Pub Date : 2025-11-03DOI: 10.1016/j.micromeso.2025.113910
Nanting Qiu , Zhihao Wei , Jinjie Sun , Heyang Sun , Meng Zhang , Yaorui Li
This study reports the successful modification of all-silica ZSM-5 zeolite through the grafting of an amide-containing ligand (diglycolamide, DGA), to form a novel composite material ZSM-5-DGA. Characterization results confirm the successful grafting of DGA onto the zeolite framework while preserving the crystalline structural integrity of the original ZSM-5. Adsorption experiments reveal that ZSM-5-DGA exhibits excellent Eu(Ⅲ) extraction performance under acidic conditions, reaching a maximum equilibrium adsorption capacity of 74.79 mg/g. The adsorption behavior follows the pseudo-second-order kinetic model and the Langmuir isotherm model, indicating that chemisorption dominated by complexation is the dominant mechanism. Moreover, ZSM-5-DGA demonstrates high selectivity for Eu(Ⅲ) even in the presence of competing ions and maintains excellent recyclability. These results highlight the significant potential of ZSM-5-DGA for the selectively removing trivalent radioactive nuclides from high-level radioactive waste solutions.
{"title":"Amido podands functionalized all-silica ZSM-5 zeolite for removal of Eu(Ⅲ) from acid solution","authors":"Nanting Qiu , Zhihao Wei , Jinjie Sun , Heyang Sun , Meng Zhang , Yaorui Li","doi":"10.1016/j.micromeso.2025.113910","DOIUrl":"10.1016/j.micromeso.2025.113910","url":null,"abstract":"<div><div>This study reports the successful modification of all-silica ZSM-5 zeolite through the grafting of an amide-containing ligand (diglycolamide, DGA), to form a novel composite material ZSM-5-DGA. Characterization results confirm the successful grafting of DGA onto the zeolite framework while preserving the crystalline structural integrity of the original ZSM-5. Adsorption experiments reveal that ZSM-5-DGA exhibits excellent Eu(Ⅲ) extraction performance under acidic conditions, reaching a maximum equilibrium adsorption capacity of 74.79 mg/g. The adsorption behavior follows the pseudo-second-order kinetic model and the Langmuir isotherm model, indicating that chemisorption dominated by complexation is the dominant mechanism. Moreover, ZSM-5-DGA demonstrates high selectivity for Eu(Ⅲ) even in the presence of competing ions and maintains excellent recyclability. These results highlight the significant potential of ZSM-5-DGA for the selectively removing trivalent radioactive nuclides from high-level radioactive waste solutions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113910"},"PeriodicalIF":4.7,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145428735","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}
Pub Date : 2025-11-01DOI: 10.1016/j.micromeso.2025.113920
Hui-Dong Zhang , Xiao-Dong Li , Yan-Yu Xie , Xiu-Ying Liu , Jing-Xin Yu , Jun-Fei Wang
This study employs high-throughput computational screening to systematically assess 247 structures of pure silica zeolite structures, aiming to identify materials with superior efficacy for the selective adsorption of the greenhouse gas sulfur hexafluoride (SF6) from SF6/N2 mixtures. Utilizing Grand Canonical Monte Carlo (GCMC) simulations, we investigated the SF6/N2 adsorption behavior of these zeolite structures under three distinct operational modes: vacuum swing adsorption (VSA), pressure swing adsorption (PSA), and temperature swing adsorption (TSA). Two assessment metrics, namely the adsorbent performance score (APS) and the regenerability (R%), are introduced to evaluate the separation efficiency of zeolite structures and to underscore the critical importance of material regenerability in practical applications. The results demonstrate significant correlations between the key structural parameters of zeolites, including largest cavity diameter (LCD), accessible surface area (ASA), pore occupied accessible volume (POAV) and porosity, and the adsorption capacity, adsorption heat and selectivity for SF6. The screening results identified several zeolite structures, including UOV, IWW, SAO, and BPH, that exhibited exceptional performance in VSA, PSA, and TSA processes, characterized by their high adsorption capacity and selectivity. Furthermore, the random forest model was developed to evaluate the importance of the structural features in determining the SF6/N2 separation performance. A multiple linear regression model was also established to quantify the correlation between the SF6 adsorption capacity and structural parameters. We anticipate that this study can provide some theoretical insights to guide the experimental development of zeolite structures for SF6 separation.
{"title":"Machine learning assisted high-throughput computational investigation of SF6/N2 separation in pure silica zeolite structures","authors":"Hui-Dong Zhang , Xiao-Dong Li , Yan-Yu Xie , Xiu-Ying Liu , Jing-Xin Yu , Jun-Fei Wang","doi":"10.1016/j.micromeso.2025.113920","DOIUrl":"10.1016/j.micromeso.2025.113920","url":null,"abstract":"<div><div>This study employs high-throughput computational screening to systematically assess 247 structures of pure silica zeolite structures, aiming to identify materials with superior efficacy for the selective adsorption of the greenhouse gas sulfur hexafluoride (SF<sub>6</sub>) from SF<sub>6</sub>/N<sub>2</sub> mixtures. Utilizing Grand Canonical Monte Carlo (GCMC) simulations, we investigated the SF<sub>6</sub>/N<sub>2</sub> adsorption behavior of these zeolite structures under three distinct operational modes: vacuum swing adsorption (VSA), pressure swing adsorption (PSA), and temperature swing adsorption (TSA). Two assessment metrics, namely the adsorbent performance score (APS) and the regenerability (R%), are introduced to evaluate the separation efficiency of zeolite structures and to underscore the critical importance of material regenerability in practical applications. The results demonstrate significant correlations between the key structural parameters of zeolites, including largest cavity diameter (LCD), accessible surface area (ASA), pore occupied accessible volume (POAV) and porosity, and the adsorption capacity, adsorption heat and selectivity for SF<sub>6</sub>. The screening results identified several zeolite structures, including UOV, IWW, SAO, and BPH, that exhibited exceptional performance in VSA, PSA, and TSA processes, characterized by their high adsorption capacity and selectivity. Furthermore, the random forest model was developed to evaluate the importance of the structural features in determining the SF<sub>6</sub>/N<sub>2</sub> separation performance. A multiple linear regression model was also established to quantify the correlation between the SF<sub>6</sub> adsorption capacity and structural parameters. We anticipate that this study can provide some theoretical insights to guide the experimental development of zeolite structures for SF<sub>6</sub> separation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113920"},"PeriodicalIF":4.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145465011","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}
Pub Date : 2025-10-31DOI: 10.1016/j.micromeso.2025.113922
Qianping Wang
Chiral covalent organic frameworks (chiral COFs) have emerged as a unique subclass of crystalline porous materials that integrate ordered pore structures, high surface area, and tunable chiral environments, enabling highly efficient and recyclable heterogeneous asymmetric catalysis. Their modular architectures allow precise control over pore size, shape, and functionality, facilitating enhanced stereoscopic control through confinement effects and specific host–guest interactions. This review summarizes recent advances in chiral COFs synthesis, including post-synthetic modification, bottom–up (direct) synthesis, and template-induced synthesis, with emphasis on the correlation between pore structure engineering and chiral microenvironment formation. Representative catalytic applications—such as Michael addition, aldol reactions, α-functionalization of aldehydes, and photocatalytic transformations—are critically discussed in terms of catalytic activity, enantioselectivity, and stability. Structure–property–performance relationships are highlighted to elucidate how pore geometry, accessible surface area, and functional site distribution influence stereochemical outcomes. Finally, current challenges and future perspectives are presented, including scalable synthesis, pore structure optimization, and the integration of computational modeling for rational catalyst design. This review aims to provide a comprehensive reference for the development of chiral COFs as advanced porous catalysts for sustainable asymmetric transformations.
{"title":"Research progress on asymmetric catalysis using chiral covalent organic frameworks","authors":"Qianping Wang","doi":"10.1016/j.micromeso.2025.113922","DOIUrl":"10.1016/j.micromeso.2025.113922","url":null,"abstract":"<div><div>Chiral covalent organic frameworks (chiral COFs) have emerged as a unique subclass of crystalline porous materials that integrate ordered pore structures, high surface area, and tunable chiral environments, enabling highly efficient and recyclable heterogeneous asymmetric catalysis. Their modular architectures allow precise control over pore size, shape, and functionality, facilitating enhanced stereoscopic control through confinement effects and specific host–guest interactions. This review summarizes recent advances in chiral COFs synthesis, including post-synthetic modification, bottom–up (direct) synthesis, and template-induced synthesis, with emphasis on the correlation between pore structure engineering and chiral microenvironment formation. Representative catalytic applications—such as Michael addition, aldol reactions, α-functionalization of aldehydes, and photocatalytic transformations—are critically discussed in terms of catalytic activity, enantioselectivity, and stability. Structure–property–performance relationships are highlighted to elucidate how pore geometry, accessible surface area, and functional site distribution influence stereochemical outcomes. Finally, current challenges and future perspectives are presented, including scalable synthesis, pore structure optimization, and the integration of computational modeling for rational catalyst design. This review aims to provide a comprehensive reference for the development of chiral COFs as advanced porous catalysts for sustainable asymmetric transformations.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113922"},"PeriodicalIF":4.7,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145428734","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}
Bacterial infection has been posing a serious threat to the health of the global population and has led to millions of deaths all over the world. However, developing anti-bacterial nanomaterials with excellent bactericidal and/or bacteriostatic ability is still highly desirable. Here, we presented a simple and effective method to prepare natural, sustainable anti-bacterial material by combining curcumin, chondroitin sulfate, and mesoporous silica nanoparticles. This nanoparticle could exhibit good pH-sensitive fluorescence and anti-bacterial performances against E. coli and S. aureus. Furthermore, this nanoparticle could endow the coating with strong fluorescence and good pH-sensitive fluorescence. The prepared nanoparticles prove that it has ideal performances for advanced natural, sustainable anti-bacterial and anti-counterfeiting materials.
{"title":"Natural sustainable curcumin/chondroitin-coated fluorescent mesoporous silica nanoparticles for anti-bacterial and anti-counterfeiting","authors":"Yichun Chen , Minghui Xie , Yue Pei, Hui Ye, Wantong Lin, Wenqi Kuang, Xu Wu, Xiubin Xu","doi":"10.1016/j.micromeso.2025.113917","DOIUrl":"10.1016/j.micromeso.2025.113917","url":null,"abstract":"<div><div>Bacterial infection has been posing a serious threat to the health of the global population and has led to millions of deaths all over the world. However, developing anti-bacterial nanomaterials with excellent bactericidal and/or bacteriostatic ability is still highly desirable. Here, we presented a simple and effective method to prepare natural, sustainable anti-bacterial material by combining curcumin, chondroitin sulfate, and mesoporous silica nanoparticles. This nanoparticle could exhibit good pH-sensitive fluorescence and anti-bacterial performances against <em>E. coli</em> and <em>S. aureus</em>. Furthermore, this nanoparticle could endow the coating with strong fluorescence and good pH-sensitive fluorescence. The prepared nanoparticles prove that it has ideal performances for advanced natural, sustainable anti-bacterial and anti-counterfeiting materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113917"},"PeriodicalIF":4.7,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145465010","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}
Pub Date : 2025-10-30DOI: 10.1016/j.micromeso.2025.113921
L.F. de Sousa Lima , N.D. Santina Mohallem , D.D. Athayde , E.P. da Silva , S.L. Pereira da Silva , C. de Lima Ribeiro , G. Magalhães dos Santos , A.C. Britto de Faria , H.X. Rodrigues , E.J. Alexandrino dos Santos , R.A. Faria Alves , L.A. Ribeiro Junior , R. Nunes de Souza , C. Martins Aiube , A.M. Almeida Silva
The CO2/N2 capture performance of SAPO-34 zeolites is strongly influenced by microstructural and textural features, which are determined by the synthesis method. Here, experimental characterization and molecular simulations were combined to investigate SAPO-34 synthesized via hydrothermal and microwave routes. Hydrothermal synthesis (72 h) yielded highly crystalline materials with uniform morphology, enhanced microporosity, and a BET surface area of 769 m2/g, resulting in a CO2 uptake of 110.5 mg/g at 303 K and 100 kPa. MAS-NMR data indicated that low levels of pentacoordinated Al and higher tetrahedral P contents favor CHA crystallization and high surface area. GCMC and MD simulations reproduced the experimental isotherms, identified preferential CO2 adsorption sites in CHA cages, and confirmed that microporous models enhance confinement and selectivity. This integrated approach highlights the role of microporosity engineering in optimizing CO2 capture, guiding the design of efficient zeolite-based adsorbents.
{"title":"Microstructural and textural control of CO2/N2 adsorption in SAPO-34 zeolites: Insights from a comparative study between hydrothermal and microwave methods and molecular modeling","authors":"L.F. de Sousa Lima , N.D. Santina Mohallem , D.D. Athayde , E.P. da Silva , S.L. Pereira da Silva , C. de Lima Ribeiro , G. Magalhães dos Santos , A.C. Britto de Faria , H.X. Rodrigues , E.J. Alexandrino dos Santos , R.A. Faria Alves , L.A. Ribeiro Junior , R. Nunes de Souza , C. Martins Aiube , A.M. Almeida Silva","doi":"10.1016/j.micromeso.2025.113921","DOIUrl":"10.1016/j.micromeso.2025.113921","url":null,"abstract":"<div><div>The CO<sub>2</sub>/N<sub>2</sub> capture performance of SAPO-34 zeolites is strongly influenced by microstructural and textural features, which are determined by the synthesis method. Here, experimental characterization and molecular simulations were combined to investigate SAPO-34 synthesized via hydrothermal and microwave routes. Hydrothermal synthesis (72 h) yielded highly crystalline materials with uniform morphology, enhanced microporosity, and a BET surface area of 769 m<sup>2</sup>/g, resulting in a CO<sub>2</sub> uptake of 110.5 mg/g at 303 K and 100 kPa. MAS-NMR data indicated that low levels of pentacoordinated Al and higher tetrahedral P contents favor CHA crystallization and high surface area. GCMC and MD simulations reproduced the experimental isotherms, identified preferential CO<sub>2</sub> adsorption sites in CHA cages, and confirmed that microporous models enhance confinement and selectivity. This integrated approach highlights the role of microporosity engineering in optimizing CO<sub>2</sub> capture, guiding the design of efficient zeolite-based adsorbents.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113921"},"PeriodicalIF":4.7,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145518287","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}
Pub Date : 2025-10-30DOI: 10.1016/j.micromeso.2025.113919
Tzonka Mineva , Karima Ata , Shadi Al-Nahari , Vincent Sarou-Kanian , Pierre Florian , Bruno Alonso
We undertook a detailed NMR characterization of the prototypical host-guest zeolite TPA-F-Silicalite-1, made of tetrapropylammonium cations (TPA), fluoride and the MFI silica framework. The use of a high magnetic field (B0 = 20 T) and very fast MAS frequency (νMAS = 100 kHz) greatly improves the 1H resolution in the related 1D spectrum and 2D 1H–1H and 1H-13C correlation spectra, enabling eight distinct 1H peaks to be identified, whereas TPA shows only three peaks in solution NMR. We also analyzed a 2D 1H-29Si NMR correlation spectrum on a 29Si labelled sample allowing to decipher the location of the propyl (Pr) arms in MFI channels. In parallel, we conducted complementary Density Functional Theory calculations using two approaches: geometry optimization and ab initio molecular dynamics (AIMD) based on Born-Oppenheimer molecular dynamics (BOMD). On the basis of the highly resolved experimental NMR spectra together with the BOMD calculated NMR parameters, new sets of 1H and 13C NMR peaks were assigned. The BOMD simulation (5.2 ps trajectory length) allows further analysis of the structure and dynamics of the TPA guest, confined in the Silicalite-1 host. From the obtained results, there is no evidence of any major restriction of H motions (C-H stretching, H-C-H bending, methyl rotation) due to sterically constrained Pr arms located in MFI zigzag channels. We found however that Pr arms in zigzag channels remain in trans conformation, while the conformation of Pr arms in straight channels alternates between trans and gauche.
{"title":"New advances in the understanding of host-guest zeolite materials through NMR experimental and theoretical approaches: the TPA-F-Silicalite-1 case","authors":"Tzonka Mineva , Karima Ata , Shadi Al-Nahari , Vincent Sarou-Kanian , Pierre Florian , Bruno Alonso","doi":"10.1016/j.micromeso.2025.113919","DOIUrl":"10.1016/j.micromeso.2025.113919","url":null,"abstract":"<div><div>We undertook a detailed NMR characterization of the prototypical host-guest zeolite TPA-F-Silicalite-1, made of tetrapropylammonium cations (TPA), fluoride and the MFI silica framework. The use of a high magnetic field (B<sub>0</sub> = 20 T) and very fast MAS frequency (ν<sub>MAS</sub> = 100 kHz) greatly improves the <sup>1</sup>H resolution in the related 1D spectrum and 2D <sup>1</sup>H–<sup>1</sup>H and <sup>1</sup>H-<sup>13</sup>C correlation spectra, enabling eight distinct <sup>1</sup>H peaks to be identified, whereas TPA shows only three peaks in solution NMR. We also analyzed a 2D <sup>1</sup>H-<sup>29</sup>Si NMR correlation spectrum on a <sup>29</sup>Si labelled sample allowing to decipher the location of the propyl (Pr) arms in MFI channels. In parallel, we conducted complementary Density Functional Theory calculations using two approaches: geometry optimization and <em>ab initio</em> molecular dynamics (AIMD) based on Born-Oppenheimer molecular dynamics (BOMD). On the basis of the highly resolved experimental NMR spectra together with the BOMD calculated NMR parameters, new sets of <sup>1</sup>H and <sup>13</sup>C NMR peaks were assigned. The BOMD simulation (5.2 ps trajectory length) allows further analysis of the structure and dynamics of the TPA guest, confined in the Silicalite-1 host. From the obtained results, there is no evidence of any major restriction of H motions (C-H stretching, H-C-H bending, methyl rotation) due to sterically constrained Pr arms located in MFI zigzag channels. We found however that Pr arms in zigzag channels remain in trans conformation, while the conformation of Pr arms in straight channels alternates between trans and gauche.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113919"},"PeriodicalIF":4.7,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425238","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}
P-La modification has been industrially demonstrated as a successful approach to enhance the hydrothermal stability of ZSM-5 zeolites. ZSM-5 is widely used as the catalytic component in processes such as fluid catalytic cracking (FCC) and methanol-to-propylene (MTP), which involve harsh reaction/regeneration conditions. With the P-La modified ZSM-5 as the research subject, the interactions among phosphorus, lanthanum, and ZSM-5 during modification and their influence on catalytic performance were systematically investigated through characterization methods including XRD, 27Al, 29Si, 31P MAS NMR, and 2D31P{27Al} D-HMQC MAS NMR. The mechanism on enhancement of hydrothermal stability of ZSM-5 zeolite through interactions among P, La and ZSM-5 was proposed. Specifically, during the modification, phosphorus and lanthanum tends to form LaPO4 and lanxthanum polyphosphate species. This P-La interaction not only suppresses blockage of channels and damage on framework of ZSM-5 caused by lanthanum, but also significantly reduces the degree of phosphorus polymerization, facilitating the re-dispersion of phosphorus during hydrothermal treatment and ultimately strengthening the interaction between phosphorus and ZSM-5. Directed by the mechanism, the P-La modified approach was optimized, and the subsequent impregnation of P and La onto ZSM-5 strategy was developed to further improve the hydrothermal stability of ZSM-5.
P-La改性是提高ZSM-5沸石水热稳定性的一种成功的工业方法。ZSM-5作为催化组分广泛应用于催化裂化（FCC）和甲醇制丙烯（MTP）等反应/再生条件苛刻的工艺中。以P-La改性ZSM-5为研究对象，通过XRD、27Al、29Si、31P MAS NMR、2D31P{27Al} D-HMQC MAS NMR等表征方法，系统研究了改性过程中磷、镧、ZSM-5之间的相互作用及其对催化性能的影响。提出了P、La和ZSM-5相互作用增强ZSM-5沸石水热稳定性的机理。具体来说，在改性过程中，磷和镧倾向于形成LaPO4和多磷酸镧。这种P-La相互作用不仅抑制了镧对ZSM-5通道的堵塞和对骨架的破坏，而且显著降低了磷的聚合程度，促进了水热处理过程中磷的再分散，最终加强了磷与ZSM-5的相互作用。针对这一机理，对P-La改性方法进行了优化，并制定了后续P和La浸渍ZSM-5的策略，进一步提高ZSM-5的水热稳定性。
{"title":"Rational design of P-La modified ZSM-5 from perspectives on interactions among La P and ZSM-5","authors":"Ruihan Yang, Ying Ouyang, Longxiao Yang, Jianqiang Liu, Enhui Xing, Yibin Luo, Xingtian Shu","doi":"10.1016/j.micromeso.2025.113918","DOIUrl":"10.1016/j.micromeso.2025.113918","url":null,"abstract":"<div><div>P-La modification has been industrially demonstrated as a successful approach to enhance the hydrothermal stability of ZSM-5 zeolites. ZSM-5 is widely used as the catalytic component in processes such as fluid catalytic cracking (FCC) and methanol-to-propylene (MTP), which involve harsh reaction/regeneration conditions. With the P-La modified ZSM-5 as the research subject, the interactions among phosphorus, lanthanum, and ZSM-5 during modification and their influence on catalytic performance were systematically investigated through characterization methods including XRD, <sup>27</sup>Al, <sup>29</sup>Si, <sup>31</sup>P MAS NMR, and 2D<sup>31</sup>P{<sup>27</sup>Al} D-HMQC MAS NMR. The mechanism on enhancement of hydrothermal stability of ZSM-5 zeolite through interactions among P, La and ZSM-5 was proposed. Specifically, during the modification, phosphorus and lanthanum tends to form LaPO<sub>4</sub> and lanxthanum polyphosphate species. This P-La interaction not only suppresses blockage of channels and damage on framework of ZSM-5 caused by lanthanum, but also significantly reduces the degree of phosphorus polymerization, facilitating the re-dispersion of phosphorus during hydrothermal treatment and ultimately strengthening the interaction between phosphorus and ZSM-5. Directed by the mechanism, the P-La modified approach was optimized, and the subsequent impregnation of P and La onto ZSM-5 strategy was developed to further improve the hydrothermal stability of ZSM-5.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113918"},"PeriodicalIF":4.7,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145465009","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}
Pub Date : 2025-10-30DOI: 10.1016/j.micromeso.2025.113915
Lili Gong, Ju Bai, Can Wang, Zhenyuan Li, Linglong Shan
Two-dimensional (2D) metal-organic framework (MOF) nanosheets are promising fillers for gas separation membranes, owing to their high aspect ratios and tunable pore architectures. Realizing their full application potential requires precise control over nanosheet morphology and sizes to optimize membrane performance. This work employs crystal growth kinetics modulation to tailor the morphology and size of ZIF-67-based nanosheets incorporated into mixed matrix membranes (MMMs) targeting superior CO2/CH4 separation. Strategy (i): Adjusting early-stage nucleation kinetics yielded two distinct ZIF-L nanosheet types: disk-like (ZIF-L-I) and leaf-like (ZIF-L-II). ZIF-L-II, synthesized with higher ligand molar ratio, possessed larger lateral dimensions and more favorable pore characteristics, significantly enhancing gas separation. Strategy (ii): Amino-functionalized ionic liquid (IL) was introduced to further modulate the size of ZIF-L-II nanosheets. The IL's amino groups served as capping agents by coordinating preferentially with Co ions, restricting framework extension without altering crystallinity. The ILs loading amount dictated the final nanosheet size, but did not alter their crystalline phase. Critically, the IL also exhibits affinity for CO2, augmenting its transport. At 48 % IL addition, the CO2 permeability of the 10 wt% IL-ZIF-L-II/PI membrane surged from 289 Barrer to 493 Barrer, without significant selectivity loss. The synergistic combination of kinetically-controlled synthesis (yielding larger and leaf-like nanosheets) and IL-mediated size regulation (providing both capping and CO2-philic functions) resulted in a 70 % enhancement in CO2 permeability.
二维（2D）金属有机框架（MOF）纳米片由于其高长宽比和可调节的孔隙结构，是很有前途的气体分离膜填料。为了充分发挥其应用潜力，需要精确控制纳米片的形态和尺寸，以优化膜的性能。这项工作采用晶体生长动力学调节来定制基于zif -67的纳米片的形态和尺寸，并将其结合到混合基质膜（MMMs）中，以实现卓越的CO2/CH4分离。策略(i)：调整早期成核动力学产生两种不同的ZIF-L纳米片类型：圆盘状（ZIF-L- i）和叶状（ZIF-L- ii）。配体摩尔比较高的ZIF-L-II具有更大的横向尺寸和更有利的孔隙特征，显著提高了气体分离效果。策略（ii）：引入氨基功能化离子液体（IL）来进一步调节ZIF-L-II纳米片的尺寸。IL的氨基通过优先与Co离子配位作为封盖剂，在不改变结晶度的情况下限制了框架的延伸。il的装载量决定了最终纳米片的尺寸，但没有改变它们的晶相。关键的是，IL也表现出对二氧化碳的亲和力，增加了它的运输。当IL添加量为48%时，10 wt% IL- zif - l - ii /PI膜的CO2渗透率从289 Barrer增加到493 Barrer，没有明显的选择性损失。动力学控制的合成（产生更大的叶状纳米片）和il介导的尺寸调节（提供封盖和亲二氧化碳功能）的协同组合导致二氧化碳渗透率提高了70%。
{"title":"Precisely tuning morphology and size of ZIF-67-based nanosheets in mixed matrix membranes for advanced CO2/CH4 separation","authors":"Lili Gong, Ju Bai, Can Wang, Zhenyuan Li, Linglong Shan","doi":"10.1016/j.micromeso.2025.113915","DOIUrl":"10.1016/j.micromeso.2025.113915","url":null,"abstract":"<div><div>Two-dimensional (2D) metal-organic framework (MOF) nanosheets are promising fillers for gas separation membranes, owing to their high aspect ratios and tunable pore architectures. Realizing their full application potential requires precise control over nanosheet morphology and sizes to optimize membrane performance. This work employs crystal growth kinetics modulation to tailor the morphology and size of ZIF-67-based nanosheets incorporated into mixed matrix membranes (MMMs) targeting superior CO<sub>2</sub>/CH<sub>4</sub> separation. Strategy (i): Adjusting early-stage nucleation kinetics yielded two distinct ZIF-L nanosheet types: disk-like (ZIF-L-I) and leaf-like (ZIF-L-II). ZIF-L-II, synthesized with higher ligand molar ratio, possessed larger lateral dimensions and more favorable pore characteristics, significantly enhancing gas separation. Strategy (ii): Amino-functionalized ionic liquid (IL) was introduced to further modulate the size of ZIF-L-II nanosheets. The IL's amino groups served as capping agents by coordinating preferentially with Co ions, restricting framework extension without altering crystallinity. The ILs loading amount dictated the final nanosheet size, but did not alter their crystalline phase. Critically, the IL also exhibits affinity for CO<sub>2</sub>, augmenting its transport. At 48 % IL addition, the CO<sub>2</sub> permeability of the 10 wt% IL-ZIF-L-II/PI membrane surged from 289 Barrer to 493 Barrer, without significant selectivity loss. The synergistic combination of kinetically-controlled synthesis (yielding larger and leaf-like nanosheets) and IL-mediated size regulation (providing both capping and CO<sub>2</sub>-philic functions) resulted in a 70 % enhancement in CO<sub>2</sub> permeability.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113915"},"PeriodicalIF":4.7,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425235","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}
Pub Date : 2025-10-30DOI: 10.1016/j.micromeso.2025.113909
Zixuan Ye , Qingwen Fan , Cheng Xiong , Dashan Wang , Rongbin Zhang , Runping Ye , Gang Feng
The synthesis of 2,6-dimethylnaphthalene (2,6-DMN) via the alkyl transfer reaction between 2-methylnaphthalene (2-MN) and C10 aromatic hydrocarbons (C10A) is cost-effective and exhibits excellent stability, making it a highly promising pathway. However, the conversion of 2-MN still requires improvement. In this work, a range of Ni-modified H-ZSM-12/Beta were synthesized and utilized in alkyl transfer reactions conducted under a hydrogen atmosphere. H-ZSM-12/Beta fully utilizes its pore channel space, exhibits predominantly weak acidity, and demonstrates enhanced catalytic performance compared to individual molecular sieves. The further introduction of Ni supports the microporous structure and precisely regulates the shape of the pore channels. Meanwhile, it promotes the hydrogen spillover effect and accelerates the replenishment of proton active sites, which substantially boosts the catalytic performance. The results indicate that H-ZSM-12/Beta achieved an average 2-MN conversion rate of 56.7 % in 6 h. The 5 % Ni/ZSM-12/Beta achieved an average 2-MN conversion rate of 62.8 % in 6 h. No significant deactivation was observed within 6 h of the reaction. Therefore, the catalyst exhibits significant potential for the alkyl-transfer synthesis of 2,6-DMN from 2-MN and C10A.
{"title":"Cocrystallized zeolites of Ni-modified H-ZSM-12/Beta catalysts enhancing the synthesis of 2,6-dimethylnaphthalene by transalkylation of C10 aromatics with 2-methylnaphthalene","authors":"Zixuan Ye , Qingwen Fan , Cheng Xiong , Dashan Wang , Rongbin Zhang , Runping Ye , Gang Feng","doi":"10.1016/j.micromeso.2025.113909","DOIUrl":"10.1016/j.micromeso.2025.113909","url":null,"abstract":"<div><div>The synthesis of 2,6-dimethylnaphthalene (2,6-DMN) via the alkyl transfer reaction between 2-methylnaphthalene (2-MN) and C<sub>10</sub> aromatic hydrocarbons (C<sub>10</sub>A) is cost-effective and exhibits excellent stability, making it a highly promising pathway. However, the conversion of 2-MN still requires improvement. In this work, a range of Ni-modified H-ZSM-12/Beta were synthesized and utilized in alkyl transfer reactions conducted under a hydrogen atmosphere. H-ZSM-12/Beta fully utilizes its pore channel space, exhibits predominantly weak acidity, and demonstrates enhanced catalytic performance compared to individual molecular sieves. The further introduction of Ni supports the microporous structure and precisely regulates the shape of the pore channels. Meanwhile, it promotes the hydrogen spillover effect and accelerates the replenishment of proton active sites, which substantially boosts the catalytic performance. The results indicate that H-ZSM-12/Beta achieved an average 2-MN conversion rate of 56.7 % in 6 h. The 5 % Ni/ZSM-12/Beta achieved an average 2-MN conversion rate of 62.8 % in 6 h. No significant deactivation was observed within 6 h of the reaction. Therefore, the catalyst exhibits significant potential for the alkyl-transfer synthesis of 2,6-DMN from 2-MN and C<sub>10</sub>A.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113909"},"PeriodicalIF":4.7,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145465008","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}
Pub Date : 2025-10-29DOI: 10.1016/j.micromeso.2025.113912
Michael Fischer , Daniel A. Chaney , Osasere Austine Uwumwonse , Erik Neumann , Iris Spieß , Christin Wiggers , Ella M. Schmidt
The aluminium phosphate framework materials, such as AlPO-5, exhibit an inherent structural flexibility due to the connectivity of their rigid tetrahedral building blocks. This structural flexibility is critical to their ability to accommodate a wide range of organic guest molecules and/or heteroatoms, where subtle distortions of the framework do not compromise the overall framework integrity. Here, we use a combination of single-crystal diffuse scattering and ab initio molecular dynamics simulations to understand the framework dynamics in AlPO-5. AlPO-5 adopts the AFI topology, where the average structure is typically described as a framework in which one of the Al-O-P bond angles approaches 180°. This configuration is considered both energetically unfavorable and unrealistic, creating a form of bond frustration that is alleviated by collective distortions that keep the Al- and P-tetrahedra rigid. Through a combination of synchrotron based diffuse X-ray scattering and ab initio molecular dynamic simulations we demonstrate that in the AlPO-5 framework these distortions are likely dynamic and the real structure dynamically transforms between different distorted states, which can be approximated by a three-fold superstructure along the -axis.
{"title":"Accessing dynamic disorder in AlPO4-5 with single crystal diffuse scattering and ab initio molecular dynamics simulations","authors":"Michael Fischer , Daniel A. Chaney , Osasere Austine Uwumwonse , Erik Neumann , Iris Spieß , Christin Wiggers , Ella M. Schmidt","doi":"10.1016/j.micromeso.2025.113912","DOIUrl":"10.1016/j.micromeso.2025.113912","url":null,"abstract":"<div><div>The aluminium phosphate framework materials, such as AlPO<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>-5, exhibit an inherent structural flexibility due to the connectivity of their rigid tetrahedral building blocks. This structural flexibility is critical to their ability to accommodate a wide range of organic guest molecules and/or heteroatoms, where subtle distortions of the framework do not compromise the overall framework integrity. Here, we use a combination of single-crystal diffuse scattering and <em>ab initio</em> molecular dynamics simulations to understand the framework dynamics in AlPO<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>-5. AlPO<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>-5 adopts the AFI topology, where the average structure is typically described as a framework in which one of the Al-O-P bond angles approaches 180°. This configuration is considered both energetically unfavorable and unrealistic, creating a form of bond frustration that is alleviated by collective distortions that keep the Al- and P-tetrahedra rigid. Through a combination of synchrotron based diffuse X-ray scattering and <em>ab initio</em> molecular dynamic simulations we demonstrate that in the AlPO<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>-5 framework these distortions are likely dynamic and the real structure dynamically transforms between different distorted states, which can be approximated by a three-fold superstructure along the <span><math><mi>c</mi></math></span>-axis.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113912"},"PeriodicalIF":4.7,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145428777","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}
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