Pub Date : 2025-12-31DOI: 10.1016/j.micromeso.2025.114022
John Senith Ravishan Fernando , Venkatesh Bollabathini , Quoc Duy Ho , Kåre B. Jørgensen , Eva Rauls , Sachin Maruti Chavan
This study presents a systematic investigation of per-hydroxy pillar[5]arene (P[5]A-OH) -based Supramolecular Organic Frameworks for CO2 adsorption. The research emphasizes the critical roles of recrystallization and activation processes in transforming P[5]A-OH into a porous structure conducive to efficient CO2 uptake. The water vapour adsorption and adsorption cyclability for CO2 under dry and humid conditions are reported for the first time for P[5]A-OH. The material exhibited a CO2 adsorption capacity of 2.16 mmol g−1 at 298 K and 1 bar, with CO2/N2 IAST selectivity of 72 and excellent structural and CO2 adsorption cyclic stability under dry and humid conditions, highlighting its potential as a robust and cyclable adsorbent for CO2 separation.
{"title":"Adaptive per-hydroxy pillar[5]arene-based frameworks for selective CO2 adsorption under humid conditions","authors":"John Senith Ravishan Fernando , Venkatesh Bollabathini , Quoc Duy Ho , Kåre B. Jørgensen , Eva Rauls , Sachin Maruti Chavan","doi":"10.1016/j.micromeso.2025.114022","DOIUrl":"10.1016/j.micromeso.2025.114022","url":null,"abstract":"<div><div>This study presents a systematic investigation of <em>per</em>-hydroxy pillar[5]arene (P[5]A-OH) -based Supramolecular Organic Frameworks for CO<sub>2</sub> adsorption. The research emphasizes the critical roles of recrystallization and activation processes in transforming P[5]A-OH into a porous structure conducive to efficient CO<sub>2</sub> uptake. The water vapour adsorption and adsorption cyclability for CO<sub>2</sub> under dry and humid conditions are reported for the first time for P[5]A-OH. The material exhibited a CO<sub>2</sub> adsorption capacity of 2.16 mmol g<sup>−1</sup> at 298 K and 1 bar, with CO<sub>2</sub>/N<sub>2</sub> IAST selectivity of 72 and excellent structural and CO<sub>2</sub> adsorption cyclic stability under dry and humid conditions, highlighting its potential as a robust and cyclable adsorbent for CO<sub>2</sub> separation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114022"},"PeriodicalIF":4.7,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921899","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}
Carbon capture, utilization, storage (CCUS), particularly post-combustion CO2 capture, relies heavily on efficient gas separation materials. Zeolites have shown great potential as adsorbents due to their tunable structures and adsorption properties. In this work, Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations were employed to investigate the competitive adsorption and diffusion behaviors of CO2 and N2 in M-ZSM-5 (M = Li, Na, K) under flue gas conditions. It was notably found that although the adsorption of pure N2 increases with pressure in these zeolites, N2 uptake becomes negligible in competitive flue gas mixtures, while CO2 adsorption remains largely unaffected. This behavior leads to a significant enhancement in CO2/N2 selectivity. Among all samples, Li-ZSM-5 exhibited the highest performance, with a CO2 uptake of 2.41 mol/kg and a selectivity of 640 for CO2 over N2 at 303 K and 1 bar, which is attributed to the strong electrostatic interactions introduced by cation modification. These findings highlight the promising application of cation-exchanged ZSM-5 zeolites for efficient CO2 separation from flue gas.
{"title":"Competitive adsorption and diffusion of CO2/N2 in M-ZSM-5 for post-combustion capture: A molecular simulation insight","authors":"Ziyi Zhao, Weixin Qian, Hongfang Ma, Weiyong Ying, Haitao Zhang, Peiqing Yuan","doi":"10.1016/j.micromeso.2025.114024","DOIUrl":"10.1016/j.micromeso.2025.114024","url":null,"abstract":"<div><div>Carbon capture, utilization, storage (CCUS), particularly post-combustion CO<sub>2</sub> capture, relies heavily on efficient gas separation materials. Zeolites have shown great potential as adsorbents due to their tunable structures and adsorption properties. In this work, Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations were employed to investigate the competitive adsorption and diffusion behaviors of CO<sub>2</sub> and N<sub>2</sub> in M-ZSM-5 (M = Li, Na, K) under flue gas conditions. It was notably found that although the adsorption of pure N<sub>2</sub> increases with pressure in these zeolites, N<sub>2</sub> uptake becomes negligible in competitive flue gas mixtures, while CO<sub>2</sub> adsorption remains largely unaffected. This behavior leads to a significant enhancement in CO<sub>2</sub>/N<sub>2</sub> selectivity. Among all samples, Li-ZSM-5 exhibited the highest performance, with a CO<sub>2</sub> uptake of 2.41 mol/kg and a selectivity of 640 for CO<sub>2</sub> over N<sub>2</sub> at 303 K and 1 bar, which is attributed to the strong electrostatic interactions introduced by cation modification. These findings highlight the promising application of cation-exchanged ZSM-5 zeolites for efficient CO<sub>2</sub> separation from flue gas.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114024"},"PeriodicalIF":4.7,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921896","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 : 2025-12-30DOI: 10.1016/j.micromeso.2025.114023
Ru Tian , Hengfan Yao , Yanping Huang , Qingguo Wang
The removal of low concentration of manganese (Mn(II)) from surface water poses a challenge in drinking water treatment. This study developed a chitosan-modified zeolite (CMZ) to effectively adsorb Mn(II) at low concentrations (e.g., 0.255 mg/L). Characterization revealed that CMZ possessed a specific surface area 22.4 times larger than artificial zeolite, and thermogravimetric analysis quantified the chitosan loading at 14.85 wt%, confirming successful modification. The amino and hydroxyl groups served as the primary adsorption sites. CMZ performed effectively over a wide pH range (5–8), and its efficiency was largely unaffected by common coexisting ions, except for Ca2+. Adsorption kinetics and isotherms were well-described by the pseudo-second-order and Langmuir models, respectively, indicating a chemisorption-dominated, monolayer process. The mechanism involved both ion exchange and surface complexation. These findings demonstrate that CMZ is a highly promising adsorbent for removing low concentration of Mn(II) from drinking water sources.
{"title":"Removal of low concentration manganese in surface drinking water sources by chitosan-modified zeolite: performance and mechanism","authors":"Ru Tian , Hengfan Yao , Yanping Huang , Qingguo Wang","doi":"10.1016/j.micromeso.2025.114023","DOIUrl":"10.1016/j.micromeso.2025.114023","url":null,"abstract":"<div><div>The removal of low concentration of manganese (Mn(II)) from surface water poses a challenge in drinking water treatment. This study developed a chitosan-modified zeolite (CMZ) to effectively adsorb Mn(II) at low concentrations (e.g., 0.255 mg/L). Characterization revealed that CMZ possessed a specific surface area 22.4 times larger than artificial zeolite, and thermogravimetric analysis quantified the chitosan loading at 14.85 wt%, confirming successful modification. The amino and hydroxyl groups served as the primary adsorption sites. CMZ performed effectively over a wide pH range (5–8), and its efficiency was largely unaffected by common coexisting ions, except for Ca<sup>2+</sup>. Adsorption kinetics and isotherms were well-described by the pseudo-second-order and Langmuir models, respectively, indicating a chemisorption-dominated, monolayer process. The mechanism involved both ion exchange and surface complexation. These findings demonstrate that CMZ is a highly promising adsorbent for removing low concentration of Mn(II) from drinking water sources.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114023"},"PeriodicalIF":4.7,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881886","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 : 2025-12-27DOI: 10.1016/j.micromeso.2025.114020
Qiao Yu , Tao Wang , Zhilin Chen, Chao Xiao
Understanding of the main factors affecting the silanol defects (Si–OH) of zeolite is vital for its catalysis and adsorption properties. Taking silicalite-1 (MFI) as an example, a systematic investigation of synthesis temperature, TPAOH addition, ethanol addition, and K addition on the silanol defects of silicalite-1 was conducted using pure reagents excluding the effect of metal impurities. Silicalite-1 synthesized form pure tetraethyl orthosilicate (TEOS) and tetrapropylammonium hydroxide (TPAOH) contains a relatively high concentration of silanol nests with a Q3/Q4 ratio of 10.0% in the 29Si MAS NMR spectra. The introduction of trace alkali metal ions above 0.02 mol% effectively reduces the defect concentration of silicalite-1. Moreover, the effect of K reaches a plateau as K/Si ratio beyond 0.2 mol% does not lead to further reduction of structural defects. Lowering the synthesis temperature to 125 °C results in smaller crystal sizes, irregular morphologies, and a slight decrease in silanol nests. Decrease of the TPAOH amount increases the crystal size from 139 nm to 224 nm, but has little effect on the silanol defect concentration. Ethanol from controlled addition reduces the silanol defects somewhat.
了解影响沸石硅醇缺陷（Si-OH）的主要因素对其催化和吸附性能具有重要意义。以硅石-1 （MFI）为例，采用排除金属杂质影响的纯试剂，系统研究了合成温度、TPAOH加成、乙醇加成和K加成对硅石-1硅醇缺陷的影响。由纯正硅酸四乙酯（TEOS）和四丙基氢氧化铵（TPAOH）合成的硅烷-1含有相对高浓度的硅烷醇巢，在29Si MAS NMR光谱中Q3/Q4比为10.0%。引入0.02 mol%以上的微量碱金属离子，有效降低了硅石-1的缺陷浓度。此外，当K/Si比超过0.2 mol%时，K的影响达到一个平台，不再导致结构缺陷的进一步减少。将合成温度降低到125℃，晶体尺寸变小，形貌不规则，硅烷醇巢略有减少。TPAOH用量的减少使晶体尺寸从139 nm增加到224 nm，但对硅烷醇缺陷浓度影响不大。控制加成的乙醇在一定程度上减少了硅烷醇的缺陷。
{"title":"A systematic investigation of synthesis conditions on the silanol defects of silicalite-1","authors":"Qiao Yu , Tao Wang , Zhilin Chen, Chao Xiao","doi":"10.1016/j.micromeso.2025.114020","DOIUrl":"10.1016/j.micromeso.2025.114020","url":null,"abstract":"<div><div>Understanding of the main factors affecting the silanol defects (Si–OH) of zeolite is vital for its catalysis and adsorption properties. Taking silicalite-1 (MFI) as an example, a systematic investigation of synthesis temperature, TPAOH addition, ethanol addition, and K addition on the silanol defects of silicalite-1 was conducted using pure reagents excluding the effect of metal impurities. Silicalite-1 synthesized form pure tetraethyl orthosilicate (TEOS) and tetrapropylammonium hydroxide (TPAOH) contains a relatively high concentration of silanol nests with a Q<sup>3</sup>/Q<sup>4</sup> ratio of 10.0% in the <sup>29</sup>Si MAS NMR spectra. The introduction of trace alkali metal ions above 0.02 mol% effectively reduces the defect concentration of silicalite-1. Moreover, the effect of K reaches a plateau as K/Si ratio beyond 0.2 mol% does not lead to further reduction of structural defects. Lowering the synthesis temperature to 125 °C results in smaller crystal sizes, irregular morphologies, and a slight decrease in silanol nests. Decrease of the TPAOH amount increases the crystal size from 139 nm to 224 nm, but has little effect on the silanol defect concentration. Ethanol from controlled addition reduces the silanol defects somewhat.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114020"},"PeriodicalIF":4.7,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881885","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 : 2025-12-26DOI: 10.1016/j.micromeso.2025.114021
Loriane Didier , Alan Sam , Cecilia Herrero , Rodolfo Venegas , Benoit Coasne
Equilibrium and non-equilibrium molecular dynamics simulations are used to decipher the mechanisms that rule the diffusion and permeability of pure fluids and mixtures inside a cage-like nanoporous material. In more detail, we consider the case of methane, carbon dioxide and their mixture within the RHO zeolite – which is made up of nanometric cages connected by narrow subnanometric windows. The fluid molecular structure is found to significantly affect both the self and collective dynamics; while carbon dioxide (CO) transport slows down in a monotonous fashion upon increasing the fluid adsorbed amount , methane (CH) transport displays a non-monotonous behavior upon increasing . We identify that such differences arise from the fluid organization within the nanoporosity which strongly affects the characteristic caging time (or equivalently the transfer rate through the narrow windows). In particular, we show that the increase in the self-diffusivity for CH at large arises from the fluid redistribution within the zeolite cages and windows. Upon investigating mixture transport as induced by a chemical potential gradient (or equivalently a pressure gradient), we find that local segregation of the mixture components significantly affects the induced flow. While a homogeneous flow is observed in the case of fully miscible mixtures, immiscible mixtures exhibit a marked different behavior as the two fluid components respond differently to the applied driving force. We show that such finding can be rationalized using a simple thermodynamic model based on the Gibbs-Duhem equation combined with Stokes equation for momentum conservation.
{"title":"Self-diffusion and permeability of methane, carbon dioxide, and their mixture in zeolite: Cage effect, fluid redistribution, and nanosegregation","authors":"Loriane Didier , Alan Sam , Cecilia Herrero , Rodolfo Venegas , Benoit Coasne","doi":"10.1016/j.micromeso.2025.114021","DOIUrl":"10.1016/j.micromeso.2025.114021","url":null,"abstract":"<div><div>Equilibrium and non-equilibrium molecular dynamics simulations are used to decipher the mechanisms that rule the diffusion and permeability of pure fluids and mixtures inside a cage-like nanoporous material. In more detail, we consider the case of methane, carbon dioxide and their mixture within the RHO zeolite – which is made up of nanometric cages connected by narrow subnanometric windows. The fluid molecular structure is found to significantly affect both the self and collective dynamics; while carbon dioxide (CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>) transport slows down in a monotonous fashion upon increasing the fluid adsorbed amount <span><math><msub><mrow><mi>n</mi></mrow><mrow><mi>a</mi></mrow></msub></math></span>, methane (CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>) transport displays a non-monotonous behavior upon increasing <span><math><msub><mrow><mi>n</mi></mrow><mrow><mi>a</mi></mrow></msub></math></span>. We identify that such differences arise from the fluid organization within the nanoporosity which strongly affects the characteristic caging time (or equivalently the transfer rate through the narrow windows). In particular, we show that the increase in the self-diffusivity for CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> at large <span><math><msub><mrow><mi>n</mi></mrow><mrow><mi>a</mi></mrow></msub></math></span> arises from the fluid redistribution within the zeolite cages and windows. Upon investigating mixture transport as induced by a chemical potential gradient (or equivalently a pressure gradient), we find that local segregation of the mixture components significantly affects the induced flow. While a homogeneous flow is observed in the case of fully miscible mixtures, immiscible mixtures exhibit a marked different behavior as the two fluid components respond differently to the applied driving force. We show that such finding can be rationalized using a simple thermodynamic model based on the Gibbs-Duhem equation combined with Stokes equation for momentum conservation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114021"},"PeriodicalIF":4.7,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921901","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 : 2025-12-25DOI: 10.1016/j.micromeso.2025.114019
Jiahang Fan , Jiaqi Huang , Teng Chen , Xiaohong Zheng , Fenghui Guo , Mengyao Yang , Qianchao Ma , Liangjie Fu , Xin Min , Zhaohui Huang
This study synthesized magnetic 4A zeolite (MZA) via an innovative ultrafast Joule heating (UJH) combined with hydrothermal method using hard kaolin and industrial solid waste red mud as raw materials. The synthesized MZA was applied to treat heavy metal ion-contaminated water caused by the ternary lithium-ion battery industry, achieving the “waste-treating-waste' objective. Specifically, UJH first treated red mud at 1100 °C for 20 s (no reducing gas) to convert its iron into magnetite and Si-Al-Na components into soluble species, and simultaneously treated hard kaolin at 800 °C for 20 s to form metakaolin. Subsequently. Metakaolin, reduced red mud, and NaOH (mass ratio 1:0.2:1) were mixed and hydrothermally treated at 90 °C for 10 h to yield MZA. The maximum adsorption capacities of MZA for Ni2+, Co2+, Mn2+, and Cu2+ are 80.71 mg/g, 82.73 mg/g, 85.91 mg/g, and 207.20 mg/g, respectively. Adsorption follows the pseudo-second-order kinetic model and Langmuir isotherm model. In the quaternary mixed system, MZA shows high selectivity for Cu2+, and the adsorption priority of MZA for these heavy metal ions follows the order of Cu2+>Mn2+>Co2+>Ni2+. After five adsorption-desorption cycles, the removal rates of Cu2+ and Ni2+ by MZA only decreased by 2.48 % and 3.72 %, respectively. Moreover, MZA maintains efficient magnetic separation performance. In summary, the energy-saving, eco-friendly, and safe MZA synthesis strategy provides a promising friendly approach for heavy metal wastewater treatment.
{"title":"Synthesis of magnetic zeolite 4A using thermally reduced red mud and metakaolin via ultrafast Joule heating for heavy metal ion removal from industrial wastewater","authors":"Jiahang Fan , Jiaqi Huang , Teng Chen , Xiaohong Zheng , Fenghui Guo , Mengyao Yang , Qianchao Ma , Liangjie Fu , Xin Min , Zhaohui Huang","doi":"10.1016/j.micromeso.2025.114019","DOIUrl":"10.1016/j.micromeso.2025.114019","url":null,"abstract":"<div><div>This study synthesized magnetic 4A zeolite (MZA) via an innovative ultrafast Joule heating (UJH) combined with hydrothermal method using hard kaolin and industrial solid waste red mud as raw materials. The synthesized MZA was applied to treat heavy metal ion-contaminated water caused by the ternary lithium-ion battery industry, achieving the “waste-treating-waste' objective. Specifically, UJH first treated red mud at 1100 °C for 20 s (no reducing gas) to convert its iron into magnetite and Si-Al-Na components into soluble species, and simultaneously treated hard kaolin at 800 °C for 20 s to form metakaolin. Subsequently. Metakaolin, reduced red mud, and NaOH (mass ratio 1:0.2:1) were mixed and hydrothermally treated at 90 °C for 10 h to yield MZA. The maximum adsorption capacities of MZA for Ni<sup>2+</sup>, Co<sup>2+</sup>, Mn<sup>2+</sup>, and Cu<sup>2+</sup> are 80.71 mg/g, 82.73 mg/g, 85.91 mg/g, and 207.20 mg/g, respectively. Adsorption follows the pseudo-second-order kinetic model and Langmuir isotherm model. In the quaternary mixed system, MZA shows high selectivity for Cu<sup>2+</sup>, and the adsorption priority of MZA for these heavy metal ions follows the order of Cu<sup>2+</sup>>Mn<sup>2+</sup>>Co<sup>2+</sup>>Ni<sup>2+</sup>. After five adsorption-desorption cycles, the removal rates of Cu<sup>2+</sup> and Ni<sup>2+</sup> by MZA only decreased by 2.48 % and 3.72 %, respectively. Moreover, MZA maintains efficient magnetic separation performance. In summary, the energy-saving, eco-friendly, and safe MZA synthesis strategy provides a promising friendly approach for heavy metal wastewater treatment.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114019"},"PeriodicalIF":4.7,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838955","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 : 2025-12-25DOI: 10.1016/j.micromeso.2025.114016
Xu Liao , Shuai Liu , Xianmin Kuang , Yingwei Zhou , Quanan Xiao , Baiqing Chen , Jiao He , Jinqing Lin
To overcome the low catalytic efficiency in CO2 cycloaddition resulting from the limited ionic density of hyper-crosslinked ionic polymers (HIPs) prepared via in situ ionic site generation during hyper-crosslinking, we developed a one-pot synthesis approach for pyridine-based HIPs by reacting 4-phenylpyridine or 4-benzylpyridine with 1,4-bis(bromomethyl)benzene. The results revealed that the polymers synthesized using 4-benzylpyridine exhibited a higher nitrogen content and ionic density compared to that derived from 4-phenylpyridine. Notably, [HBPR]Br-1 achieved the highest nitrogen content (2.37 wt%) and theoretical ionic density (1.69 mmol g−1) when synthesized with an equimolar ratio of 4-benzylpyridine and 1,4-bis(bromomethyl)benzene. Owing to its high ionic density, [HBPR]Br-1 displayed good catalytic activity, affording a 96 % yield in the CO2/styrene oxide cycloaddition at 100 °C, 0.5 MPa CO2 in 10 h without the need for co-catalysts. Furthermore, a series of catalytic tests confirmed its competitive substrate compatibility, cyclic stability and practicability. Remarkably, [HBPR]Br-1 maintained high catalytic performance in simulated flue gas, achieving a 95 % yield of styrene carbonate at 100 °C and 0.5 MPa in 24 h. This work introduces a new one-pot approach for preparing pyridine-based HIPs featuring high ionic density and highlights the crucial impact of ionic density on enhancing catalytic efficiency in CO2 cycloaddition.
{"title":"Pyridine-based hyper-crosslinked ionic polymers with high ionic density: One-pot synthesis and application in efficient CO2 conversion","authors":"Xu Liao , Shuai Liu , Xianmin Kuang , Yingwei Zhou , Quanan Xiao , Baiqing Chen , Jiao He , Jinqing Lin","doi":"10.1016/j.micromeso.2025.114016","DOIUrl":"10.1016/j.micromeso.2025.114016","url":null,"abstract":"<div><div>To overcome the low catalytic efficiency in CO<sub>2</sub> cycloaddition resulting from the limited ionic density of hyper-crosslinked ionic polymers (HIPs) prepared via in situ ionic site generation during hyper-crosslinking, we developed a one-pot synthesis approach for pyridine-based HIPs by reacting 4-phenylpyridine or 4-benzylpyridine with 1,4-bis(bromomethyl)benzene. The results revealed that the polymers synthesized using 4-benzylpyridine exhibited a higher nitrogen content and ionic density compared to that derived from 4-phenylpyridine. Notably, [HBPR]Br-1 achieved the highest nitrogen content (2.37 wt%) and theoretical ionic density (1.69 mmol g<sup>−1</sup>) when synthesized with an equimolar ratio of 4-benzylpyridine and 1,4-bis(bromomethyl)benzene. Owing to its high ionic density, [HBPR]Br-1 displayed good catalytic activity, affording a 96 % yield in the CO<sub>2</sub>/styrene oxide cycloaddition at 100 °C, 0.5 MPa CO<sub>2</sub> in 10 h without the need for co-catalysts. Furthermore, a series of catalytic tests confirmed its competitive substrate compatibility, cyclic stability and practicability. Remarkably, [HBPR]Br-1 maintained high catalytic performance in simulated flue gas, achieving a 95 % yield of styrene carbonate at 100 °C and 0.5 MPa in 24 h. This work introduces a new one-pot approach for preparing pyridine-based HIPs featuring high ionic density and highlights the crucial impact of ionic density on enhancing catalytic efficiency in CO<sub>2</sub> cycloaddition.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114016"},"PeriodicalIF":4.7,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838954","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}
Novel hybrid nanocomposites were tentatively prepared by grinding, heating and purifying in Soxhlet preset amounts of lawsone and methyl orange dyes with the microporous palygorskite clay mineral, i.e., following the ancient recipe of the famed Maya Blue pigment. These composites were investigated in the various synthesis steps with a multi-analytical approach (XRPD, FE-SEM-EDS, BET-SSA, TGA-DSC, UV–Vis, ATR-FT-IR and Fluorescence spectroscopies), which allowed understanding their structural features and physicochemical properties, unveiling the nature and sites of the interactions existing between the host and the guest. Also, their stability was evaluated through harsh chemical attacks, monitoring colour changes and spectral features.
The obtained outcomes proved that lawsone forms a stable hybrid composite after heating with palygorskite, establishing H-bonds between the C=O groups on its quinonoid ring and the structural/zeolitic water in the grooves carving the clay fibrils surface. Such a stability, coupled to an observed colour shift after pH fluctuations (yellow in acids; orange in alkalis), suggests that this composite might be used as a solid-state, reversible acid-base indicator, a colorimetric-electrochemical sensor for anions or for bio-reduction of pollutants in remediation activities.
Methyl orange, on the other hand, undergoes systematic degradation when heated together with palygorskite, forming byproducts unable of efficiently binding to the host framework. Despite a presumed affinity of palygorskite for absorbing azo dyes, methyl orange is not firmly stabilized on the host structure due to an incipient mutual electrostatic repulsion that prevents bonding and shielding during grinding, paving the way for an inevitable decay of the molecule after heating.
{"title":"Structural and physicochemical properties of Mayan-inspired hybrid nanocomposites obtained by complexing palygorskite to lawsone and methyl orange","authors":"Roberto Giustetto , Nadia Barbero , Francesca Bonino , Virginia Guiotto , Carlotta Pontremoli , Gabriele Ricchiardi","doi":"10.1016/j.micromeso.2025.114018","DOIUrl":"10.1016/j.micromeso.2025.114018","url":null,"abstract":"<div><div>Novel hybrid nanocomposites were tentatively prepared by grinding, heating and purifying in Soxhlet preset amounts of lawsone and methyl orange dyes with the microporous palygorskite clay mineral, i.e., following the ancient recipe of the famed <em>Maya Blue</em> pigment. These composites were investigated in the various synthesis steps with a multi-analytical approach (XRPD, FE-SEM-EDS, BET-SSA, TGA-DSC, UV–Vis, ATR-FT-IR and Fluorescence spectroscopies), which allowed understanding their structural features and physicochemical properties, unveiling the nature and sites of the interactions existing between the host and the guest. Also, their stability was evaluated through harsh chemical attacks, monitoring colour changes and spectral features.</div><div>The obtained outcomes proved that lawsone forms a stable hybrid composite after heating with palygorskite, establishing H-bonds between the C=O groups on its quinonoid ring and the structural/zeolitic water in the grooves carving the clay fibrils surface. Such a stability, coupled to an observed colour shift after pH fluctuations (yellow in acids; orange in alkalis), suggests that this composite might be used as a solid-state, reversible acid-base indicator, a colorimetric-electrochemical sensor for anions or for bio-reduction of pollutants in remediation activities.</div><div>Methyl orange, on the other hand, undergoes systematic degradation when heated together with palygorskite, forming byproducts unable of efficiently binding to the host framework. Despite a presumed affinity of palygorskite for absorbing azo dyes, methyl orange is not firmly stabilized on the host structure due to an incipient mutual electrostatic repulsion that prevents bonding and shielding during grinding, paving the way for an inevitable decay of the molecule after heating.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114018"},"PeriodicalIF":4.7,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881887","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}
Zeolites with uniform pore sizes, high specific surface areas, excellent thermal and hydrothermal stability play a pivotal role in the field of chemical industry. Their applications have yielded substantial economic and social benefits. Despite their widespread utilization, the current synthesis for preparing zeolites still face challenges in terms of environmental sustainability, which strongly limits their further applications. Recent researches have witnessed notable progresses in developing sustainable synthesis of zeolites, including organotemplate-free, solvent-free, and near-neutral synthesis. Notably, the integration of organotemplate-free and solvent-free routes, as well as the combination of solvent-free and near-neutral routes, enables a more sustainable pathway for zeolite production. Very importantly, many zeolite products such as pure silica Beta and Al-rich Beta zeolites using these novel routes have already been scaled up for industrial production. These sustainable syntheses are expected to markedly lower production costs and minimize waste generation, thereby contributing positively to the carbon neutrality in the future.
{"title":"Sustainable synthesis of zeolites","authors":"Jiaqi Shi, Qinming Wu, Xiangju Meng, Feng-Shou Xiao","doi":"10.1016/j.micromeso.2025.114017","DOIUrl":"10.1016/j.micromeso.2025.114017","url":null,"abstract":"<div><div>Zeolites with uniform pore sizes, high specific surface areas, excellent thermal and hydrothermal stability play a pivotal role in the field of chemical industry. Their applications have yielded substantial economic and social benefits. Despite their widespread utilization, the current synthesis for preparing zeolites still face challenges in terms of environmental sustainability, which strongly limits their further applications. Recent researches have witnessed notable progresses in developing sustainable synthesis of zeolites, including organotemplate-free, solvent-free, and near-neutral synthesis. Notably, the integration of organotemplate-free and solvent-free routes, as well as the combination of solvent-free and near-neutral routes, enables a more sustainable pathway for zeolite production. Very importantly, many zeolite products such as pure silica Beta and Al-rich Beta zeolites using these novel routes have already been scaled up for industrial production. These sustainable syntheses are expected to markedly lower production costs and minimize waste generation, thereby contributing positively to the carbon neutrality in the future.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114017"},"PeriodicalIF":4.7,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838950","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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