Li Lyu , Sarayute Chansai , Joseph Hurd , Ruojia Xin , Jared An Cheang Wong , Daniel Lee , Christopher Hardacre , Yilai Jiao , Xiaolei Fan , Xiaoxia Ou

Cellulose nanocrystals (CNCs) are biomass-derived materials with tunable surface properties, which can be used as additives for facilitating mesoporous zeolite synthesis. Herein, cationic cellulose nanocrystals (quaternary ammonium-modified, CNC-N) and unmodified cellulose nanocrystals (hydroxyl-terminated, CNC-OH) were employed to assist the synthesis of mesoporous silicalite-1 (S-1) zeolites with the reduced usage of tetrapropylammonium (TPA, TPA/SiO₂ = 0.04). Parametric studies were conducted to obtain the well-crystallised mesoporous S-1 zeolites. Results showed that the CNC-N could more effectively produce hydrophobic S-1 zeolites with fewer internal silanol defects and higher mesoporosity (e.g., mesoporosity, f_meso, was 31, 20 and 22 % for S-1 templated by CNC-N, CNC-OH and without CNCs, respectively), which was expected to favour the adsorption of non-polar volatile organic compounds (VOCs). According to the characterisation data of the materials at different stages of the synthesis, the CNC-N could induce strong interaction with the anionic silicate species (via electrostatic force), resulting in ‘deposition’ of silicate and TPA on CNC-N, which exhibited slow non-classical crystallisation behaviour that led to the formation of intergrown S-1 (explaining the improved mesoporosity) with fewer internal silanol defects (due to the slow crystallisation). The obtained mesoporous S-1 showed improved performance in toluene adsorption compared to other reference zeolites under investigation. Findings of the work demonstrated the potential of cationic CNCs as the additives for pore/silanol defects engineering of zeolitic materials.

{"title":"Cationic cellulose nanocrystals assisted synthesis of mesoporous Silicalite-1 zeolites with fewer silanol defects","authors":"Run Zou , Li Lyu , Sarayute Chansai , Joseph Hurd , Ruojia Xin , Jared An Cheang Wong , Daniel Lee , Christopher Hardacre , Yilai Jiao , Xiaolei Fan , Xiaoxia Ou","doi":"10.1016/j.micromeso.2024.113448","DOIUrl":"10.1016/j.micromeso.2024.113448","url":null,"abstract":"<div><div>Cellulose nanocrystals (CNCs) are biomass-derived materials with tunable surface properties, which can be used as additives for facilitating mesoporous zeolite synthesis. Herein, cationic cellulose nanocrystals (quaternary ammonium-modified, CNC-N) and unmodified cellulose nanocrystals (hydroxyl-terminated, CNC-OH) were employed to assist the synthesis of mesoporous silicalite-1 (S-1) zeolites with the reduced usage of tetrapropylammonium (TPA, TPA/SiO<sub>2</sub> = 0.04). Parametric studies were conducted to obtain the well-crystallised mesoporous S-1 zeolites. Results showed that the CNC-N could more effectively produce hydrophobic S-1 zeolites with fewer internal silanol defects and higher mesoporosity (e.g., mesoporosity, <em>f</em><sub><em>meso</em></sub>, was 31, 20 and 22 % for S-1 templated by CNC-N, CNC-OH and without CNCs, respectively), which was expected to favour the adsorption of non-polar volatile organic compounds (VOCs). According to the characterisation data of the materials at different stages of the synthesis, the CNC-N could induce strong interaction with the anionic silicate species (<em>via</em> electrostatic force), resulting in ‘deposition’ of silicate and TPA on CNC-N, which exhibited slow non-classical crystallisation behaviour that led to the formation of intergrown S-1 (explaining the improved mesoporosity) with fewer internal silanol defects (due to the slow crystallisation). The obtained mesoporous S-1 showed improved performance in toluene adsorption compared to other reference zeolites under investigation. Findings of the work demonstrated the potential of cationic CNCs as the additives for pore/silanol defects engineering of zeolitic materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113448"},"PeriodicalIF":4.8,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100628","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The ordered mesoporous TS-1 synthesized with geometrically matched surfactant and its application in the deep oxidative desulfurization

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-07 DOI: 10.1016/j.micromeso.2024.113447

Shuting Du, Tianyang Wang, Wanyu Dou, Jinxu Feng, Yue Huang, Chengpeng Li

Deep oxidative desulfurization from hydrocarbon fuels has attracted an extensive attention of researchers owing to it can be reduced the toxic sulfur dioxide emissions efficiently during combustion. In this work, we identify the ordered mesoporous structure of hierarchical TS-1 as a key factor in enhancing catalytic performance for oxidative desulfurization reactions. We synthesized an intracrystalline ordered mesoporous TS-1 catalyst by introducing a geometrically compatible surfactant containing a diquaternary ammonium group, an azobenzene segment, and an appropriately sized hydrophobic alkyl tail. The developed hierarchical TS-1 catalyst exhibits superior catalytic activity in the oxidative reaction of dibenzothiophene across various temperatures, outperforming several typical hierarchical porous TS-1 catalysts reported in the literature, even at a lower reaction temperature of 30 °C. This innovative ordered mesoporous TS-1 not only presents a promising catalyst for future deep desulfurization applications but also introduces a novel strategy for designing efficient hierarchical catalytic materials through structural optimization.

{"title":"The ordered mesoporous TS-1 synthesized with geometrically matched surfactant and its application in the deep oxidative desulfurization","authors":"Shuting Du, Tianyang Wang, Wanyu Dou, Jinxu Feng, Yue Huang, Chengpeng Li","doi":"10.1016/j.micromeso.2024.113447","DOIUrl":"10.1016/j.micromeso.2024.113447","url":null,"abstract":"<div><div>Deep oxidative desulfurization from hydrocarbon fuels has attracted an extensive attention of researchers owing to it can be reduced the toxic sulfur dioxide emissions efficiently during combustion. In this work, we identify the ordered mesoporous structure of hierarchical TS-1 as a key factor in enhancing catalytic performance for oxidative desulfurization reactions. We synthesized an intracrystalline ordered mesoporous TS-1 catalyst by introducing a geometrically compatible surfactant containing a diquaternary ammonium group, an azobenzene segment, and an appropriately sized hydrophobic alkyl tail. The developed hierarchical TS-1 catalyst exhibits superior catalytic activity in the oxidative reaction of dibenzothiophene across various temperatures, outperforming several typical hierarchical porous TS-1 catalysts reported in the literature, even at a lower reaction temperature of 30 °C. This innovative ordered mesoporous TS-1 not only presents a promising catalyst for future deep desulfurization applications but also introduces a novel strategy for designing efficient hierarchical catalytic materials through structural optimization.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113447"},"PeriodicalIF":4.8,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100631","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

Retention regularities of alkanols and other small organic molecules on 13X zeolite under HILIC conditions

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-06 DOI: 10.1016/j.micromeso.2024.113443

Viktoriia D. Kazakova, Nina B. Rozhmanova, Sergey N. Lanin, Pavel N. Nesterenko

The retention regularities on a column packed with microspherical zeolite 13X particles were studied for different classes of compounds (alkanes, aromatic substances, oxygen-, nitrogen-, chlorine-, and sulfur- containing compounds) under conditions of hydrophilic interaction liquid chromatography (HILIC) using methanol and acetonitrile as mobile phases. In general, the retention (logk’) of studied substances having kinetic diameter less than zeolite pore size is proportional to their polarity. The retention of organic substances was compared for 13X and mesoporous silica columns. A special attention was paid to the retention of n- and iso-alcohols homologues, for which a electrostatically induced sieving effect was observed. It was found that retention factors (k’) of solutes on 13X depend strongly on flow rate of the mobile phases indicating the presence of kinetic selectivity effect for the micrporous adsorbent. For the first time the baseline separation was obtained for the low homologues of n-alkanols. Also, selective separation of methanol and methanol-d₄ (selectivity α = 1.274; resolution of peaks R_S = 1.32) is achieved on 50 × 4.6 mm I.D. column with acetonitrile as the eluent.

{"title":"Retention regularities of alkanols and other small organic molecules on 13X zeolite under HILIC conditions","authors":"Viktoriia D. Kazakova, Nina B. Rozhmanova, Sergey N. Lanin, Pavel N. Nesterenko","doi":"10.1016/j.micromeso.2024.113443","DOIUrl":"10.1016/j.micromeso.2024.113443","url":null,"abstract":"<div><div>The retention regularities on a column packed with microspherical zeolite 13X particles were studied for different classes of compounds (alkanes, aromatic substances, oxygen-, nitrogen-, chlorine-, and sulfur- containing compounds) under conditions of hydrophilic interaction liquid chromatography (HILIC) using methanol and acetonitrile as mobile phases. In general, the retention (log<em>k’</em>) of studied substances having kinetic diameter less than zeolite pore size is proportional to their polarity. The retention of organic substances was compared for 13X and mesoporous silica columns. A special attention was paid to the retention of <em>n-</em> and <em>iso-</em>alcohols homologues, for which a electrostatically induced sieving effect was observed. It was found that retention factors (<em>k’</em>) of solutes on 13X depend strongly on flow rate of the mobile phases indicating the presence of kinetic selectivity effect for the micrporous adsorbent. For the first time the baseline separation was obtained for the low homologues of <em>n</em>-alkanols. Also, selective separation of methanol and methanol-d<sub>4</sub> (selectivity <em>α</em> = 1.274; resolution of peaks <em>R</em><sub>S</sub> = 1.32) is achieved on 50 × 4.6 mm I.D. column with acetonitrile as the eluent.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113443"},"PeriodicalIF":4.8,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100629","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

Poisoning effect of chlorine anions in the catalytic activity of CuO/CeO2/UiO-66 for CO-PROX reaction and strategy for catalyst activation

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-05 DOI: 10.1016/j.micromeso.2024.113445

Carlos W. Dos Santos Moraes , P. Gómez Bernabéu , Katia J. Gómez Villegas , E. Guillén Bas , I. Martínez López , A. Davó Quiñonero , D. Fairén Jiménez , D. Lozano Castelló , A. Bueno López Prof.

UiO-66 was synthesized using ZrOCl₂·8H₂O as metal precursor, and CuO/CeO₂/UiO-66 catalysts were prepared and tested for preferential CO oxidation in H_2-rich streams (CO-PROX reaction), a reaction of practical significance in hydrogen purification for fuel cells. The study highlights the detrimental effect of residual chlorine anions from UiO-66 synthesis and DMF washing on the catalytic performance of CuO/CeO₂/UiO-66. An activation strategy involving rigorous water washing and thermal treatment at 160 °C under CO-PROX conditions was developed. Both steps were deemed necessary, as employing only one proved insufficient to reduce chlorine levels to non-poisoning thresholds. This activation procedure does compromise UiO-66 crystallinity and porosity, but it is justified by achieving a fully functional catalyst. TEM images confirm the uniform dispersion of the CuO/CeO₂ active phase on the UiO-66 matrix post-activation and after catalytic testing. A 16-h CO-PROX test at 160 °C with the CuO/CeO₂/UiO-66 catalyst, once activated, demonstrated stable performance throughout the extended long-term experiment. This research provides valuable insights into optimizing CuO/CeO₂/UiO-66 catalysts for CO-PROX application.

{"title":"Poisoning effect of chlorine anions in the catalytic activity of CuO/CeO2/UiO-66 for CO-PROX reaction and strategy for catalyst activation","authors":"Carlos W. Dos Santos Moraes , P. Gómez Bernabéu , Katia J. Gómez Villegas , E. Guillén Bas , I. Martínez López , A. Davó Quiñonero , D. Fairén Jiménez , D. Lozano Castelló , A. Bueno López Prof.","doi":"10.1016/j.micromeso.2024.113445","DOIUrl":"10.1016/j.micromeso.2024.113445","url":null,"abstract":"<div><div>UiO-66 was synthesized using ZrOCl<sub>2</sub>·8H<sub>2</sub>O as metal precursor, and CuO/CeO<sub>2</sub>/UiO-66 catalysts were prepared and tested for preferential CO oxidation in H<sub>2-</sub>rich streams (CO-PROX reaction), a reaction of practical significance in hydrogen purification for fuel cells. The study highlights the detrimental effect of residual chlorine anions from UiO-66 synthesis and DMF washing on the catalytic performance of CuO/CeO<sub>2</sub>/UiO-66. An activation strategy involving rigorous water washing and thermal treatment at 160 °C under CO-PROX conditions was developed. Both steps were deemed necessary, as employing only one proved insufficient to reduce chlorine levels to non-poisoning thresholds. This activation procedure does compromise UiO-66 crystallinity and porosity, but it is justified by achieving a fully functional catalyst. TEM images confirm the uniform dispersion of the CuO/CeO<sub>2</sub> active phase on the UiO-66 matrix post-activation and after catalytic testing. A 16-h CO-PROX test at 160 °C with the CuO/CeO<sub>2</sub>/UiO-66 catalyst, once activated, demonstrated stable performance throughout the extended long-term experiment. This research provides valuable insights into optimizing CuO/CeO<sub>2</sub>/UiO-66 catalysts for CO-PROX application.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113445"},"PeriodicalIF":4.8,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100122","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Exploring zeolite potential for hydrofluorocarbon capture and recycling: Insights from molecular simulations

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-04 DOI: 10.1016/j.micromeso.2024.113442

Abrar A. Elhussien , Ismail Abdulazeez , Hassan Alasiri , Wael A. Fouad

The need for efficient separation of hydrofluorocarbons for recycling and environmental protection is critical due to their substantial impact on global warming. However, conventional methods such as cryogenic distillation face significant limitations due to the azeotropic behavior of many of these hydrofluorocarbons. This study evaluates the adsorption behavior of various hydrofluorocarbons in zeolite structures, specifically Linde Type A (3A, 4A, and 5A) and Faujasite Type X (13X), using molecular dynamics and grand canonical Monte Carlo simulations. The simulations were validated against experimental data, confirming the reliability of the computational models. Adsorption isotherms were fitted using the Langmuir-Freundlich model to describe the adsorption behavior across different pressures. Focusing on fluoromethane derivatives, the study highlighted key interactions and adsorption capacities in various zeolites. The isotherms of various hydrofluorocarbons in zeolite 13X were explored, revealing differential adsorption based on molecular structure. The potential for using zeolite 13X and 5A to separate refrigerant mixtures was also studied, showing distinct selectivity patterns. Additionally, the temperature dependence of adsorption isotherms and isosteric heat was studied to gain insights into the thermodynamics of the adsorption processes. Key results indicate that zeolite 13X demonstrates strong cation-fluorine interactions, particularly effective for the adsorption of large hydrofluorocarbon molecules, which preferentially occupy 12-membered ring windows. In contrast, zeolite 5A exhibited predominant hydrogen bonding interactions at low pressures, with hydrofluorocarbon molecules occupying the smaller 8-membered ring windows. These findings underscore the selective adsorption capabilities of these zeolites, highlighting their potential application in hydrofluorocarbon separation and recycling processes.

{"title":"Exploring zeolite potential for hydrofluorocarbon capture and recycling: Insights from molecular simulations","authors":"Abrar A. Elhussien , Ismail Abdulazeez , Hassan Alasiri , Wael A. Fouad","doi":"10.1016/j.micromeso.2024.113442","DOIUrl":"10.1016/j.micromeso.2024.113442","url":null,"abstract":"<div><div>The need for efficient separation of hydrofluorocarbons for recycling and environmental protection is critical due to their substantial impact on global warming. However, conventional methods such as cryogenic distillation face significant limitations due to the azeotropic behavior of many of these hydrofluorocarbons. This study evaluates the adsorption behavior of various hydrofluorocarbons in zeolite structures, specifically Linde Type A (3A, 4A, and 5A) and Faujasite Type X (13X), using molecular dynamics and grand canonical Monte Carlo simulations. The simulations were validated against experimental data, confirming the reliability of the computational models. Adsorption isotherms were fitted using the Langmuir-Freundlich model to describe the adsorption behavior across different pressures. Focusing on fluoromethane derivatives, the study highlighted key interactions and adsorption capacities in various zeolites. The isotherms of various hydrofluorocarbons in zeolite 13X were explored, revealing differential adsorption based on molecular structure. The potential for using zeolite 13X and 5A to separate refrigerant mixtures was also studied, showing distinct selectivity patterns. Additionally, the temperature dependence of adsorption isotherms and isosteric heat was studied to gain insights into the thermodynamics of the adsorption processes. Key results indicate that zeolite 13X demonstrates strong cation-fluorine interactions, particularly effective for the adsorption of large hydrofluorocarbon molecules, which preferentially occupy 12-membered ring windows. In contrast, zeolite 5A exhibited predominant hydrogen bonding interactions at low pressures, with hydrofluorocarbon molecules occupying the smaller 8-membered ring windows. These findings underscore the selective adsorption capabilities of these zeolites, highlighting their potential application in hydrofluorocarbon separation and recycling processes.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113442"},"PeriodicalIF":4.8,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100630","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

Synthesis and structural studies of ammonium exchanged synthetic analogue of disordered aluminosilicate natrolite

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-02 DOI: 10.1016/j.micromeso.2024.113441

Manjusha J. Gavhane , R.K. Jha , Kyung-Wan Nam , Deu S. Bhange

The current article reports preparation and structural analysis of NH₄⁺ exchanged form of synthetic natrolite zeolite (NH₄-natrolite) with disordered structure wherein Si and Al occupies all the tetrahedral (T) sites in the zeolite framework. Structural data is used to gain insight into the structural parameters those influence thermal stability of its proposed H-form. NH₄-natrolite is prepared by ion-exchange method from K-natrolite (which was also obtained by ion-exchange with Na-natrolite). Na-natrolite, K-natrolite and NH₄-natrolite prepared in this study were tested for their structural, morphological and thermal analysis. Synchrotron X-ray diffraction data was utilized to estimate the crystal structures of hydrated forms of Na-natrolite, K-natrolite and NH₄-exchanged natrolites. Thermal analysis of NH₄-natrolite revealed that the dehydration is followed by removal of ammonia during calcination. The role of the size (radius) and nature (either divalent or monovalent) of the exchangeable cations present in the channels, the framework chemical content and extent of ‘T’ atom ordering have been collectively discussed and correlated with the structural behaviour of calcined NH₄-natrolite to explain its thermal stability in better way.

{"title":"Synthesis and structural studies of ammonium exchanged synthetic analogue of disordered aluminosilicate natrolite","authors":"Manjusha J. Gavhane , R.K. Jha , Kyung-Wan Nam , Deu S. Bhange","doi":"10.1016/j.micromeso.2024.113441","DOIUrl":"10.1016/j.micromeso.2024.113441","url":null,"abstract":"<div><div>The current article reports preparation and structural analysis of NH<sub>4</sub><sup>+</sup> exchanged form of synthetic natrolite zeolite (NH<sub>4</sub>-natrolite) with disordered structure wherein Si and Al occupies all the tetrahedral (T) sites in the zeolite framework. Structural data is used to gain insight into the structural parameters those influence thermal stability of its proposed H-form. NH<sub>4</sub>-natrolite is prepared by ion-exchange method from K-natrolite (which was also obtained by ion-exchange with Na-natrolite). Na-natrolite, K-natrolite and NH<sub>4</sub>-natrolite prepared in this study were tested for their structural, morphological and thermal analysis. Synchrotron X-ray diffraction data was utilized to estimate the crystal structures of hydrated forms of Na-natrolite, K-natrolite and NH<sub>4</sub>-exchanged natrolites. Thermal analysis of NH<sub>4</sub>-natrolite revealed that the dehydration is followed by removal of ammonia during calcination. The role of the size (radius) and nature (either divalent or monovalent) of the exchangeable cations present in the channels, the framework chemical content and extent of ‘T’ atom ordering have been collectively discussed and correlated with the structural behaviour of calcined NH<sub>4</sub>-natrolite to explain its thermal stability in better way.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113441"},"PeriodicalIF":4.8,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164082","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

Dynamic simulation-driven analysis of cadmium, nickel, cobalt, and iron adsorption mechanisms in zeolite LTA synthesized from bentonite 膨润土合成的沸石 LTA 对镉、镍、钴和铁的吸附机理的动态模拟分析

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-11-26 DOI: 10.1016/j.micromeso.2024.113433

Imad El Bojaddayni , Youssef El Ouardi , Mohammed Elkabous , Nafea Achalhi , Alharith Yousuf , Yasser Karzazi , Abdelkrim Ouammou , Sami Virolainen

A practical and cost-effective method was successfully developed for synthesizing high-performance zeolite LTA from bentonite clay by fine-tuning activation steps and crystallization parameters. The optimal synthesis conditions and crystallization mechanism were investigated. The synthesized zeolites were characterized using XRD, FTIR, and SEM-EDS techniques. The results highlight the significant influence of factors such as crystallization temperature, duration, and the effect of sodium hydroxide concentration on the formation of zeolites. Optimal conditions set at a crystallization temperature of 97 °C, duration of 24 h, and NaOH concentration of 4M yielded pure zeolite LTA, boasting high crystallinity levels. Achieving a peak crystallinity of 82 %. The obtained zeolite LTA showed an exceptional Cd (II) ion exchange capacity. A mechanism involving adsorption of Cd²⁺, Ni²⁺, Co²⁺, and Fe²⁺ ions in zeolite LTA at the α and β-cages has been proposed using dynamic simulation. This mechanism supports all experimental results, in particular for LTA- Cd²⁺, Cd²⁺ ions are predominantly distributed in both α and β-cages, with a denser distribution in the α-cages, indicating a strong preference for these sites due to their geometric and electronic environment. The resulted zeolite LTA demonstrated ability for successful Cd (II) removal, affirming its utility as an efficient material in environmental remediation industries.

通过对活化步骤和结晶参数进行微调，成功开发出了一种从膨润土中合成高性能沸石 LTA 的实用且具有成本效益的方法。研究了最佳合成条件和结晶机理。利用 XRD、FTIR 和 SEM-EDS 技术对合成的沸石进行了表征。结果表明，结晶温度、持续时间和氢氧化钠浓度等因素对沸石的形成有重大影响。在结晶温度为 97 °C、持续时间为 24 小时、NaOH 浓度为 4M 的最佳条件下，产生了高结晶度的纯沸石 LTA。最高结晶度达到 82%。所获得的沸石 LTA 具有优异的镉（II）离子交换能力。利用动态模拟提出了沸石 LTA α 和 β 笼中 Cd2⁺、Ni2⁺、Co2⁺ 和 Fe2⁺离子的吸附机理。该机制支持所有的实验结果，特别是对于 LTA- Cd2⁺，Cd2⁺ 离子主要分布在 α 和 β 笼中，在 α 笼中分布更密集，这表明由于其几何和电子环境，Cd2⁺ 离子对这些位点有强烈的偏好。所制备的沸石 LTA 具有成功去除镉（II）的能力，这肯定了它在环境修复行业中作为一种高效材料的实用性。

{"title":"Dynamic simulation-driven analysis of cadmium, nickel, cobalt, and iron adsorption mechanisms in zeolite LTA synthesized from bentonite","authors":"Imad El Bojaddayni , Youssef El Ouardi , Mohammed Elkabous , Nafea Achalhi , Alharith Yousuf , Yasser Karzazi , Abdelkrim Ouammou , Sami Virolainen","doi":"10.1016/j.micromeso.2024.113433","DOIUrl":"10.1016/j.micromeso.2024.113433","url":null,"abstract":"<div><div>A practical and cost-effective method was successfully developed for synthesizing high-performance zeolite LTA from bentonite clay by fine-tuning activation steps and crystallization parameters. The optimal synthesis conditions and crystallization mechanism were investigated. The synthesized zeolites were characterized using XRD, FTIR, and SEM-EDS techniques. The results highlight the significant influence of factors such as crystallization temperature, duration, and the effect of sodium hydroxide concentration on the formation of zeolites. Optimal conditions set at a crystallization temperature of 97 °C, duration of 24 h, and NaOH concentration of 4M yielded pure zeolite LTA, boasting high crystallinity levels. Achieving a peak crystallinity of 82 %. The obtained zeolite LTA showed an exceptional Cd (II) ion exchange capacity. A mechanism involving adsorption of Cd<sup>2</sup>⁺, Ni<sup>2</sup>⁺, Co<sup>2</sup>⁺, and Fe<sup>2</sup>⁺ ions in zeolite LTA at the α and β-cages has been proposed using dynamic simulation. This mechanism supports all experimental results, in particular for LTA- Cd<sup>2</sup>⁺, Cd<sup>2</sup>⁺ ions are predominantly distributed in both α and β-cages, with a denser distribution in the α-cages, indicating a strong preference for these sites due to their geometric and electronic environment. The resulted zeolite LTA demonstrated ability for successful Cd (II) removal, affirming its utility as an efficient material in environmental remediation industries.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113433"},"PeriodicalIF":4.8,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142724094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

xPd100-xCu/UiO-66-NH2 catalysts for selective 5-hydroxymethylfurfural reduction 用于选择性还原 5-羟甲基糠醛的 xPd100-xCu/UiO-66-NH2 催化剂

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-11-22 DOI: 10.1016/j.micromeso.2024.113432

Denis P. Morilov , Konstantin L. Timofeev , Aleksandra G. Golubovskaya , Olga A. Stonkus , Tamara S. Kharlamova

The present work is focused on a strategy to regulate the properties of monometallic Pd and bimetallic PdCu catalysts for selective 5-hydroxymethylfurfural (HMF) reduction via the interaction with the functional groups of the NH₂-modified Zr-based metal-organic frameworks (Zr-MOFs). xPd100-xCu/UiO-66-NH₂-X catalysts with different fractions of amino terephthalate linkers as well as Pd and Cu metals (x and 100-x, respectively) in bimetallic composition are prepared with impregnation reduction technique. The obtained samples are studied using a complex of methods, including XRD, low-temperature nitrogen adsorption, IR spectroscopy, and CO pulsed chemisorption. The effect of NH₂ groups on the adsorption properties of the Zr-MOFs towards Pd and Cu precursors and on Pd and PdCu species formation in xPd100-xCu/UiO-66-NH₂-X catalysts is considered. The formation of active particles at various stages of catalyst formation is studied in detail. 50 % fraction of NH₂ linkers is found optimal for the formation of active and selective mono- and bimetallic CuPd catalysts, while 100 % fraction significantly reduces the activity of the samples due to the strong interaction of active Pd species with the support and does not allow the formation of bimetallic catalysts.

本研究的重点是通过与 NH2 改性 Zr 基金属有机框架（Zr-MOFs）官能团的相互作用，调节用于选择性还原 5-羟甲基糠醛（HMF）的单金属 Pd 和双金属 PdCu 催化剂的性能。采用浸渍还原技术制备了 xPd100-xCu/UiO-66-NH2-X 催化剂，其中含有不同比例的对苯二甲酸氨基连接体以及双金属成分中的钯和铜金属（分别为 x 和 100-x）。研究采用了多种方法，包括 XRD、低温氮吸附、红外光谱和 CO 脉冲化学吸附。研究考虑了 NH2 基团对 Zr-MOFs 对 Pd 和 Cu 前驱体的吸附特性以及对 xPd100-xCu/UiO-66-NH2-X 催化剂中 Pd 和 PdCu 物种形成的影响。详细研究了催化剂形成过程中各个阶段活性颗粒的形成。研究发现，50% 的 NH2 链接剂是形成活性和选择性单金属和双金属铜钯催化剂的最佳成分，而 100% 的 NH2 链接剂会显著降低样品的活性，因为活性钯物种会与载体发生强烈的相互作用，并且无法形成双金属催化剂。

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引用次数: 0

Waste-to-resource strategy through green synthesis of PET-derived metal-organic frameworks for efficient photocatalytic dye degradation 通过绿色合成 PET 衍生的金属有机框架实现高效光催化染料降解的变废为宝战略

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-11-21 DOI: 10.1016/j.micromeso.2024.113431

Fang-yu Liang , Yi-Hao Chen , Hsiu-Wei Huang , Yen-Chang Chen , Po-Jung Huang

Wastewater contaminated with dyes poses significant environmental and health hazards, including oxygen depletion and carcinogenesis. Photocatalytic technology offers a sustainable and efficient solution by harnessing abundant solar energy to drive chemical reactions, making it a cost-effective method for water treatment. Metal-Organic Frameworks (MOFs), known for their high surface area, porosity, and chemical tunability, are particularly promising materials for such applications. In this study, we developed a green synthesis method to repurpose polyethylene terephthalate (PET) bottles into terephthalic acid, which was then used to synthesize PET-MIL-101(Cr) (denoted as PM-101(Cr)). The synthesis process avoids the use of organic solvents such as HF or DMF to prevent secondary pollution. Further modification of PM-101(Cr) through nitration produced PET-NO₂-MIL-101(Cr) (PO-101(Cr)), which was subsequently reduced to form amine-functionalized PET-NH₂-MIL-101(Cr) (PH-101(Cr)). PH-101(Cr) demonstrated a dye removal efficiency of over 95 % within 4 h of blue light irradiation, surpassing the performance of PM-101(Cr). Additionally, after four catalytic cycles, PH-101(Cr) maintained a reduction efficiency above 95 % for 6 h, indicating its robust potential for effective dye treatment. In summary, PH-101(Cr) efficiently degrades methylene blue dye under blue LED light, achieving both waste recycling and environmental remediation for improved sustainability.

被染料污染的废水会对环境和健康造成严重危害，包括耗氧和致癌。光催化技术利用丰富的太阳能驱动化学反应，提供了一种可持续的高效解决方案，是一种经济有效的水处理方法。金属有机框架（MOFs）以其高比表面积、多孔性和化学可调性而著称，是此类应用中特别有前景的材料。在本研究中，我们开发了一种将聚对苯二甲酸乙二醇酯（PET）瓶转化为对苯二甲酸的绿色合成方法，然后利用对苯二甲酸合成 PET-MIL-101(Cr)（简称 PM-101(Cr)）。合成过程避免使用 HF 或 DMF 等有机溶剂，以防止二次污染。通过硝化进一步改性 PM-101(Cr)，生成 PET-NO2-MIL-101(Cr) (PO-101(Cr))，随后将其还原成胺功能化 PET-NH2-MIL-101(Cr) (PH-101(Cr))。PH-101(Cr) 在蓝光照射 4 小时内的染料去除率超过 95%，超过 PM-101(Cr)。此外，经过四次催化循环后，PH-101(Cr) 的还原效率在 6 小时内保持在 95% 以上，这表明它具有有效处理染料的强大潜力。总之，PH-101(Cr) 可在蓝色 LED 光下高效降解亚甲基蓝染料，实现废物回收和环境修复，提高可持续性。

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引用次数: 0

Hierarchically ordered truncated single crystal mesoporous ZIF-8 as a solid platform for lipase immobilization 作为脂肪酶固定化固体平台的分层有序截短单晶介孔 ZIF-8

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-11-21 DOI: 10.1016/j.micromeso.2024.113430

Yang Zhou , Zhenzhu xia , Frank Peprah Addai , Jinping Chen , Chengxiang Feng , Zongjian Zhen , Juan Han , Feng Lin , Zhirong Wang , Yun Wang

Most pristine metal organic frameworks (MOFs) are inherently microporous. To introduce desired porosity for easy enzyme infiltration and immobilization, polystyrene spheres was used as sacrificial template to design hierarchical ordered micro-mesoporous truncated single-crystalline ZIF-8 (SOM-ZIF-8). The surface area and pore diameter of the SOM-ZIF-8 were 821 m²/g and 7.09 nm which changed to 669 m²/g and 4.98 nm respectively, after lipase immobilization, suggesting the pores and surface of the SOM-ZIF-8 served as binding sites for the enzyme, and could reach a loading capacity of 134 mg/g after 24 h. The optimal conditions for achieving maximum lipase activity for free LipaseELP, ZIF-8@LipaseELP and SOM-ZIF-8@LipaseELP were pH 7.8 at 45 °C, and maintained 33.67 %, 45.6 % and 57.78 % residual activity after incubation at 80 °C for 2 h. The specific activity towards tributyrin and p-nitrophenyl acetate were observed to be SOM-ZIF-8@LipaseELP (0.25 and 45.85 U/mg) compared to ZIF-8@LipaseELP (0.211 and 43.62 U/mg) and LipaseELP (0.179 and 41.09 U/mg) respectively. The SOM-ZIF-8@LipaseELP could further be recovered and reused for 9 rounds while maintaining 73.8 % of its original activity. This study demonstrates that introducing mesoporous structures into ZIF-8 could improve its binding enzyme property for enhanced hydrolytic function.

大多数原始金属有机框架（MOFs）本身都具有微孔。为了引入所需的多孔性以方便酶的渗透和固定，我们使用聚苯乙烯球作为牺牲模板，设计出了分层有序的微多孔截短单晶 ZIF-8 （SOM-ZIF-8）。脂肪酶固定后，SOM-ZIF-8 的表面积和孔径分别为 821 m2/g 和 7.09 nm，而脂肪酶固定后分别变为 669 m2/g 和 4.98 nm。与 ZIF-8@LipaseELP （0.211 和 43.62 U/mg ）和 LipaseELP （0.179 和 41.09 U/mg ）相比，SOM-ZIF-8@LipaseELP 对三丁炔和对硝基苯乙酸的特异性活性分别为 0.25 和 45.85 U/mg 。SOM-ZIF-8@LipaseELP 还可以回收并重复使用 9 轮，同时保持其 73.8% 的原始活性。这项研究表明，在 ZIF-8 中引入介孔结构可以改善其结合酶的特性，从而增强水解功能。

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引用次数: 0