Pub Date : 2025-03-04DOI: 10.1016/j.micromeso.2025.113577
Zehong Zhu , Qingxin Wu , Xueying Wang , Haiyang Zhang , Jian Li , Yanzhao Dong , Yongsheng Xu , Yunsheng Dai , Jinli Zhang
Here, the spiral mesoporous hydrothermal carbonaceous nanospheres (SMHNs) were designed and fabricated from pentose precursors to enhance gas diffusion in acetylene hydrochlorination. Through the optimization of hydrothermal conditions, the optimized SMCNs-800 material showcased the highest catalytic activity with an acetylene conversion of 77 % under the condition of GHSV (C2H2) = 30 h−1. The structural analysis indicated that the material with helical structure could provide larger pore sizes and abundant defect sites, exposing more active sites. The structure-activity relationship among acid-base properties of the catalyst surface, the adsorption-desorption capacity for the reactants and the catalytic activity jointly demonstrated that pyridine-N and -C=O could provide abundant basic sites for the adsorption and activation of H-Cl, thus accelerating the process of acetylene hydrochlorination reaction.
{"title":"Acetylene hydrochlorination catalyzed by N/O-doped spiral mesoporous carbonaceous nanospheres","authors":"Zehong Zhu , Qingxin Wu , Xueying Wang , Haiyang Zhang , Jian Li , Yanzhao Dong , Yongsheng Xu , Yunsheng Dai , Jinli Zhang","doi":"10.1016/j.micromeso.2025.113577","DOIUrl":"10.1016/j.micromeso.2025.113577","url":null,"abstract":"<div><div>Here, the spiral mesoporous hydrothermal carbonaceous nanospheres (SMHNs) were designed and fabricated from pentose precursors to enhance gas diffusion in acetylene hydrochlorination. Through the optimization of hydrothermal conditions, the optimized SMCNs-800 material showcased the highest catalytic activity with an acetylene conversion of 77 % under the condition of GHSV (C<sub>2</sub>H<sub>2</sub>) = 30 h<sup>−1</sup>. The structural analysis indicated that the material with helical structure could provide larger pore sizes and abundant defect sites, exposing more active sites. The structure-activity relationship among acid-base properties of the catalyst surface, the adsorption-desorption capacity for the reactants and the catalytic activity jointly demonstrated that pyridine-N and -C=O could provide abundant basic sites for the adsorption and activation of H-Cl, thus accelerating the process of acetylene hydrochlorination reaction.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113577"},"PeriodicalIF":4.8,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549142","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 : 2025-03-04DOI: 10.1016/j.micromeso.2025.113576
Taotao Lu , Hui Li , Yanping Zheng , Lei Shi , Rong Nie , Liang Zhao , Yanxing Qi
Pillar[5]arene, a novel class of pillar-shaped macrocyclic hosts, has demonstrated significant potential across diverse fields due to its symmetrical pillar-shaped structures, flexible functionalization, and unique host–guest interactions. Moreover, pillar[5]arene-based functional materials have garnered considerable interest owning to their unique topological and chemical structures, as well as their physicochemical properties. In this review, we discuss the exceptional properties of pillar[5]arene-based silicon materials. Specifically, we summarize the preparation of complex pillar[5]arene-based silicon materials and their applications in molecular recognition, chromatographic separation, adsorption and controllable release (including pH, electron, temperature, ions, gas, multiresponsive controlled release and osmotic release). Finally, we outline the future perspectives of pillar[5]arene chemistry. We anticipate that this review will serve as a valuable reference for researchers in the field and inspire new discoveries related to pillar[5]arene-based materials.
{"title":"Progress in pillar[5]arene-based silicon porous materials: From preparation to applications","authors":"Taotao Lu , Hui Li , Yanping Zheng , Lei Shi , Rong Nie , Liang Zhao , Yanxing Qi","doi":"10.1016/j.micromeso.2025.113576","DOIUrl":"10.1016/j.micromeso.2025.113576","url":null,"abstract":"<div><div>Pillar[5]arene, a novel class of pillar-shaped macrocyclic hosts, has demonstrated significant potential across diverse fields due to its symmetrical pillar-shaped structures, flexible functionalization, and unique host–guest interactions. Moreover, pillar[5]arene-based functional materials have garnered considerable interest owning to their unique topological and chemical structures, as well as their physicochemical properties. In this review, we discuss the exceptional properties of pillar[5]arene-based silicon materials. Specifically, we summarize the preparation of complex pillar[5]arene-based silicon materials and their applications in molecular recognition, chromatographic separation, adsorption and controllable release (including pH, electron, temperature, ions, gas, multiresponsive controlled release and osmotic release). Finally, we outline the future perspectives of pillar[5]arene chemistry. We anticipate that this review will serve as a valuable reference for researchers in the field and inspire new discoveries related to pillar[5]arene-based materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113576"},"PeriodicalIF":4.8,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549145","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 : 2025-03-01DOI: 10.1016/j.micromeso.2025.113572
Shaoqing Jin, Qiangqiang Luo, Xueyan Fan, Hongmin Sun, Weimin Yang
Although Ti-MWW zeolite has received lots of attention due to its superior catalytic oxidation performance, it's still challenging to obtain boron-free Ti-MWW zeolite with few defects and high catalytic performance by a simple way. Herein, secondary acid treatment was utilized to modify the structure of Ti-MWW zeolite and its catalytic behavior. It was found that almost all the framework boron atoms could be removed by secondary acid treatment under different conditions. However, different from secondary acid treatment under low-temperature & high-acid concentration (LTHC) condition, that under high-temperature & low-acid concentration (HTLC) condition can heal the silanol nests originally existing and formed during boron removal through silicon migration, remarkably improving the hydrophobicity, the micro-environment of framework TiO4 species (Fw-TiO4) and thus the catalytic activity in 1-hexene epoxidation in spite of a certain amount of inactive anatase TiO2 species formed. This study would be helpful for the post modification and understanding of Ti-MWW zeolite.
{"title":"Effect of secondary acid treatment on the structure of Ti-MWW zeolite and its catalytic performance","authors":"Shaoqing Jin, Qiangqiang Luo, Xueyan Fan, Hongmin Sun, Weimin Yang","doi":"10.1016/j.micromeso.2025.113572","DOIUrl":"10.1016/j.micromeso.2025.113572","url":null,"abstract":"<div><div>Although Ti-MWW zeolite has received lots of attention due to its superior catalytic oxidation performance, it's still challenging to obtain boron-free Ti-MWW zeolite with few defects and high catalytic performance by a simple way. Herein, secondary acid treatment was utilized to modify the structure of Ti-MWW zeolite and its catalytic behavior. It was found that almost all the framework boron atoms could be removed by secondary acid treatment under different conditions. However, different from secondary acid treatment under low-temperature & high-acid concentration (LTHC) condition, that under high-temperature & low-acid concentration (HTLC) condition can heal the silanol nests originally existing and formed during boron removal through silicon migration, remarkably improving the hydrophobicity, the micro-environment of framework TiO<sub>4</sub> species (Fw-TiO<sub>4</sub>) and thus the catalytic activity in 1-hexene epoxidation in spite of a certain amount of inactive anatase TiO<sub>2</sub> species formed. This study would be helpful for the post modification and understanding of Ti-MWW zeolite.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113572"},"PeriodicalIF":4.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549144","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 : 2025-03-01DOI: 10.1016/j.micromeso.2025.113574
Elen Maria Feliciano Pereira , Alejandro Lopez-Castillo , Leandro Martins
The activity of the chabazite zeolite in the Methanol to Olefins (MTO) reaction is tightly connected to the organic intermediates confined in its pores. The intermediates and the pores of near dimensions construct a reciprocal reaction environment for the MTO, known as the hydrocarbon pool (HP) mechanism. The chabazite structure (CHA) stands out in MTO due to the three-dimensional system of large pores connected by small openings, allowing the confinement of the intermediates, allowing small olefins to diffuse in and out. Herein, the organic intermediates in the HP arose as soon as the CHA catalyst was subjected to reaction temperature under a methanol flow. HP was identified to be composed of bridged-ring alkanes (at very low temperatures) and polyaromatics of up to five rings, which grew throughout the reaction, leading to the deactivation of the catalyst. The most active species are the least polymeric. The systematic increase in reaction temperature from 190 to 450 °C revealed a combined change of the zeolite's crystalline structure, which elongates into the c-direction, while olefins are formed. DFT computational simulations confirmed confinement is a spontaneous process forming a hybrid organic-inorganic environment active in the MTO reaction. Other DFT results expanded the understanding of the molecular confinement related to interaction energies with and without system deformation in obtaining geometric parameters beyond the experimental resolution.
{"title":"Evolution of active intermediates in MTO reaction on a Chabazite catalyst","authors":"Elen Maria Feliciano Pereira , Alejandro Lopez-Castillo , Leandro Martins","doi":"10.1016/j.micromeso.2025.113574","DOIUrl":"10.1016/j.micromeso.2025.113574","url":null,"abstract":"<div><div>The activity of the chabazite zeolite in the Methanol to Olefins (MTO) reaction is tightly connected to the organic intermediates confined in its pores. The intermediates and the pores of near dimensions construct a reciprocal reaction environment for the MTO, known as the hydrocarbon pool (HP) mechanism. The chabazite structure (CHA) stands out in MTO due to the three-dimensional system of large pores connected by small openings, allowing the confinement of the intermediates, allowing small olefins to diffuse in and out. Herein, the organic intermediates in the HP arose as soon as the CHA catalyst was subjected to reaction temperature under a methanol flow. HP was identified to be composed of bridged-ring alkanes (at very low temperatures) and polyaromatics of up to five rings, which grew throughout the reaction, leading to the deactivation of the catalyst. The most active species are the least polymeric. The systematic increase in reaction temperature from 190 to 450 °C revealed a combined change of the zeolite's crystalline structure, which elongates into the c-direction, while olefins are formed. DFT computational simulations confirmed confinement is a spontaneous process forming a hybrid organic-inorganic environment active in the MTO reaction. Other DFT results expanded the understanding of the molecular confinement related to interaction energies with and without system deformation in obtaining geometric parameters beyond the experimental resolution.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113574"},"PeriodicalIF":4.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549143","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 : 2025-02-28DOI: 10.1016/j.micromeso.2025.113570
Haoyan Zhou , Mei Zu , Shiquan Li , Yuanxi Chang , Chenglong Lv , Haifeng Cheng
The development of materials that simulate the visible and near-infrared (Vis-NIR) spectral characteristics of vegetation is crucial in the field of biomimetic camouflage. In this research, a novel spectral simulation material based on ion-exchanged zeolites has been synthesized, designed to simulate the spectral characteristics of green and yellow foliage. The structure and microscopic morphology of ion-exchanged zeolite was checked by XRD, FTIR, SEM techniques. Also, N2 physisorption analyses and UV–Vis–NIR spectroscopy were use to analyzed the effect of ion exchange concentration on its water vapor adsorption capacity and spectral reflectance. The introduction of metal cations can mimic the absorption of different pigments in visible bands in plant leaves. Meanwhile, the analysis shows that exchange with chromium and iron cations resulted in a maximum increase in specific surface area to 604 and 582 m2/g, respectively, and consequently the increase in water adsorption capacity with approximately the same rate (13.1 %, 9.3 %), which further enhances the similarity of the near-infrared spectra. Subsequently, bionic coatings were prepared using ion-exchanged zeolites as pigments, and the spectral correlation coefficient of the Vis-NIR spectrum between bionic coatings and green and yellow leaves reached 0.95 and 0.96, which effectively solved the problem of accurately simulating the same color and spectrum as vegetation in the 400–2500 nm wavelength range.
{"title":"Ion-exchanged zeolite for simulating the Vis-NIR spectra characteristics of natural leaves","authors":"Haoyan Zhou , Mei Zu , Shiquan Li , Yuanxi Chang , Chenglong Lv , Haifeng Cheng","doi":"10.1016/j.micromeso.2025.113570","DOIUrl":"10.1016/j.micromeso.2025.113570","url":null,"abstract":"<div><div>The development of materials that simulate the visible and near-infrared (Vis-NIR) spectral characteristics of vegetation is crucial in the field of biomimetic camouflage. In this research, a novel spectral simulation material based on ion-exchanged zeolites has been synthesized, designed to simulate the spectral characteristics of green and yellow foliage. The structure and microscopic morphology of ion-exchanged zeolite was checked by XRD, FTIR, SEM techniques. Also, N<sub>2</sub> physisorption analyses and UV–Vis–NIR spectroscopy were use to analyzed the effect of ion exchange concentration on its water vapor adsorption capacity and spectral reflectance. The introduction of metal cations can mimic the absorption of different pigments in visible bands in plant leaves. Meanwhile, the analysis shows that exchange with chromium and iron cations resulted in a maximum increase in specific surface area to 604 and 582 m<sup>2</sup>/g, respectively, and consequently the increase in water adsorption capacity with approximately the same rate (13.1 %, 9.3 %), which further enhances the similarity of the near-infrared spectra. Subsequently, bionic coatings were prepared using ion-exchanged zeolites as pigments, and the spectral correlation coefficient of the Vis-NIR spectrum between bionic coatings and green and yellow leaves reached 0.95 and 0.96, which effectively solved the problem of accurately simulating the same color and spectrum as vegetation in the 400–2500 nm wavelength range.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"390 ","pages":"Article 113570"},"PeriodicalIF":4.8,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552478","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 : 2025-02-27DOI: 10.1016/j.micromeso.2025.113560
Tian Zhao, Fuli Luo, Pengcheng Xiao, Saiqun Nie, Jiayao Chen, Yi Chen
This review systematically explores the application and research progress of metal-organic frameworks (MOFs) based composites in electrocatalysis. Firstly, we introduce a variety of preparation methods for MOFs-based composites, including in situ doping/substitution, hydrothermal/solvent-thermal methods, solution impregnation, dual-solvent impregnation, and sandwich assembly, with a focus on analyzing the effects of different methods on the structure and properties of the materials. Secondly, the practical applications of MOFs-based composites in electrocatalytic reactions, including hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, nitrogen reduction reaction, and carbon dioxide reduction, are elaborated in detail, with emphasis on their excellent properties and catalytic mechanisms. Finally, we look forward to the future development trend of MOFs-based composites, and believe that with the emergence of novel synthesis technologies and idealized design methods, MOFs-based composites will show greater potential for applications in areas such as renewable energy conversion and environmental governance. In summary, this review provides a comprehensive perspective and in-depth analysis of the electrocatalytic studies of MOFs-based composites.
{"title":"Strategies for the preparation of MOFs-based composites and their research progress in electrocatalysis","authors":"Tian Zhao, Fuli Luo, Pengcheng Xiao, Saiqun Nie, Jiayao Chen, Yi Chen","doi":"10.1016/j.micromeso.2025.113560","DOIUrl":"10.1016/j.micromeso.2025.113560","url":null,"abstract":"<div><div>This review systematically explores the application and research progress of metal-organic frameworks (MOFs) based composites in electrocatalysis. Firstly, we introduce a variety of preparation methods for MOFs-based composites, including in situ doping/substitution, hydrothermal/solvent-thermal methods, solution impregnation, dual-solvent impregnation, and sandwich assembly, with a focus on analyzing the effects of different methods on the structure and properties of the materials. Secondly, the practical applications of MOFs-based composites in electrocatalytic reactions, including hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, nitrogen reduction reaction, and carbon dioxide reduction, are elaborated in detail, with emphasis on their excellent properties and catalytic mechanisms. Finally, we look forward to the future development trend of MOFs-based composites, and believe that with the emergence of novel synthesis technologies and idealized design methods, MOFs-based composites will show greater potential for applications in areas such as renewable energy conversion and environmental governance. In summary, this review provides a comprehensive perspective and in-depth analysis of the electrocatalytic studies of MOFs-based composites.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113560"},"PeriodicalIF":4.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143529013","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}
Tartrazine (TZ) and erythrosine B (EB) dyes are extensively utilized as colorants in numerous commercial applications, including pharmaceuticals, textiles, and consumer products. However, their widespread use leads to the discharge of dye-containing wastewater, posing significant risks to aquatic ecosystems and human health. In this study, the simultaneous removal of these dyes was systematically investigated using MnFe-layered double hydroxides (LDHs)/PVDF as a composite membrane. A polyvinylidene fluoride (PVDF) polymer membrane was synthesized using the phase inversion method and subsequently modified with MnFe-LDH nanoparticles. The structural, morphological, and physicochemical properties of the prepared materials were characterized using XRD, BET, FT-IR, FE-SEM, EDS, and contact angle analyses. Critical operational parameters influencing the adsorption process, such as dye concentration, adsorption time, and adsorbent dosage, were systematically studied and optimized using response surface methodology (RSM) based on central composite design (CCD). In addition, the pH of the solution was optimized as a single independent variable. The impact of each parameter on the removal efficiency of the dyes was thoroughly analyzed. Optimization studies identified the following optimal conditions: Adsorption time = 15 min, the amount of adsorbent = 0.015 g, pH = 5, TZ = 16 mg/L, and EB = 13 mg/L. Under these conditions, removal efficiencies of 94.74 % and 92.13 % were achieved for TZ and EB dyes, respectively. The adsorption behavior was best described by the Langmuir isotherm model, indicating monolayer adsorption on a homogeneous surface. Kinetic evaluations revealed that the adsorption processes adhered closely to pseudo-first-order kinetic models. This study provides valuable insights into the development and application of MnFe-LDHs/PVDF composite membranes, highlighting their potential as effective materials for mitigating dye pollution in wastewater treatment systems.
{"title":"Simultaneous removal of tartrazine and erythrosine B using MnFe-layered double hydroxide nanoparticles modified PVDF polymer membrane","authors":"Parsa Haroonian , Mehrorang Ghaedi , Hamedreza Javadian , Claudia Belviso , Mahboobeh Abbasi","doi":"10.1016/j.micromeso.2025.113569","DOIUrl":"10.1016/j.micromeso.2025.113569","url":null,"abstract":"<div><div>Tartrazine (TZ) and erythrosine B (EB) dyes are extensively utilized as colorants in numerous commercial applications, including pharmaceuticals, textiles, and consumer products. However, their widespread use leads to the discharge of dye-containing wastewater, posing significant risks to aquatic ecosystems and human health. In this study, the simultaneous removal of these dyes was systematically investigated using MnFe-layered double hydroxides (LDHs)/PVDF as a composite membrane. A polyvinylidene fluoride (PVDF) polymer membrane was synthesized using the phase inversion method and subsequently modified with MnFe-LDH nanoparticles. The structural, morphological, and physicochemical properties of the prepared materials were characterized using XRD, BET, FT-IR, FE-SEM, EDS, and contact angle analyses. Critical operational parameters influencing the adsorption process, such as dye concentration, adsorption time, and adsorbent dosage, were systematically studied and optimized using response surface methodology (RSM) based on central composite design (CCD). In addition, the pH of the solution was optimized as a single independent variable. The impact of each parameter on the removal efficiency of the dyes was thoroughly analyzed. Optimization studies identified the following optimal conditions: Adsorption time = 15 min, the amount of adsorbent = 0.015 g, pH = 5, TZ = 16 mg/L, and EB = 13 mg/L. Under these conditions, removal efficiencies of 94.74 % and 92.13 % were achieved for TZ and EB dyes, respectively. The adsorption behavior was best described by the Langmuir isotherm model, indicating monolayer adsorption on a homogeneous surface. Kinetic evaluations revealed that the adsorption processes adhered closely to pseudo-first-order kinetic models. This study provides valuable insights into the development and application of MnFe-LDHs/PVDF composite membranes, highlighting their potential as effective materials for mitigating dye pollution in wastewater treatment systems.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113569"},"PeriodicalIF":4.8,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526789","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 : 2025-02-26DOI: 10.1016/j.micromeso.2025.113561
Zahra Kazemivalipour, Ali Nematollahzadeh, Taher Ataei-Germi, Zahra Vaseghi
Gradation of particles with a specific size range is crucial as it significantly impacts their properties and potential applications. In the present study, a mesoporous silica microsphere (MSMs) was synthesized and the surface chemistry was tuned by polydopamine (PDA) coating as a bioinspired polymer on the pore surfaces. The matrix solid-phase dispersion (MSPD) approach was exploited for the size classification of halloysite nanotubes (HNTs) of varying lengths. For this, the nanotubes were mixed with the as-prepared MSMs or with the PDA-modified silica microspheres (MSM/PDA) and packed in a column. The column was eluted with an aqueous solution of various pHs. The surface chemistry of MSM/PDA packings in synergy with their size exclusion nature led to the retention of the nanotubes of a specific size in the column. The results showed that the separation of HNTs by the MSM/PDA was carried out in far greater amounts (approximately 10-fold) compared with that of MSMs. The highest separation percentage of 32.87 % was achieved at pH 9 of the influent when MSM/PDA was used as packing. In addition, the size distribution analysis of HNTs in the first 10 mL of the effluent revealed that HNTs of average size of 442 nm with a lower polydispersity index value of 0.23 are achievable. Also, the various mathematical models were fitted to the experimental data for both MSMs-HNT and MSM/PDA-HNT packings. It was found that the second-order kinetic model well-suited the size separation of the nanotubes.
{"title":"Bioinspired size separation of halloysite nanotubes by polydopamine-modified porous silica particles in matrix solid-phase dispersion fixed-bed column","authors":"Zahra Kazemivalipour, Ali Nematollahzadeh, Taher Ataei-Germi, Zahra Vaseghi","doi":"10.1016/j.micromeso.2025.113561","DOIUrl":"10.1016/j.micromeso.2025.113561","url":null,"abstract":"<div><div>Gradation of particles with a specific size range is crucial as it significantly impacts their properties and potential applications. In the present study, a mesoporous silica microsphere (MSMs) was synthesized and the surface chemistry was tuned by polydopamine (PDA) coating as a bioinspired polymer on the pore surfaces. The matrix solid-phase dispersion (MSPD) approach was exploited for the size classification of halloysite nanotubes (HNTs) of varying lengths. For this, the nanotubes were mixed with the as-prepared MSMs or with the PDA-modified silica microspheres (MSM/PDA) and packed in a column. The column was eluted with an aqueous solution of various pHs. The surface chemistry of MSM/PDA packings in synergy with their size exclusion nature led to the retention of the nanotubes of a specific size in the column. The results showed that the separation of HNTs by the MSM/PDA was carried out in far greater amounts (approximately 10-fold) compared with that of MSMs. The highest separation percentage of 32.87 % was achieved at pH 9 of the influent when MSM/PDA was used as packing. In addition, the size distribution analysis of HNTs in the first 10 mL of the effluent revealed that HNTs of average size of 442 nm with a lower polydispersity index value of 0.23 are achievable. Also, the various mathematical models were fitted to the experimental data for both MSMs-HNT and MSM/PDA-HNT packings. It was found that the second-order kinetic model well-suited the size separation of the nanotubes.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113561"},"PeriodicalIF":4.8,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143520266","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 : 2025-02-24DOI: 10.1016/j.micromeso.2025.113559
Xinyu Chen, Jinhai Leng, Fengying Ma, Jianqing Wu, Yi Jin, Miao Yu, Haomin Huang, Shanshan Shang, Daiqi Ye
Excessive CO2 emissions significantly contribute to global warming, promoting the advancement of carbon capture and storage (CCS) technologies. Metal-organic frameworks (MOFs) are promising candidates for selective CO2 adsorption; however, their effectiveness is often compromised in humid environments, such as flue gas streams. To overcome this limitation, this study synthesizes six isostructural DABCO-pillared MOFs (DMOFs) by finely tuning metal nodes (from Zn to Ni) and integrating methyl (-CH3) functional groups on the organic ligand to enhance CO2 adsorption performance, especially under humid conditions. Single gas adsorption isotherms reveal that the Ni-TM DMOF achieves the highest CO2 adsorption capacity of 5.0 mmol g−1 and maintains 100 % regenerability after five cycles. Binary CO2/N2 dynamic breakthrough experiments further demonstrate that the Ni-TM DMOF excels in both CO2 uptake and CO2/N2 separation performance under both dry and humid conditions (80 % relative humidity). Mechanistic insights from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations elucidate the molecular interactions between CO2 and the DMOF structure, revealing that CO2 adsorption predominantly occurs via physisorption, enhanced by C-H·O interaction from the -CH3 groups. This work provides a strategic approach for enhancing the stability and efficiency of MOFs in industrial CO2 sequestration applications.
{"title":"Highly controllable CO2 capture performance under varied humidity conditions by finely tuned metal and organic ligand compositions of DMOF adsorbents","authors":"Xinyu Chen, Jinhai Leng, Fengying Ma, Jianqing Wu, Yi Jin, Miao Yu, Haomin Huang, Shanshan Shang, Daiqi Ye","doi":"10.1016/j.micromeso.2025.113559","DOIUrl":"10.1016/j.micromeso.2025.113559","url":null,"abstract":"<div><div>Excessive CO<sub>2</sub> emissions significantly contribute to global warming, promoting the advancement of carbon capture and storage (CCS) technologies. Metal-organic frameworks (MOFs) are promising candidates for selective CO<sub>2</sub> adsorption; however, their effectiveness is often compromised in humid environments, such as flue gas streams. To overcome this limitation, this study synthesizes six isostructural DABCO-pillared MOFs (DMOFs) by finely tuning metal nodes (from Zn to Ni) and integrating methyl (-CH<sub>3</sub>) functional groups on the organic ligand to enhance CO<sub>2</sub> adsorption performance, especially under humid conditions. Single gas adsorption isotherms reveal that the Ni-TM DMOF achieves the highest CO<sub>2</sub> adsorption capacity of 5.0 mmol g<sup>−1</sup> and maintains 100 % regenerability after five cycles. Binary CO<sub>2</sub>/N<sub>2</sub> dynamic breakthrough experiments further demonstrate that the Ni-TM DMOF excels in both CO<sub>2</sub> uptake and CO<sub>2</sub>/N<sub>2</sub> separation performance under both dry and humid conditions (80 % relative humidity). Mechanistic insights from <em>in situ</em> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations elucidate the molecular interactions between CO<sub>2</sub> and the DMOF structure, revealing that CO<sub>2</sub> adsorption predominantly occurs <em>via</em> physisorption, enhanced by C-H·O interaction from the -CH<sub>3</sub> groups. This work provides a strategic approach for enhancing the stability and efficiency of MOFs in industrial CO<sub>2</sub> sequestration applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113559"},"PeriodicalIF":4.8,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512206","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 : 2025-02-22DOI: 10.1016/j.micromeso.2025.113556
Yichen Feng , Linghao Li , Jian Huang , Wei Wang , Bowen Lu , Siyu Yang , Haiwei Xu , Ying Shi , Zile Hua
Using silicalite-1 and TS-1 nanozeolites as precursors, a new combination process consisting of sequential alkali-etching and Ti-grafting treatment has been designed for preparation of hierarchically structured titanosilicate catalysts. The alkali-etching process creates abundant mesopores and Si-OH groups in the nanozeolite precursors, effectively increasing the titanium loadings and accelerating the mass transfer during the reactions. Benefiting from the developed micro/mesoporous structures, the adjustable Ti loadings and the intrinsic hydrophobicity of precursor nanozeolites, the resultant catalysts demonstrate superior performance toward the catalytic oxidation desulfurization (ODS) of fuels, i.e. in 3 h, the complete conversion of thiophene (Th), benzothiophene (BT) and dibenzothiophene (DBT) which are three typical refractory sulfur compounds with diverse reducibility and molecule sizes in fuels.
{"title":"Ti-grafting functionalization on alkali-etched nanozeolites to enhance their catalytic performance toward oxidation desulfurization of fuels","authors":"Yichen Feng , Linghao Li , Jian Huang , Wei Wang , Bowen Lu , Siyu Yang , Haiwei Xu , Ying Shi , Zile Hua","doi":"10.1016/j.micromeso.2025.113556","DOIUrl":"10.1016/j.micromeso.2025.113556","url":null,"abstract":"<div><div>Using silicalite-1 and TS-1 nanozeolites as precursors, a new combination process consisting of sequential alkali-etching and Ti-grafting treatment has been designed for preparation of hierarchically structured titanosilicate catalysts. The alkali-etching process creates abundant mesopores and Si-OH groups in the nanozeolite precursors, effectively increasing the titanium loadings and accelerating the mass transfer during the reactions. Benefiting from the developed micro/mesoporous structures, the adjustable Ti loadings and the intrinsic hydrophobicity of precursor nanozeolites, the resultant catalysts demonstrate superior performance toward the catalytic oxidation desulfurization (ODS) of fuels, i.e. in 3 h, the complete conversion of thiophene (Th), benzothiophene (BT) and dibenzothiophene (DBT) which are three typical refractory sulfur compounds with diverse reducibility and molecule sizes in fuels.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"389 ","pages":"Article 113556"},"PeriodicalIF":4.8,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512205","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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