Pub Date : 2025-12-17DOI: 10.1016/j.micromeso.2025.114000
Rong Lei, Rutong Zhang, Xiaolei Fu, Lu Li, Yuhuan Nie, Qibin Chen
Despite the significant progress in the synthesis of hypercrosslinked polymers (HCPs), the precise construction of HCPs with unique nano- and microstructures without using template remains a great challenge. In this study, a uniquely nanotubular HCP had been synthesized via an ortho-substitution strategy activated by electron-donating groups introduced, using 4,4′-biphenyldiol (BPD) and p-dichloroxylene (DCX) as building block and crosslinker, respectively. More strikingly, nanotubular HCPs derived from achiral BPD and DCX afford the enantioselective recognition ability to some extent, hereafter denoted as chiral HCP (CHCP). All CHCPs tend to spontaneously form the ultra-thin sheet at the first stage, subsequently roll-up and self-assemble into nanotubes. In order to further improve the enantioselectivity, a certain amount of D- or L-phenylalanine (D- or L-Phe) was used as chiral selector to improve the chiral environment, affording the corresponding nanotubular D- and L-CHCPs. Moreover, the combination of the nanotubular CHCP with the chiral selector can exert a significant synergic effect on improving the enantioselectivity, according to the differential pulse voltammetry (DPV). Our findings suggest that the ortho-substitution strategy proposed in this work represents a fundamentally new approach that opens significant opportunities for the manipulation of HCP structures and the enhancement in the specifically functional property of new materials.
{"title":"Chiral tubular hypercrosslinked polymers from orientational rolling-up of nanosheet directed by ortho-position substitution","authors":"Rong Lei, Rutong Zhang, Xiaolei Fu, Lu Li, Yuhuan Nie, Qibin Chen","doi":"10.1016/j.micromeso.2025.114000","DOIUrl":"10.1016/j.micromeso.2025.114000","url":null,"abstract":"<div><div>Despite the significant progress in the synthesis of hypercrosslinked polymers (HCPs), the precise construction of HCPs with unique nano- and microstructures without using template remains a great challenge. In this study, a uniquely nanotubular HCP had been synthesized via an ortho-substitution strategy activated by electron-donating groups introduced, using 4,4′-biphenyldiol (BPD) and <em>p</em>-dichloroxylene (DCX) as building block and crosslinker, respectively. More strikingly, nanotubular HCPs derived from achiral BPD and DCX afford the enantioselective recognition ability to some extent, hereafter denoted as chiral HCP (CHCP). All CHCPs tend to spontaneously form the ultra-thin sheet at the first stage, subsequently roll-up and self-assemble into nanotubes. In order to further improve the enantioselectivity, a certain amount of <em>D-</em> or <em>L</em>-phenylalanine (<em>D-</em> or <em>L</em>-Phe) was used as chiral selector to improve the chiral environment, affording the corresponding nanotubular <em>D</em>- and <em>L</em>-CHCPs. Moreover, the combination of the nanotubular CHCP with the chiral selector can exert a significant synergic effect on improving the enantioselectivity, according to the differential pulse voltammetry (DPV). Our findings suggest that the ortho-substitution strategy proposed in this work represents a fundamentally new approach that opens significant opportunities for the manipulation of HCP structures and the enhancement in the specifically functional property of new materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114000"},"PeriodicalIF":4.7,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145789881","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 : 2025-12-17DOI: 10.1016/j.micromeso.2025.114003
Panpan Zhai , Yapeng Li , Zhipan Liu , Zhanling Ma , Dehua Wang , Beibei Gao
A series of hierarchical SAPO-34 molecular sieves were successfully synthesized through the organosilane-assisted method, employing low-cost 3-aminopropyltriethoxysilane (APTES) as a mesoporous template and partial silica source. The influence of APTES content on the crystallinity, pore structures, acidity, and catalytic performance of the products in the methanol-to-olefins (MTO) reaction was systematically investigated by XRD, XRF, SEM, N2 adsorption-desorption, NH3-TPD measurements and a fixed-bed reactor. It revealed that the introduction of APTES created mesopores and simultaneously modulated the acidic properties, notably reducing both the strength and density of strong acid sites. Compared to the conventional microporous SAPO-34-C, the hierarchical SAPO-34 catalysts, particularly SAPO-34-0.1, demonstrated a superior catalytic lifetime and enhanced selectivity to light olefins in the MTO reaction. This performance enhancement could be attributed to their hierarchical pore systems and the moderated acidities. However, excessive APTES addition (SAPO-34-0.2) led to a decline in crystallinity and a consequent reduction in catalytic stability.
{"title":"Low-cost organosilane-assisted synthesis of hierarchical SAPO-34 with improved stability in methanol-to-olefins reaction","authors":"Panpan Zhai , Yapeng Li , Zhipan Liu , Zhanling Ma , Dehua Wang , Beibei Gao","doi":"10.1016/j.micromeso.2025.114003","DOIUrl":"10.1016/j.micromeso.2025.114003","url":null,"abstract":"<div><div>A series of hierarchical SAPO-34 molecular sieves were successfully synthesized through the organosilane-assisted method, employing low-cost 3-aminopropyltriethoxysilane (APTES) as a mesoporous template and partial silica source. The influence of APTES content on the crystallinity, pore structures, acidity, and catalytic performance of the products in the methanol-to-olefins (MTO) reaction was systematically investigated by XRD, XRF, SEM, N<sub>2</sub> adsorption-desorption, NH<sub>3</sub>-TPD measurements and a fixed-bed reactor. It revealed that the introduction of APTES created mesopores and simultaneously modulated the acidic properties, notably reducing both the strength and density of strong acid sites. Compared to the conventional microporous SAPO-34-C, the hierarchical SAPO-34 catalysts, particularly SAPO-34-0.1, demonstrated a superior catalytic lifetime and enhanced selectivity to light olefins in the MTO reaction. This performance enhancement could be attributed to their hierarchical pore systems and the moderated acidities. However, excessive APTES addition (SAPO-34-0.2) led to a decline in crystallinity and a consequent reduction in catalytic stability.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114003"},"PeriodicalIF":4.7,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838953","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 : 2025-12-13DOI: 10.1016/j.micromeso.2025.113998
Yongjin Wang , Ran Hou , Xiaoxia Zhang , Tuanyuan Hou , Junjie Liao , Weiren Bao , Liping Chang
The application of blast furnace gas for combined heat and power generation is constrained by SO2 emissions produced from the combustion of its hydrogen sulfide (H2S) content, requiring deep desulfurization to comply with stringent environmental regulations. Among various desulfurization materials, faujasite (FAU) zeolites exhibit distinct advantages owing to their stable framework and tunable acid-base properties. However, systematic studies on the key factors affecting their H2S adsorption performance are still lacking, especially regarding the structure–activity relationship between framework composition and active sites. To address the aforementioned challenges, in this work, a series of FAU zeolites with systematically varied SiO2/Al2O3 ratios were employed as sorbents for H2S removal. FAU2.7 and FAU5.0 are low-SiO2/Al2O3, Na-type FAU zeolites with high framework Al content. FAU5.4 is obtained via ion exchange of FAU5.0 to the H-type, and high-silica Na-free zeolite sorbents (FAU7.4–FAU111.4) are prepared by steam dealumination of FAU5.0, using breakthrough experiments, XRD, Py-FTIR, NH3-TPD, CO2-TPD, and in situ FTIR to analyze desulfurization behavior from the perspectives of Lewis acid site (LAS) density, thermal stability, and dissociative chemisorption mechanism. The results indicate that zeolites with a low SiO2/Al2O3 ratio, such as FAU2.7, which possess high Al framework content and abundant thermally stable LAS, can achieve dissociative adsorption of H2S into HS− and H+. These species are then chemically fixed through acid–base synergism, yielding a breakthrough sulfur capacity (QBSC) of up to 836 mg S/100 g. In contrast, high SiO2/Al2O3 zeolites suffer from severe framework dealumination and drastically reduced acid site density, relying primarily on weak physisorption and failing to stabilize sulfur species, with a significantly reduced QBSC of 7 mg S/100 g. A positive correlation was established between the LAS and the QBSC value. This study reveals the intrinsic relationship between the acidic site configuration of FAU zeolites and the dissociative adsorption of H2S, providing theoretical guidance for the rational design of high-performance desulfurization sorbents.
{"title":"SiO2/Al2O3 ratio modulated Lewis acidity governs H2S adsorption on FAU zeolites","authors":"Yongjin Wang , Ran Hou , Xiaoxia Zhang , Tuanyuan Hou , Junjie Liao , Weiren Bao , Liping Chang","doi":"10.1016/j.micromeso.2025.113998","DOIUrl":"10.1016/j.micromeso.2025.113998","url":null,"abstract":"<div><div>The application of blast furnace gas for combined heat and power generation is constrained by SO<sub>2</sub> emissions produced from the combustion of its hydrogen sulfide (H<sub>2</sub>S) content, requiring deep desulfurization to comply with stringent environmental regulations. Among various desulfurization materials, faujasite (FAU) zeolites exhibit distinct advantages owing to their stable framework and tunable acid-base properties. However, systematic studies on the key factors affecting their H<sub>2</sub>S adsorption performance are still lacking, especially regarding the structure–activity relationship between framework composition and active sites. To address the aforementioned challenges, in this work, a series of FAU zeolites with systematically varied SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratios were employed as sorbents for H<sub>2</sub>S removal. FAU<sub>2.7</sub> and FAU<sub>5.0</sub> are low-SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub>, Na-type FAU zeolites with high framework Al content. FAU<sub>5.4</sub> is obtained via ion exchange of FAU<sub>5.0</sub> to the H-type, and high-silica Na-free zeolite sorbents (FAU<sub>7.4</sub>–FAU<sub>111.4</sub>) are prepared by steam dealumination of FAU<sub>5.0</sub>, using breakthrough experiments, XRD, Py-FTIR, NH<sub>3</sub>-TPD, CO<sub>2</sub>-TPD, and in situ FTIR to analyze desulfurization behavior from the perspectives of Lewis acid site (LAS) density, thermal stability, and dissociative chemisorption mechanism. The results indicate that zeolites with a low SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratio, such as FAU<sub>2.7</sub>, which possess high Al framework content and abundant thermally stable LAS, can achieve dissociative adsorption of H<sub>2</sub>S into HS<sup>−</sup> and H<sup>+</sup>. These species are then chemically fixed through acid–base synergism, yielding a breakthrough sulfur capacity (Q<sub>BSC</sub>) of up to 836 mg S/100 g. In contrast, high SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> zeolites suffer from severe framework dealumination and drastically reduced acid site density, relying primarily on weak physisorption and failing to stabilize sulfur species, with a significantly reduced Q<sub>BSC</sub> of 7 mg S/100 g. A positive correlation was established between the LAS and the Q<sub>BSC</sub> value. This study reveals the intrinsic relationship between the acidic site configuration of FAU zeolites and the dissociative adsorption of H<sub>2</sub>S, providing theoretical guidance for the rational design of high-performance desulfurization sorbents.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113998"},"PeriodicalIF":4.7,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787341","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 : 2025-12-13DOI: 10.1016/j.micromeso.2025.113982
Jianwen Lan , Shuang Liu , Jiayang Zhang, Yang Cheng, Xu Yang
A nitrogen-enriched Zn-based metal-organic framework Zn-MA-Htdc-RT was facilely synthesized via a room-temperature method, wherein easily removable ammonium hydroxide served as the deprotonating agent. Compared with the conventional solvothermal method and other widely adopted room-temperature synthesis strategies, this approach remarkably shortened the preparation cycle to 2 h, featuring prominent advantages of energy efficiency and environmental benignity. Endowed with amine groups (Lewis base sites) and Zn metal centers (Lewis acid sites), Zn-MA-Htdc-RT exhibited excellent catalytic performance in the cycloaddition reaction of CO2 with epoxides. Under mild and solvent-free conditions (60 °C, 1.0 MPa CO2, 6 h), the yield of propylene carbonate (PC) reached up to 99 % with full conversion. Notably, even at room temperature, an impressive PC yield of 87 % could be achieved by extending the reaction time to 24 h. Furthermore, Zn-MA-Htdc-RT demonstrated satisfactory reusability and broad applicability towards various epoxide substrates. Collectively, this green, rapid, and room-temperature synthetic route for the high-performance nitrogen-rich Zn-MA-Htdc-RT provides a competitive alternative for the capture and utilization of CO2.
{"title":"The room-temperature and rapid synthesis of nitrogen-rich metal organic framework for effectively catalyzing the CO2 cycloaddition with epoxides","authors":"Jianwen Lan , Shuang Liu , Jiayang Zhang, Yang Cheng, Xu Yang","doi":"10.1016/j.micromeso.2025.113982","DOIUrl":"10.1016/j.micromeso.2025.113982","url":null,"abstract":"<div><div>A nitrogen-enriched Zn-based metal-organic framework Zn-MA-Htdc-RT was facilely synthesized via a room-temperature method, wherein easily removable ammonium hydroxide served as the deprotonating agent. Compared with the conventional solvothermal method and other widely adopted room-temperature synthesis strategies, this approach remarkably shortened the preparation cycle to 2 h, featuring prominent advantages of energy efficiency and environmental benignity. Endowed with amine groups (Lewis base sites) and Zn metal centers (Lewis acid sites), Zn-MA-Htdc-RT exhibited excellent catalytic performance in the cycloaddition reaction of CO<sub>2</sub> with epoxides. Under mild and solvent-free conditions (60 °C, 1.0 MPa CO<sub>2</sub>, 6 h), the yield of propylene carbonate (PC) reached up to 99 % with full conversion. Notably, even at room temperature, an impressive PC yield of 87 % could be achieved by extending the reaction time to 24 h. Furthermore, Zn-MA-Htdc-RT demonstrated satisfactory reusability and broad applicability towards various epoxide substrates. Collectively, this green, rapid, and room-temperature synthetic route for the high-performance nitrogen-rich Zn-MA-Htdc-RT provides a competitive alternative for the capture and utilization of CO<sub>2</sub>.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113982"},"PeriodicalIF":4.7,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787340","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 : 2025-12-13DOI: 10.1016/j.micromeso.2025.113996
Manjula M. Kandage, Michal Marszewski
High-entropy oxides (HEOs) are rapidly finding applications in catalysis, energy storage, and energy conversion, thanks to their unique properties, such as high compositional complexity, diversity of chemical environments in the material and on its surface, as well as a high potential for synergistic and cocktail effects. However, as HEOs are frequently synthesized using solids-state or similar high-temperature methods, they also feature rather low surface areas and pore volumes, which negatively impacts their performance in applications involving surface and interface phenomena. The present work demonstrates two extensions to the Pechini-type synthesis of high-entropy oxides that aim to afford mesoporous HEOs with well-developed pore structures. Five example HEOs, with varied compositions and structures, were used as model HEOs, including fluorite (Gd0.2La0.2Y0.2Hf0.2Zr0.2)O2-x, spinel (Al1/6Co1/6Cr1/6Fe1/6Mn1/6Ni1/6)3O4, perovskite (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3, perovskite (Na0.2K0.2Ca0.2La0.2Ce0.2)TiO3, and rock-salt (Co0.2Cu0.2Mg0.2Ni0.2Zn0.2)O. These HEOs were tested in (i) a hard-templating Pechini synthesis with Ludox SM-AS colloidal silica as the template and (ii) a two-step Pechini synthesis with the carbon template generated in-situ, and compared with HEOs synthesized using the original Pechini-type synthesis. Both extensions successfully afforded mesoporous HEOs with well-developed pore structures, with the former method affording materials with specific surface areas up to 142 m2 g–1 and total pore volumes up to 0.19 cm3 g–1 while the latter up to 164 m2 g–1 and 0.25 cm3 g–1, respectively. Both strategies have similar set of limitations, including low crystallinity and limited compatibility. Thus, both methods seem to be complimentary strategies for the synthesis of mesoporous HEOs, chosen mainly based on the compatibility with the target HEO.
{"title":"Extension of Pechini synthesis of high-entropy oxides: Preparation of mesoporous high-entropy materials","authors":"Manjula M. Kandage, Michal Marszewski","doi":"10.1016/j.micromeso.2025.113996","DOIUrl":"10.1016/j.micromeso.2025.113996","url":null,"abstract":"<div><div>High-entropy oxides (HEOs) are rapidly finding applications in catalysis, energy storage, and energy conversion, thanks to their unique properties, such as high compositional complexity, diversity of chemical environments in the material and on its surface, as well as a high potential for synergistic and cocktail effects. However, as HEOs are frequently synthesized using solids-state or similar high-temperature methods, they also feature rather low surface areas and pore volumes, which negatively impacts their performance in applications involving surface and interface phenomena. The present work demonstrates two extensions to the Pechini-type synthesis of high-entropy oxides that aim to afford mesoporous HEOs with well-developed pore structures. Five example HEOs, with varied compositions and structures, were used as model HEOs, including fluorite (Gd<sub>0.2</sub>La<sub>0.2</sub>Y<sub>0.2</sub>Hf<sub>0.2</sub>Zr<sub>0.2</sub>)O<sub>2-x</sub>, spinel (Al<sub>1/6</sub>Co<sub>1/6</sub>Cr<sub>1/6</sub>Fe<sub>1/6</sub>Mn<sub>1/6</sub>Ni<sub>1/6</sub>)<sub>3</sub>O<sub>4</sub>, perovskite (Na<sub>0.2</sub>Bi<sub>0.2</sub>Ba<sub>0.2</sub>Sr<sub>0.2</sub>Ca<sub>0.2</sub>)TiO<sub>3</sub>, perovskite (Na<sub>0.2</sub>K<sub>0.2</sub>Ca<sub>0.2</sub>La<sub>0.2</sub>Ce<sub>0.2</sub>)TiO<sub>3</sub>, and rock-salt (Co<sub>0.2</sub>Cu<sub>0.2</sub>Mg<sub>0.2</sub>Ni<sub>0.2</sub>Zn<sub>0.2</sub>)O. These HEOs were tested in (i) a hard-templating Pechini synthesis with Ludox SM-AS colloidal silica as the template and (ii) a two-step Pechini synthesis with the carbon template generated in-situ, and compared with HEOs synthesized using the original Pechini-type synthesis. Both extensions successfully afforded mesoporous HEOs with well-developed pore structures, with the former method affording materials with specific surface areas up to 142 m<sup>2</sup> g<sup>–1</sup> and total pore volumes up to 0.19 cm<sup>3</sup> g<sup>–1</sup> while the latter up to 164 m<sup>2</sup> g<sup>–1</sup> and 0.25 cm<sup>3</sup> g<sup>–1</sup>, respectively. Both strategies have similar set of limitations, including low crystallinity and limited compatibility. Thus, both methods seem to be complimentary strategies for the synthesis of mesoporous HEOs, chosen mainly based on the compatibility with the target HEO.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113996"},"PeriodicalIF":4.7,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787342","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 : 2025-12-11DOI: 10.1016/j.micromeso.2025.113993
Anna A. Lysova, Konstantin A. Kovalenko, Anton S. Nizovtsev, Danil N. Dybtsev, Vladimir P. Fedin
C3H6 adsorption on a family of NIIC-20-G (G = glycol) MOFs is carried out. The C3H6 adsorption capacities at 1 bar vary from 109.3 to 168 ml⋅g−1 (273 K) and from 74.2 to 113.3 ml⋅g−1 (298 K), depending on the nature of G. The following highest IAST adsorption selectivity values (S) are obtained at 298 K, 1:1 gas mixture, 1 bar: S(C3H6/CO2) = 7.4, S(C3H6/CH4) = 587.0, S(C3H6/C2H6) = 4.4, S(C3H6/C2H4) = 7.0, S(C3H8/C3H6) = 2.1. The isosteric heats of the C3H6 adsorption range from 32.4 to 38.0 kJ∙mol−1, which are lower than that of C3H8, suggesting enthalpy-driven preferential adsorption of propane over propylene. Theoretical DFT and GCMC calculations support the experimental results and provide more detailed information on the nature of adsorption centers of propane and propylene molecules. Multiple breakthrough separation experiments are carried out for NIIC-20-Pr (Pr = propyleneglycol) using different C3H6/C2H4 and C3H8/C3H6 gas mixtures. The productivity of ethylene ranges from 2.60 to 2.94 mol∙kg−1, the propylene productivity is 0.56 mol kg−1. Given the remarkable fundamental adsorption characteristics, the NIIC-20-G porous materials should be considered among the best solutions for efficient and economically viable separation of industrially important gas mixtures.
{"title":"Tunable selective adsorption and efficient purification of propylene on a series of mesoporous metal-organic frameworks","authors":"Anna A. Lysova, Konstantin A. Kovalenko, Anton S. Nizovtsev, Danil N. Dybtsev, Vladimir P. Fedin","doi":"10.1016/j.micromeso.2025.113993","DOIUrl":"10.1016/j.micromeso.2025.113993","url":null,"abstract":"<div><div>C<sub>3</sub>H<sub>6</sub> adsorption on a family of <strong>NIIC-20-G</strong> (G = glycol) MOFs is carried out. The C<sub>3</sub>H<sub>6</sub> adsorption capacities at 1 bar vary from 109.3 to 168 ml⋅g<sup>−1</sup> (273 K) and from 74.2 to 113.3 ml⋅g<sup>−1</sup> (298 K), depending on the nature of G. The following highest IAST adsorption selectivity values (<em>S</em>) are obtained at 298 K, 1:1 gas mixture, 1 bar: <em>S</em>(C<sub>3</sub>H<sub>6</sub>/CO<sub>2</sub>) = 7.4, <em>S</em>(C<sub>3</sub>H<sub>6</sub>/CH<sub>4</sub>) = 587.0, <em>S</em>(C<sub>3</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>6</sub>) = 4.4, <em>S</em>(C<sub>3</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub>) = 7.0, <em>S</em>(C<sub>3</sub>H<sub>8</sub>/C<sub>3</sub>H<sub>6</sub>) = 2.1. The isosteric heats of the C<sub>3</sub>H<sub>6</sub> adsorption range from 32.4 to 38.0 kJ∙mol<sup>−1</sup>, which are lower than that of C<sub>3</sub>H<sub>8</sub>, suggesting enthalpy-driven preferential adsorption of propane over propylene. Theoretical DFT and GCMC calculations support the experimental results and provide more detailed information on the nature of adsorption centers of propane and propylene molecules. Multiple breakthrough separation experiments are carried out for <strong>NIIC-20-Pr</strong> (Pr = propyleneglycol) using different C<sub>3</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> and C<sub>3</sub>H<sub>8</sub>/C<sub>3</sub>H<sub>6</sub> gas mixtures. The productivity of ethylene ranges from 2.60 to 2.94 mol∙kg<sup>−1</sup>, the propylene productivity is 0.56 mol kg<sup>−1</sup>. Given the remarkable fundamental adsorption characteristics, the <strong>NIIC-20-G</strong> porous materials should be considered among the best solutions for efficient and economically viable separation of industrially important gas mixtures.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113993"},"PeriodicalIF":4.7,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734084","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 : 2025-12-11DOI: 10.1016/j.micromeso.2025.113995
Fatma Yelda Ünlü , Melih Beşir Arvas , Hadi Jahangiri , Hasan Gökçe , Nilüfer Koçyiğit , İbrahim Özçeşmeci , Caner Ünlü
Simple, in situ routes to tune ZIF-8 particle size, interfacial chemistry, and redox functionality—without post-processing—remain limited. In this work, we present a single-step, in situ phthalocyanine (Pc) additive strategy that modulates ZIF-8 crystallization. Without carbonization or extra processing, the approach reduces particle size, adjusts surface/near-surface chemistry, and—when metalated Pc is used—yields a persistent interfacial redox signature. Under identical activation, N2 sorption retained the microporous ZIF-8 response while developing a hierarchical-like texture consistent with slit-like/interaggregate voids. Detailed surface analysis indicated that Pc was located at or near interfaces with preservation of the sodalite framework. Electrochemical measurements under identical conditions indicated an enhanced interfacial response relative to pristine ZIF-8. Overall, phthalocyanine-guided growth offers a practical, modular handle to tune particle size, interfacial chemistry, and interfacial redox in ZIF-8 using a simple drop-in molecular additive, relevant to adsorption and other transport-limited applications.
{"title":"Molecular additive control of MOF crystallization: effect of phthalocyanine on size and interfacial redox response of ZIF-8","authors":"Fatma Yelda Ünlü , Melih Beşir Arvas , Hadi Jahangiri , Hasan Gökçe , Nilüfer Koçyiğit , İbrahim Özçeşmeci , Caner Ünlü","doi":"10.1016/j.micromeso.2025.113995","DOIUrl":"10.1016/j.micromeso.2025.113995","url":null,"abstract":"<div><div>Simple, in situ routes to tune ZIF-8 particle size, interfacial chemistry, and redox functionality—without post-processing—remain limited. In this work, we present a single-step, in situ phthalocyanine (Pc) additive strategy that modulates ZIF-8 crystallization. Without carbonization or extra processing, the approach reduces particle size, adjusts surface/near-surface chemistry, and—when metalated Pc is used—yields a persistent interfacial redox signature. Under identical activation, N<sub>2</sub> sorption retained the microporous ZIF-8 response while developing a hierarchical-like texture consistent with slit-like/interaggregate voids. Detailed surface analysis indicated that Pc was located at or near interfaces with preservation of the sodalite framework. Electrochemical measurements under identical conditions indicated an enhanced interfacial response relative to pristine ZIF-8. Overall, phthalocyanine-guided growth offers a practical, modular handle to tune particle size, interfacial chemistry, and interfacial redox in ZIF-8 using a simple drop-in molecular additive, relevant to adsorption and other transport-limited applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113995"},"PeriodicalIF":4.7,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734047","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 : 2025-12-11DOI: 10.1016/j.micromeso.2025.113989
Yajuan Tu , Yuxin Hou , Xinyang He , Ming Ouyang , Ruoyi Chen , Xiang Wang , Xingyun Guan , Peng Liu , Mingli Fu , Steven L. Suib , Pingxiao Wu , Daiqi Ye
Natural nanofibrous palygorskite with micropores, nanotubular halloysite with mesopores, and disc-shaped diatomite with macropores exhibit distinct advantages in dispersing metal oxide particles due to their regular porosity, mechanical adhesion, and thermal stability. Three natural porous minerals with typical morphology were employed as supports for Cu-Co oxides in the catalytic oxidation of butyl acetate. XRD and Raman reveal that spinel-structured Cu0.72Co2.28O4 and tenorite-structured CuO are main phases on three supports, while SEM and TEM suggest that halloysite and palygorskite are better than diatomite in dispersing Cu-Co oxide particles. Due to high dispersion, superior reducibility, and moderate Co3+-O2-, the halloysite-supported Cu-Co oxides exhibit the lowest T50 of butyl acetate conversion at 232 °C among three supported catalysts. Natural porous supports modulate the spinel lattice, improve the adsorption of butyl acetate, provide surface hydroxyls in oxidation, and enhance the thermal stability of Cu-Co oxides. The gaseous O2 supplements the surface chemisorbed oxygen and lattice oxygen, which participate in the complete oxidation of butyl acetate. Above results indicate that natural porous minerals are potential supports to transition metal oxides for VOCs oxidation.
{"title":"Cu-Co oxides supported on porous minerals for catalytic oxidation of butyl acetate: Particle dispersion, catalytic performance, and oxidation mechanism","authors":"Yajuan Tu , Yuxin Hou , Xinyang He , Ming Ouyang , Ruoyi Chen , Xiang Wang , Xingyun Guan , Peng Liu , Mingli Fu , Steven L. Suib , Pingxiao Wu , Daiqi Ye","doi":"10.1016/j.micromeso.2025.113989","DOIUrl":"10.1016/j.micromeso.2025.113989","url":null,"abstract":"<div><div>Natural nanofibrous palygorskite with micropores, nanotubular halloysite with mesopores, and disc-shaped diatomite with macropores exhibit distinct advantages in dispersing metal oxide particles due to their regular porosity, mechanical adhesion, and thermal stability. Three natural porous minerals with typical morphology were employed as supports for Cu-Co oxides in the catalytic oxidation of butyl acetate. XRD and Raman reveal that spinel-structured Cu<sub>0.72</sub>Co<sub>2.28</sub>O<sub>4</sub> and tenorite-structured CuO are main phases on three supports, while SEM and TEM suggest that halloysite and palygorskite are better than diatomite in dispersing Cu-Co oxide particles. Due to high dispersion, superior reducibility, and moderate Co<sup>3+</sup>-O<sup>2-</sup>, the halloysite-supported Cu-Co oxides exhibit the lowest T<sub>50</sub> of butyl acetate conversion at 232 °C among three supported catalysts. Natural porous supports modulate the spinel lattice, improve the adsorption of butyl acetate, provide surface hydroxyls in oxidation, and enhance the thermal stability of Cu-Co oxides. The gaseous O<sub>2</sub> supplements the surface chemisorbed oxygen and lattice oxygen, which participate in the complete oxidation of butyl acetate. Above results indicate that natural porous minerals are potential supports to transition metal oxides for VOCs oxidation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113989"},"PeriodicalIF":4.7,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734049","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 : 2025-12-10DOI: 10.1016/j.micromeso.2025.113990
G. Guicheney , S. Dorge , H. Nouali , B. Lebeau , Philippe Fioux , M. Soulard , J. Patarin , M. Molière , M. Vierling , A.C. Houdon , J.F. Brilhac
In order to reduce the negative impact of water vapor on the cyclic SO2 adsorption performance of a CuO/SBA-15 material, the addition of CeO2 to the copper active phase was performed at different Ce/Cu molar ratios and temperatures of the adsorption/regeneration cycles. The addition of CeO2 to the CuO/SBA15 adsorbent with a Ce/Cu molar ratio of 0.68 increases the SO2 adsorption capacity at the breakthrough by a factor of 3.4 (387 mgSO2/gCuO vs 114 mgSO2/gCuO) with good performance over 20 cycles of SO2 adsorption/regeneration under wet conditions at 450 °C. These enhancements are explained by a synergy effect between CuO and CeO2 on the SO2 adsorption reactions and a substantial decrease in the migration of the CuO active phase during adsorption/regeneration cycles under water vapor.
为了降低水蒸气对CuO/SBA-15材料循环SO2吸附性能的负面影响，在不同的Ce/Cu摩尔比和吸附/再生循环温度下，对铜活性相进行了CeO2的添加。在Ce/Cu摩尔比为0.68的CuO/SBA15吸附剂中添加CeO2，在突破处的SO2吸附量增加了3.4倍（387 mgSO2/gCuO vs 114 mgSO2/gCuO），并在450℃湿条件下进行了20次SO2吸附/再生。这些增强可以解释为CuO和CeO2在SO2吸附反应中的协同作用，以及在水蒸气下吸附/再生循环中CuO活性相迁移的显著减少。
{"title":"Influence of the CeO2 addition on the CuO/SBA-15 adsorbent performance for a DeSOx process under wet conditions","authors":"G. Guicheney , S. Dorge , H. Nouali , B. Lebeau , Philippe Fioux , M. Soulard , J. Patarin , M. Molière , M. Vierling , A.C. Houdon , J.F. Brilhac","doi":"10.1016/j.micromeso.2025.113990","DOIUrl":"10.1016/j.micromeso.2025.113990","url":null,"abstract":"<div><div>In order to reduce the negative impact of water vapor on the cyclic SO<sub>2</sub> adsorption performance of a CuO/SBA-15 material, the addition of CeO<sub>2</sub> to the copper active phase was performed at different Ce/Cu molar ratios and temperatures of the adsorption/regeneration cycles. The addition of CeO<sub>2</sub> to the CuO/SBA15 adsorbent with a Ce/Cu molar ratio of 0.68 increases the SO<sub>2</sub> adsorption capacity at the breakthrough by a factor of 3.4 (387 mg<sub>SO2</sub>/g<sub>CuO</sub> vs 114 mg<sub>SO2</sub>/g<sub>CuO</sub>) with good performance over 20 cycles of SO<sub>2</sub> adsorption/regeneration under wet conditions at 450 °C. These enhancements are explained by a synergy effect between CuO and CeO<sub>2</sub> on the SO<sub>2</sub> adsorption reactions and a substantial decrease in the migration of the CuO active phase during adsorption/regeneration cycles under water vapor.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113990"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787307","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 : 2025-12-10DOI: 10.1016/j.micromeso.2025.113992
Alejandro Suárez-Méndez , Fernanda Castelán-González , Rubén Mendoza-Cruz , Lázaro Huerta , Jonas S. Albuquerque , Gustavo A. Fuentes , Tatiana E. Klimova
NiPt catalysts supported on SAPO-11 zeolite were synthesized with the aim to inquire into the influence of the support's Si/Al molar ratio (0.075–0.60) on the activity and selectivity of the catalysts in the hydrodeoxygenation of anisole. An increase in Si content led to a reduction in the crystallinity of SAPO-11, attributed to the higher number of SiO2 islands (extra-framework silica species). Acidity of supports and catalysts passed through the maximum at a Si/Al molar ratio of 0.15 and then decreased with further increase in Si/Al ratio. All the NiPt/SAPO-11 catalysts demonstrated high activity in the hydrodeoxygenation of anisole in a batch reactor at 250 °C and 6.8 MPa of H2 pressure, achieving conversions of 96–98 % at 6 h reaction time. The best activity results were obtained with the NiPt/SAPO-11 catalysts with Si/Al molar ratios in the supports between 0.30 and 0.60. Supports with lower Si/Al molar ratios (0.075 and 0.15) resulted in lower activity, which was attributed to an increase in the fraction of NiAl2O4 with Ni2+ species non-reducible upon the activation conditions used (400 °C, 4 h). Regarding selectivity to cyclohexane, catalysts with intermediate Si/Al ratios (0.15–0.45) exhibited higher selectivity (∼94–96 %) than other catalysts, attributed to their elevated acidity as measured by temperature-programmed desorption of ammonia. Finally, the experimental data were fitted to a kinetic model that considered the hydrogenation-deoxygenation pathway, correlating the kinetic constants with the metal-acid characteristics of the catalysts, namely, the amount of reduced Ni and total amount of acid sites.
{"title":"NiPt/SAPO-11 catalysts for hydrodeoxygenation of anisole to cyclohexane: effect of the support's Si/al molar ratio on catalytic performance","authors":"Alejandro Suárez-Méndez , Fernanda Castelán-González , Rubén Mendoza-Cruz , Lázaro Huerta , Jonas S. Albuquerque , Gustavo A. Fuentes , Tatiana E. Klimova","doi":"10.1016/j.micromeso.2025.113992","DOIUrl":"10.1016/j.micromeso.2025.113992","url":null,"abstract":"<div><div>NiPt catalysts supported on SAPO-11 zeolite were synthesized with the aim to inquire into the influence of the support's Si/Al molar ratio (0.075–0.60) on the activity and selectivity of the catalysts in the hydrodeoxygenation of anisole. An increase in Si content led to a reduction in the crystallinity of SAPO-11, attributed to the higher number of SiO<sub>2</sub> islands (extra-framework silica species). Acidity of supports and catalysts passed through the maximum at a Si/Al molar ratio of 0.15 and then decreased with further increase in Si/Al ratio. All the NiPt/SAPO-11 catalysts demonstrated high activity in the hydrodeoxygenation of anisole in a batch reactor at 250 °C and 6.8 MPa of H<sub>2</sub> pressure, achieving conversions of 96–98 % at 6 h reaction time. The best activity results were obtained with the NiPt/SAPO-11 catalysts with Si/Al molar ratios in the supports between 0.30 and 0.60. Supports with lower Si/Al molar ratios (0.075 and 0.15) resulted in lower activity, which was attributed to an increase in the fraction of NiAl<sub>2</sub>O<sub>4</sub> with Ni<sup>2+</sup> species non-reducible upon the activation conditions used (400 °C, 4 h). Regarding selectivity to cyclohexane, catalysts with intermediate Si/Al ratios (0.15–0.45) exhibited higher selectivity (∼94–96 %) than other catalysts, attributed to their elevated acidity as measured by temperature-programmed desorption of ammonia. Finally, the experimental data were fitted to a kinetic model that considered the hydrogenation-deoxygenation pathway, correlating the kinetic constants with the metal-acid characteristics of the catalysts, namely, the amount of reduced Ni and total amount of acid sites.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113992"},"PeriodicalIF":4.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734085","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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