Pub Date : 2025-04-01DOI: 10.1016/j.micromeso.2025.113622
Zi-Yue Liu , Jiang-wen Yan , Qianji Han , Jin-Can Zhao , Lei Liu , Ruihan Wang , Shan-Qing Yang , Jian-Long Du
SF6 has been widely used as an insulating medium, but it can also cause serious greenhouse effect. The efficient separation of SF6 appears very important and challenging. A stable and scalable synthesis of Al-MOF (MOF-303) is reported in the present work, which possesses an appropriate pore size (6.79 Å) that matches the dynamic diameter of SF6 molecules (5.2 Å). MOF-303 shows a higher adsorption capacity of SF6 (49.70 cm3/g) at low pressure (10 kPa) and ambient temperature, and the excellent adsorption selectivity of SF6/N2 (10:90) achieves 183.37 at ambient conditions. Meanwhile, breakthrough experiments exhibit that MOF-303 can efficiently separate high purify SF6 form SF6/N2 mixtures at ambient conditions. The relevant experimental conclusions have been further verified by theoretical calculations. The stronger binding energy between MOF-303 and SF6 molecule should be responsible for the efficient SF6 adsorption and separation. More importantly, the adsorption capacity of SF6 by the particle sample has decreased, but it still exhibits excellent gas separation ability. The results will contribute to the design efficient and practical gas separation materials.
{"title":"A stable Al-MOF based on pore size control strategy for efficient SF6/N2 separation","authors":"Zi-Yue Liu , Jiang-wen Yan , Qianji Han , Jin-Can Zhao , Lei Liu , Ruihan Wang , Shan-Qing Yang , Jian-Long Du","doi":"10.1016/j.micromeso.2025.113622","DOIUrl":"10.1016/j.micromeso.2025.113622","url":null,"abstract":"<div><div>SF<sub>6</sub> has been widely used as an insulating medium, but it can also cause serious greenhouse effect. The efficient separation of SF<sub>6</sub> appears very important and challenging. A stable and scalable synthesis of Al-MOF (MOF-303) is reported in the present work, which possesses an appropriate pore size (6.79 Å) that matches the dynamic diameter of SF<sub>6</sub> molecules (5.2 Å). MOF-303 shows a higher adsorption capacity of SF<sub>6</sub> (49.70 cm<sup>3</sup>/g) at low pressure (10 kPa) and ambient temperature, and the excellent adsorption selectivity of SF<sub>6</sub>/N<sub>2</sub> (10:90) achieves 183.37 at ambient conditions. Meanwhile, breakthrough experiments exhibit that MOF-303 can efficiently separate high purify SF<sub>6</sub> form SF<sub>6</sub>/N<sub>2</sub> mixtures at ambient conditions. The relevant experimental conclusions have been further verified by theoretical calculations. The stronger binding energy between MOF-303 and SF<sub>6</sub> molecule should be responsible for the efficient SF<sub>6</sub> adsorption and separation. More importantly, the adsorption capacity of SF<sub>6</sub> by the particle sample has decreased, but it still exhibits excellent gas separation ability. The results will contribute to the design efficient and practical gas separation materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113622"},"PeriodicalIF":4.8,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783547","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}
The phenol hydroxylation reaction represents a promising green strategy for the sustainable production of dihydroxybenzene. However, the high cost and mass transfer limitations associated with traditional titanium silicalite-1 (TS-1) catalysts significantly hinder their industrial scalability. In this study, a novel chelating-agent-protected technique, combined with a tetrapropylammonium hydroxide (TPAOH) hydrothermal treatment strategy, was developed to achieve the uniform incorporation of nickel ions into the TS-1 framework. This dual approach effectively redistributed the charge density, modulated the surface acidity, and introduced hierarchical structures, thereby addressing the intrinsic diffusion and catalytic limitations of conventional microporous TS-1. Unlike conventional nickel modification methods, the chelating-agent-protected strategy successfully prevented nickel ion reduction or the formation of nickel oxide particles, ensuring highly dispersed and framework-integrated nickel species. The incorporation of nickel further enhanced the synergistic interaction with titanium, significantly reducing the binding energy of tetrahedral framework titanium (Ti4+) and enhancing the electrophilicity of active catalytic sites. These structural and electronic improvements translated into superior catalytic performance, with the framework-engineered nickel-modified catalyst (CSD(1.68)@HTS-1) achieving a phenol conversion rate of 31.0 %, compared to 25.3 % for unmodified HTS-1. Furthermore, the selectivity for hydroquinone increased from 57.8 % to 59.3 %. The CSD(1.68)@HTS-1 catalyst also demonstrated excellent structural stability and recyclability, maintaining consistent activity and selectivity over multiple reaction cycles. This innovative framework-engineering strategy provides a cost-effective and scalable approach for the design of high-performance nickel-modified zeolite catalysts, offering new insights into the development of sustainable and efficient catalytic systems for industrial applications.
{"title":"Chelating-agent-protected nickel incorporation into TS-1 framework for enhanced phenol hydroxylation catalysis with improved stability and efficiency","authors":"Zhitao Lv , Siyu Zhang , Yufei Zhou , Jiebai Li , Guangguang Guan , Yilai Jiao","doi":"10.1016/j.micromeso.2025.113611","DOIUrl":"10.1016/j.micromeso.2025.113611","url":null,"abstract":"<div><div>The phenol hydroxylation reaction represents a promising green strategy for the sustainable production of dihydroxybenzene. However, the high cost and mass transfer limitations associated with traditional titanium silicalite-1 (TS-1) catalysts significantly hinder their industrial scalability. In this study, a novel chelating-agent-protected technique, combined with a tetrapropylammonium hydroxide (TPAOH) hydrothermal treatment strategy, was developed to achieve the uniform incorporation of nickel ions into the TS-1 framework. This dual approach effectively redistributed the charge density, modulated the surface acidity, and introduced hierarchical structures, thereby addressing the intrinsic diffusion and catalytic limitations of conventional microporous TS-1. Unlike conventional nickel modification methods, the chelating-agent-protected strategy successfully prevented nickel ion reduction or the formation of nickel oxide particles, ensuring highly dispersed and framework-integrated nickel species. The incorporation of nickel further enhanced the synergistic interaction with titanium, significantly reducing the binding energy of tetrahedral framework titanium (Ti<sup>4+</sup>) and enhancing the electrophilicity of active catalytic sites. These structural and electronic improvements translated into superior catalytic performance, with the framework-engineered nickel-modified catalyst (CSD(1.68)@HTS-1) achieving a phenol conversion rate of 31.0 %, compared to 25.3 % for unmodified HTS-1. Furthermore, the selectivity for hydroquinone increased from 57.8 % to 59.3 %. The CSD(1.68)@HTS-1 catalyst also demonstrated excellent structural stability and recyclability, maintaining consistent activity and selectivity over multiple reaction cycles. This innovative framework-engineering strategy provides a cost-effective and scalable approach for the design of high-performance nickel-modified zeolite catalysts, offering new insights into the development of sustainable and efficient catalytic systems for industrial applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113611"},"PeriodicalIF":4.8,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739154","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 : 2025-03-26DOI: 10.1016/j.micromeso.2025.113619
Sina Neshati, Zaher Hashisho
The study explores the effectiveness of metal-organic frameworks (MOFs) in capturing volatile organic compounds (VOCs). Specifically, it investigates the effect of polarity and aromaticity of VOCs on their adsorption behavior on two MOFs, CuBTC and FeBTC. Cyclic adsorption breakthroughs and isotherms were completed using toluene, 2-methylpyridine, n-hexane, and 2-methyl-2-butanol as adsorbates to assess the frameworks' adsorption and regeneration capabilities. X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetry analysis, Fourier transform infrared spectroscopy and nitrogen adsorption/desorption isotherm were used to evaluate the MOFs' crystallinity, thermal stability, and surface properties. The results suggest that CuBTC demonstrates superior adsorption capabilities for all tested VOCs, due to its larger surface area and higher crystallinity. However, FeBTC has a broader pore sizes, allowing faster VOC mass transfer rates and accommodating larger molecules, albeit with slightly lower adsorption capacities. Notably, VOCs with polar and aromatic properties, such as 2-methylpyridine, exhibited higher adsorption levels due to increased π-π interactions within the frameworks. However, regeneration of 2-methylpyridine was challenging due to chemisorption, forming strong, irreversible metal–nitrogen coordination bonds. Toluene and 2-methyl-2-bustanol showed similar adsorption capacities and could be effectively regenerated, indicating physisorption mechanisms involving π–π interactions and polar interactions, respectively. N-hexane exhibited the lowest adsorption capacities, relying on weaker van der Waals forces. These results highlight the promising potential of CuBTC and FeBTC in mitigating air pollution. The research also offers valuable insights for tailoring MOFs to contaminants' molecular properties, and advances our understanding of MOF applications in air quality engineering.
{"title":"Adsorption dynamics of aromatic and polar volatile organic compounds on metal-organic frameworks","authors":"Sina Neshati, Zaher Hashisho","doi":"10.1016/j.micromeso.2025.113619","DOIUrl":"10.1016/j.micromeso.2025.113619","url":null,"abstract":"<div><div>The study explores the effectiveness of metal-organic frameworks (MOFs) in capturing volatile organic compounds (VOCs). Specifically, it investigates the effect of polarity and aromaticity of VOCs on their adsorption behavior on two MOFs, CuBTC and FeBTC. Cyclic adsorption breakthroughs and isotherms were completed using toluene, 2-methylpyridine, n-hexane, and 2-methyl-2-butanol as adsorbates to assess the frameworks' adsorption and regeneration capabilities. X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetry analysis, Fourier transform infrared spectroscopy and nitrogen adsorption/desorption isotherm were used to evaluate the MOFs' crystallinity, thermal stability, and surface properties. The results suggest that CuBTC demonstrates superior adsorption capabilities for all tested VOCs, due to its larger surface area and higher crystallinity. However, FeBTC has a broader pore sizes, allowing faster VOC mass transfer rates and accommodating larger molecules, albeit with slightly lower adsorption capacities. Notably, VOCs with polar and aromatic properties, such as 2-methylpyridine, exhibited higher adsorption levels due to increased π-π interactions within the frameworks. However, regeneration of 2-methylpyridine was challenging due to chemisorption, forming strong, irreversible metal–nitrogen coordination bonds. Toluene and 2-methyl-2-bustanol showed similar adsorption capacities and could be effectively regenerated, indicating physisorption mechanisms involving π–π interactions and polar interactions, respectively. N-hexane exhibited the lowest adsorption capacities, relying on weaker van der Waals forces. These results highlight the promising potential of CuBTC and FeBTC in mitigating air pollution. The research also offers valuable insights for tailoring MOFs to contaminants' molecular properties, and advances our understanding of MOF applications in air quality engineering.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113619"},"PeriodicalIF":4.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.micromeso.2025.113620
Mohamed Gamal Mohamed , Abdul Basit , Manivannan Madhu , K. Aravinthkumar , Awad I. Said , Devaraj Manoj , Wei-Lung Tseng , Shiao-Wei Kuo
Conjugated microporous polymers (CMPs) have emerged as highly versatile materials, garnering significant attention in recent years due to their unique structural and functional properties. This study presents the development and synthesis of a CMP based on Py-TBNBZ, achieved via a well-established [4 + 4] Schiff base reaction. The reaction involves two primary building blocks: 4,4′,4″,4‴-(pyrene-1,3,6,8-tetrayl)tetrabenzaldehyde (PyBZ-4CHO) and 4,4′,4″,4‴-(dibenzo[g,p]chrysene-2,7,10,15-tetrayl)tetraaniline (TBNBZ-4NH2). The structural and morphological characteristics of the synthesized Py-TBNBZ CMP material were systematically analyzed using advanced experimental techniques, confirming the successful formation of a robust framework. The Py-TBNBZ CMP prepared in this study showed a BET surface area (SBET) of 497 m2 g−1. Thermal analysis indicated a decomposition temperature (Td10) of 476 °C and a notable char yield of 74 wt%, as confirmed through BET and TGA measurements. One of the most notable features of the Py-TBNBZ CMP is its strong fluorescence, which enabled its application in chemical sensing. The material exhibited exceptional sensitivity and selectivity, allowing for the detection of K+ and Fe2+ ions and precise pH monitoring over a broad pH range (pH 2–10). The underlying sensing mechanisms were investigated and elucidated. Additionally, the Py-TBNBZ CMP demonstrated remarkable adsorption capabilities for hazardous gas vapors, including ammonia (NH3) and hydrogen chloride (HCl), underscoring its potential for environmental remediation. The flexibility of the Py-TBNBZ CMP distinguishes it from other CMPs and porous materials, enabling superior performance, enhanced applicability, and improved operational efficiency. This work highlights the advanced capabilities of Py-TBNBZ CMP and contributes to the ongoing development of innovative materials for adsorption, environmental protection, and next-generation sensing technologies.
{"title":"Conjugated microporous polymer containing pyrene and Dibenzo[g,p]chrysene moieties as a luminescent powerhouse for multi-target sensing and environmental safety","authors":"Mohamed Gamal Mohamed , Abdul Basit , Manivannan Madhu , K. Aravinthkumar , Awad I. Said , Devaraj Manoj , Wei-Lung Tseng , Shiao-Wei Kuo","doi":"10.1016/j.micromeso.2025.113620","DOIUrl":"10.1016/j.micromeso.2025.113620","url":null,"abstract":"<div><div>Conjugated microporous polymers (CMPs) have emerged as highly versatile materials, garnering significant attention in recent years due to their unique structural and functional properties. This study presents the development and synthesis of a CMP based on Py-TBNBZ, achieved via a well-established [4 + 4] Schiff base reaction. The reaction involves two primary building blocks: 4,4′,4″,4‴-(pyrene-1,3,6,8-tetrayl)tetrabenzaldehyde (PyBZ-4CHO) and 4,4′,4″,4‴-(dibenzo[g,p]chrysene-2,7,10,15-tetrayl)tetraaniline (TBNBZ-4NH<sub>2</sub>). The structural and morphological characteristics of the synthesized Py-TBNBZ CMP material were systematically analyzed using advanced experimental techniques, confirming the successful formation of a robust framework. The Py-TBNBZ CMP prepared in this study showed a BET surface area (S<sub>BET</sub>) of 497 m<sup>2</sup> g<sup>−1</sup>. Thermal analysis indicated a decomposition temperature (<em>T</em><sub><em>d10</em></sub>) of 476 °C and a notable char yield of 74 wt%, as confirmed through BET and TGA measurements. One of the most notable features of the Py-TBNBZ CMP is its strong fluorescence, which enabled its application in chemical sensing. The material exhibited exceptional sensitivity and selectivity, allowing for the detection of K<sup>+</sup> and Fe<sup>2+</sup> ions and precise pH monitoring over a broad pH range (pH 2–10). The underlying sensing mechanisms were investigated and elucidated. Additionally, the Py-TBNBZ CMP demonstrated remarkable adsorption capabilities for hazardous gas vapors, including ammonia (NH<sub>3</sub>) and hydrogen chloride (HCl), underscoring its potential for environmental remediation. The flexibility of the Py-TBNBZ CMP distinguishes it from other CMPs and porous materials, enabling superior performance, enhanced applicability, and improved operational efficiency. This work highlights the advanced capabilities of Py-TBNBZ CMP and contributes to the ongoing development of innovative materials for adsorption, environmental protection, and next-generation sensing technologies.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113620"},"PeriodicalIF":4.8,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734586","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 : 2025-03-25DOI: 10.1016/j.micromeso.2025.113610
Svitlana Gryn , Mykhailo Kurmach , Pavlo Yaremov , Oleksiy Shvets , Sergei Alekseev , Susanne Wintzheimer , Karl Mandel
Herein we report on the design of hierarchical zeolite supraparticles from hydrothermally-derived 100 nm TS-1 zeolite nanoparticles (NPs) by means of spray-drying. These supraparticles, with a large surface area (up to 678 m2/g), possess a biporous structure that is composed of zeolitic micropores (0.9–1.1 nm) and secondary mesopores. Depending on the synthesis conditions, it is possible to prepare supraparticles, formed by separate NPs and wide (50 nm) interparticular pores or by zeolitic NPs, tightly glued together by amorphous mesoporous titanosilicate. According to the UV–vis spectrometry data and FTIR studies of adsorbed pyridine, the active sites of “separated” supraparticles are presented mainly by Lewis sites associated with [TiO4] species isolated in the zeolite matrix, while “glued” supraparticles possess a significant fraction of [TiO5] and [TiO6] species.
The supraparticles demonstrate sufficiently high catalytic activity in the industrially valuable two-stage synthesis of cyclic carbonate (4-phenyl-1,3-dioxolan-2-one) from styrene and carbon dioxide, in the presence of tert-butyl hydroperoxide as an oxidant and tetrabutylammonium iodide as a co-catalyst. We found that the selectivity to the target cyclic carbonate increased with an external specific surface area growth, probably due to the facilitated withdrawal of reaction products from the zeolite pores.
{"title":"Design of hierarchical TS-1 zeolites using spray-drying for enhanced catalytic activity in cyclic carbonate formation","authors":"Svitlana Gryn , Mykhailo Kurmach , Pavlo Yaremov , Oleksiy Shvets , Sergei Alekseev , Susanne Wintzheimer , Karl Mandel","doi":"10.1016/j.micromeso.2025.113610","DOIUrl":"10.1016/j.micromeso.2025.113610","url":null,"abstract":"<div><div>Herein we report on the design of hierarchical zeolite supraparticles from hydrothermally-derived 100 nm TS-1 zeolite nanoparticles (NPs) by means of spray-drying. These supraparticles, with a large surface area (up to 678 m<sup>2</sup>/g), possess a biporous structure that is composed of zeolitic micropores (0.9–1.1 nm) and secondary mesopores. Depending on the synthesis conditions, it is possible to prepare supraparticles, formed by separate NPs and wide (50 nm) interparticular pores or by zeolitic NPs, tightly glued together by amorphous mesoporous titanosilicate. According to the UV–vis spectrometry data and FTIR studies of adsorbed pyridine, the active sites of “separated” supraparticles are presented mainly by Lewis sites associated with [TiO<sub>4</sub>] species isolated in the zeolite matrix, while “glued” supraparticles possess a significant fraction of [TiO<sub>5</sub>] and [TiO<sub>6</sub>] species.</div><div>The supraparticles demonstrate sufficiently high catalytic activity in the industrially valuable two-stage synthesis of cyclic carbonate (4-phenyl-1,3-dioxolan-2-one) from styrene and carbon dioxide, in the presence of <em>tert</em>-butyl hydroperoxide as an oxidant and tetrabutylammonium iodide as a co-catalyst. We found that the selectivity to the target cyclic carbonate increased with an external specific surface area growth, probably due to the facilitated withdrawal of reaction products from the zeolite pores.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113610"},"PeriodicalIF":4.8,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739150","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 : 2025-03-22DOI: 10.1016/j.micromeso.2025.113609
Roberta Albino dos Reis , Martín A. Fernández-Baldo , Renan S. Nunes , Amedea B. Seabra
Metal-Organic Frameworks (MOFs) have emerged as promising materials for addressing modern agricultural challenges due to their exceptional porosity, high surface area, and chemical versatility. These crystalline frameworks enable the controlled release of agrochemicals, such as fertilizers, pesticides, and herbicides, improving resource efficiency and reducing environmental contamination. MOFs also exhibit multifunctionality, including water retention, pollutant remediation, and soil monitoring, offering solutions to issues like nutrient leaching, water scarcity, and pest resistance. ni Moreover, MOFs have been used as platform for biomolecules immobilization in the development of biosensors applied to agricultural area. Despite their transformative potential, challenges related to cost, scalability, and regulatory frameworks remain significant barriers to widespread adoption. This review explores the properties, applications, and limitations of MOFs in agriculture, emphasizing their role in advancing sustainable farming practices and highlighting perspectives for their integration into precision agriculture.
{"title":"Metal-organic frameworks: An overview of a possible solution for modern agriculture","authors":"Roberta Albino dos Reis , Martín A. Fernández-Baldo , Renan S. Nunes , Amedea B. Seabra","doi":"10.1016/j.micromeso.2025.113609","DOIUrl":"10.1016/j.micromeso.2025.113609","url":null,"abstract":"<div><div>Metal-Organic Frameworks (MOFs) have emerged as promising materials for addressing modern agricultural challenges due to their exceptional porosity, high surface area, and chemical versatility. These crystalline frameworks enable the controlled release of agrochemicals, such as fertilizers, pesticides, and herbicides, improving resource efficiency and reducing environmental contamination. MOFs also exhibit multifunctionality, including water retention, pollutant remediation, and soil monitoring, offering solutions to issues like nutrient leaching, water scarcity, and pest resistance. ni Moreover, MOFs have been used as platform for biomolecules immobilization in the development of biosensors applied to agricultural area. Despite their transformative potential, challenges related to cost, scalability, and regulatory frameworks remain significant barriers to widespread adoption. This review explores the properties, applications, and limitations of MOFs in agriculture, emphasizing their role in advancing sustainable farming practices and highlighting perspectives for their integration into precision agriculture.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113609"},"PeriodicalIF":4.8,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143687693","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 : 2025-03-21DOI: 10.1016/j.micromeso.2025.113602
Roman Barakov , Ivan Ermakov , Zakhar Enbaev , Sergey Maksimov , Andrei Smirnov , Irina Ivanova
An important stage of cascade transformation of lignocellulosic biomass to value-added chemicals is the conversion of levulinic acid and its esters in γ-valerolactone, which has a potential application as a bio-based solvent, an intermediate in the production of polymers, food additives and bio-fuels. Herein, hierarchical Zr-BEA zeolites have demonstrated high catalytic performance and reusability in this reaction under mild conditions (115 °C, atmospheric pressure). The novel approach for the preparation of these zeolites with various Zr content has been proposed. This two-step post-synthetic method includes dealumination of hierarchical Al-BEA obtained in the highly concentrated reaction mixture followed by zirconium incorporation via wet impregnation. The hierarchical Zr-BEA zeolite with the highest degree of zirconium incorporation, i.e. 42 %, calculated as the ratio of Lewis acid site concentration and Zr content, is obtained using wet impregnation in dry ethanol and ZrCl4 as a zirconium source. This catalyst provides a higher initial rate of γ-valerolactone formation, which is 1.0 mmolGVL/gcath, as compared to commercially-based Zr-BEA, for which the rate is 0.2 mmolGVL/gcath. The higher reaction rate over hierarchical zeolite is associated with the improved accessibility of its strong Lewis acid sites, which are the most active in Meerwein-Ponndorf-Verley reduction. An even higher initial rate is achieved over hierarchical Zr-BEA in the conversion of butyl levulinate since this ester does not block the basic framework oxygen of active Zr–O sites, as in the case of levulinic acid. The plausible mechanism for the transformation of levulinic acid over Lewis and Brønsted acid sites has been proposed.
{"title":"Hierarchical Zr-BEA zeolites as catalysts for the transformation of levulinic acid to γ-valerolactone under mild conditions","authors":"Roman Barakov , Ivan Ermakov , Zakhar Enbaev , Sergey Maksimov , Andrei Smirnov , Irina Ivanova","doi":"10.1016/j.micromeso.2025.113602","DOIUrl":"10.1016/j.micromeso.2025.113602","url":null,"abstract":"<div><div>An important stage of cascade transformation of lignocellulosic biomass to value-added chemicals is the conversion of levulinic acid and its esters in γ-valerolactone, which has a potential application as a bio-based solvent, an intermediate in the production of polymers, food additives and bio-fuels. Herein, hierarchical Zr-BEA zeolites have demonstrated high catalytic performance and reusability in this reaction under mild conditions (115 °C, atmospheric pressure). The novel approach for the preparation of these zeolites with various Zr content has been proposed. This two-step post-synthetic method includes dealumination of hierarchical Al-BEA obtained in the highly concentrated reaction mixture followed by zirconium incorporation <em>via</em> wet impregnation. The hierarchical Zr-BEA zeolite with the highest degree of zirconium incorporation, i.e. 42 %, calculated as the ratio of Lewis acid site concentration and Zr content, is obtained using wet impregnation in dry ethanol and ZrCl<sub>4</sub> as a zirconium source. This catalyst provides a higher initial rate of γ-valerolactone formation, which is 1.0 mmol<sub>GVL</sub>/g<sub>cat</sub>h, as compared to commercially-based Zr-BEA, for which the rate is 0.2 mmol<sub>GVL</sub>/g<sub>cat</sub>h. The higher reaction rate over hierarchical zeolite is associated with the improved accessibility of its strong Lewis acid sites, which are the most active in Meerwein-Ponndorf-Verley reduction. An even higher initial rate is achieved over hierarchical Zr-BEA in the conversion of butyl levulinate since this ester does not block the basic framework oxygen of active Zr–O sites, as in the case of levulinic acid. The plausible mechanism for the transformation of levulinic acid over Lewis and Brønsted acid sites has been proposed.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113602"},"PeriodicalIF":4.8,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143759640","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}
Water evaporation power generation (WEPG) is recognized as a novel and pollution-free energy technology. However, the regulation of water states in generating materials and their impact on power generation performance remain under-explored. In this study, a series of samples denoted as ZSM-5/Tx (where x = 0–7.00), with varying surface charges, are prepared by tailoring their Si/Al ratio. It is found that a lower Si/Al ratio results in a higher surface charge of the material. Consequently, a positive correlation between surface charge and WEPG performances is observed, with ZSM-5/Tx samples that have higher surface charges showing increased open-circuit voltage (Voc) and short-circuit current (Isc). Among all the samples, the typical ZSM-5/T3.55 sample, which has the highest surface charge, demonstrates the highest Voc of 1.35 V and Isc of 223 nA. Theoretical calculations indicate that charge accumulation between ZSM-5/Tx and water molecules increases with surface charge, i.e., 0.00038 e− for ZSM-5/T1.50, 0.0005 e− for ZSM-5/T3.55, and 0.00035 e− for ZSM-5/T7.00. The study further reveals that surface charge influences the water states of intermediate water (IW) and free water (FW) within the microchannels of ZSM-5/Tx. As the surface charge of ZSM-5/Tx increases, the IW/FW ratio follows the order of 0.72 (ZSM-5/T3.55) > 0.59 (ZSM-5/T1.50) > 0.48 (ZSM-5/T7.00) > 0.36 (ZSM-5/T0). The increase in the IW/FW ratio reduces energy consumption and enhances water evaporation, and IW is more likely to detach from ZSM-5/Tx at higher surface charges, thus improving power generation efficiency.
{"title":"Surface charge regulation for enhanced control of water states in ZSM-5 materials to boost water evaporation power generation","authors":"Jiangying Qu, Qian Yin, Zhe Jiao, Jiawei Ge, Feng Gao, Yunhao Zang","doi":"10.1016/j.micromeso.2025.113606","DOIUrl":"10.1016/j.micromeso.2025.113606","url":null,"abstract":"<div><div>Water evaporation power generation (WEPG) is recognized as a novel and pollution-free energy technology. However, the regulation of water states in generating materials and their impact on power generation performance remain under-explored. In this study, a series of samples denoted as ZSM-5/Tx (where x = 0–7.00), with varying surface charges, are prepared by tailoring their Si/Al ratio. It is found that a lower Si/Al ratio results in a higher surface charge of the material. Consequently, a positive correlation between surface charge and WEPG performances is observed, with ZSM-5/Tx samples that have higher surface charges showing increased open-circuit voltage (<em>V</em><sub><em>oc</em></sub>) and short-circuit current (<em>I</em><sub><em>sc</em></sub>). Among all the samples, the typical ZSM-5/T3.55 sample, which has the highest surface charge, demonstrates the highest <em>V</em><sub><em>oc</em></sub> of 1.35 V and <em>I</em><sub><em>sc</em></sub> of 223 nA. Theoretical calculations indicate that charge accumulation between ZSM-5/Tx and water molecules increases with surface charge, i.e., 0.00038 e<sup>−</sup> for ZSM-5/T1.50, 0.0005 e<sup>−</sup> for ZSM-5/T3.55, and 0.00035 e<sup>−</sup> for ZSM-5/T7.00. The study further reveals that surface charge influences the water states of intermediate water (IW) and free water (FW) within the microchannels of ZSM-5/Tx. As the surface charge of ZSM-5/Tx increases, the IW/FW ratio follows the order of 0.72 (ZSM-5/T3.55) > 0.59 (ZSM-5/T1.50) > 0.48 (ZSM-5/T7.00) > 0.36 (ZSM-5/T0). The increase in the IW/FW ratio reduces energy consumption and enhances water evaporation, and IW is more likely to detach from ZSM-5/Tx at higher surface charges, thus improving power generation efficiency.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113606"},"PeriodicalIF":4.8,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724342","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 : 2025-03-19DOI: 10.1016/j.micromeso.2025.113607
Yihang Jiang , Wenzhi Li , Xia Zhang , Liang Yuan
Direct oxidation of methane to methanol is a significant approach for utilizing natural gas and unconventional natural gas, reducing carbon emissions, and increasing energy efficiency. A series of Cu/SAPO-34 catalysts were successfully prepared using a simple and controllable solid ion exchange method for the continuous conversion of methane to methanol. The 1.5 wt% Cu/SAPO-34 achieves highest methanol yield of 178.3 μmol/(gcat·h), while maintaining a methanol selectivity of 47 % at 400 °C. The distribution of copper in the zeolite significantly affects its direct conversion of methane to methanol. Through ex-situ DRIFTS, EPR, and H2-TPR, all Cu/SAPO-34 catalysts contained two types of copper: one is isolated copper located on the hexagonal rings of the zeolite, which effectively conversion methane to methanol, and copper oxide nanoparticles in a cage, which easily cause over-oxidation of methanol. The in-situ DRIFTS confirmed the Cu2+-Cu+-Cu2+ redox cycle mechanism of the reaction.
{"title":"The impact of Cu distribution in Cu/SAPO-34 catalyst on the continuous direct conversion of methane to methanol","authors":"Yihang Jiang , Wenzhi Li , Xia Zhang , Liang Yuan","doi":"10.1016/j.micromeso.2025.113607","DOIUrl":"10.1016/j.micromeso.2025.113607","url":null,"abstract":"<div><div>Direct oxidation of methane to methanol is a significant approach for utilizing natural gas and unconventional natural gas, reducing carbon emissions, and increasing energy efficiency. A series of Cu/SAPO-34 catalysts were successfully prepared using a simple and controllable solid ion exchange method for the continuous conversion of methane to methanol. The 1.5 wt% Cu/SAPO-34 achieves highest methanol yield of 178.3 μmol/(g<sub>cat</sub>·h), while maintaining a methanol selectivity of 47 % at 400 °C. The distribution of copper in the zeolite significantly affects its direct conversion of methane to methanol. Through ex-situ DRIFTS, EPR, and H<sub>2</sub>-TPR, all Cu/SAPO-34 catalysts contained two types of copper: one is isolated copper located on the hexagonal rings of the zeolite, which effectively conversion methane to methanol, and copper oxide nanoparticles in a cage, which easily cause over-oxidation of methanol. The in-situ DRIFTS confirmed the Cu<sup>2+</sup>-Cu<sup>+</sup>-Cu<sup>2+</sup> redox cycle mechanism of the reaction.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113607"},"PeriodicalIF":4.8,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143685437","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 : 2025-03-19DOI: 10.1016/j.micromeso.2025.113608
Mariana Erculano da Fonseca , Gabriel de Freitas Batista , Tomaz Alves dos Santos Lima , Márcio César Pereira , Raquel Vieira Mambrini
Nanostructured materials exhibit remarkable properties, making them promising candidates for effluent treatment applications. The doped compounds can further enhance their efficiency. Herein, cerium and niobium-based nanomaterials were synthesized using an easy hydrothermal method for application in effluent treatment. Materials with different Ce:Nb molar ratios were produced and characterized using various techniques, including X-ray fluorescence, powder X-ray diffraction, adsorption-desorption isotherms of N2, Raman spectroscopy, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, scanning electron microscopy combined with energy-dispersive X-ray spectroscopy, and UV–Vis diffuse reflectance spectroscopy. The results confirmed the incorporation of niobium into the structures of the materials, which showed mesoporous characteristics, and the Rietveld refinement shows a decrease in lattice parameters, suggesting that niobium replaces some Ce ions in the CeO2 structure. A higher niobium ratio led to a larger pore diameter but a smaller surface area. Additionally, the materials exhibited absorption in the UV region and a bandgap between 2.75 and 2.85 eV, demonstrating their potential for use in photocatalytic reactions. The materials were tested for oxidation of dye compounds under ultraviolet and visible light, and the results showed a tremendous oxidative potential. The best condition presented 100 % degradation after 60 min of reaction, and after five reaction cycles, it was kept above 90 % removal. Mass spectrometry with electrospray ionization (ESI-MS) spectra and total organic carbon (TOC) rate showed the high oxidation rate of the dye. So, niobium doping in cerium oxide showed an increased catalytic potential, which does not require catalytic support or a semiconductor for photocatalysis reactions.
{"title":"Hydrothermal synthesis of mesoporous cerium oxide nanoparticles with improved properties by niobium doping","authors":"Mariana Erculano da Fonseca , Gabriel de Freitas Batista , Tomaz Alves dos Santos Lima , Márcio César Pereira , Raquel Vieira Mambrini","doi":"10.1016/j.micromeso.2025.113608","DOIUrl":"10.1016/j.micromeso.2025.113608","url":null,"abstract":"<div><div>Nanostructured materials exhibit remarkable properties, making them promising candidates for effluent treatment applications. The doped compounds can further enhance their efficiency. Herein, cerium and niobium-based nanomaterials were synthesized using an easy hydrothermal method for application in effluent treatment. Materials with different Ce:Nb molar ratios were produced and characterized using various techniques, including X-ray fluorescence, powder X-ray diffraction, adsorption-desorption isotherms of N<sub>2</sub>, Raman spectroscopy, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, scanning electron microscopy combined with energy-dispersive X-ray spectroscopy, and UV–Vis diffuse reflectance spectroscopy. The results confirmed the incorporation of niobium into the structures of the materials, which showed mesoporous characteristics, and the Rietveld refinement shows a decrease in lattice parameters, suggesting that niobium replaces some Ce ions in the CeO<sub>2</sub> structure. A higher niobium ratio led to a larger pore diameter but a smaller surface area. Additionally, the materials exhibited absorption in the UV region and a bandgap between 2.75 and 2.85 eV, demonstrating their potential for use in photocatalytic reactions. The materials were tested for oxidation of dye compounds under ultraviolet and visible light, and the results showed a tremendous oxidative potential. The best condition presented 100 % degradation after 60 min of reaction, and after five reaction cycles, it was kept above 90 % removal. Mass spectrometry with electrospray ionization (ESI-MS) spectra and total organic carbon (TOC) rate showed the high oxidation rate of the dye. So, niobium doping in cerium oxide showed an increased catalytic potential, which does not require catalytic support or a semiconductor for photocatalysis reactions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"391 ","pages":"Article 113608"},"PeriodicalIF":4.8,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143685438","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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