{"title":"配体保护和低温水热法合成包裹在 TON 沸石中的铂,用于糠醛到糠醇的形状选择性加氢反应","authors":"Xuelin Wang, Congxin Wang, Wentao Bi, Wei Qu, Zhijian Tian","doi":"10.1039/d4ta07243j","DOIUrl":null,"url":null,"abstract":"Encapsulating metal in zeolite is an effective tactic to up-regulate the catalytic selectivity of metal/zeolite catalysts in hydrogenation reaction by virtue of the spatial confinement of the zeolite microchannels. Herein, we present the synthesis of Pt encapsulated in zeolite with TON topology (Pt@ZSM-22) by adopting the ligand-protected and lowered-temperature hydrothermal crystallization. The XRD, SEM, TEM, TG-DSC-MS, and <small><sup>13</sup></small>C CP/MAS NMR are used to track the hydrothermal process. The experimental results indicate the decomposition and reduction of metal precursor ([Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small>), which usually occurs at the harsh hydrothermal conditions, is effectively restrained at the lowered hydrothermal temperature (140 °C) and with the protection of the ligand (ethylenediamine). The intact [Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small> is electrostatically adsorbed on the amorphous silicate nanoparticles (the zeolite precursor) and is encapsulated inside the ZSM-22 crystals as these nanoparticles are crystallized. The highly-dispersed and uniform Pt particles embedded inside the ZSM-22 zeolite are successfully obtained by adopting the direct H<small><sub>2</sub></small> reduction to remove the template and reduce the [Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small>. The hydrogenation of furfural to furfuryl alcohol was conducted to evaluate the selective hydrogenation performance of the encapsulated Pt@ZSM-22. The reaction results reveal the furfuryl alcohol selectivity reaches as high as 97.6% at a conversion of 99.5% over the encapsulated Pt@ZSM-22, which is superior to the supported Pt/ZSM-22. The excellent furfuryl alcohol selectivity reflects the shape selectivity conferred by the spatial confinement of the one-dimensional microchannels of ZSM-22. The CO-FT-IR, XPS, XAFS and FT-IR of adsorbed furfural are used to disclose the structure-activity relationship of Pt@ZSM-22. Our work not only successfully realizes the direct hydrothermal synthesis of metal encapsulation in zeolite with 1D straight channels but also demonstrates the great application potentials of such catalysts in selective catalysis.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":10.7000,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ligand-protected and lowered-temperature hydrothermal synthesis of platinum encapsulated in TON zeolite for shape-selective hydrogenation of furfural to furfuryl alcohol\",\"authors\":\"Xuelin Wang, Congxin Wang, Wentao Bi, Wei Qu, Zhijian Tian\",\"doi\":\"10.1039/d4ta07243j\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Encapsulating metal in zeolite is an effective tactic to up-regulate the catalytic selectivity of metal/zeolite catalysts in hydrogenation reaction by virtue of the spatial confinement of the zeolite microchannels. Herein, we present the synthesis of Pt encapsulated in zeolite with TON topology (Pt@ZSM-22) by adopting the ligand-protected and lowered-temperature hydrothermal crystallization. The XRD, SEM, TEM, TG-DSC-MS, and <small><sup>13</sup></small>C CP/MAS NMR are used to track the hydrothermal process. The experimental results indicate the decomposition and reduction of metal precursor ([Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small>), which usually occurs at the harsh hydrothermal conditions, is effectively restrained at the lowered hydrothermal temperature (140 °C) and with the protection of the ligand (ethylenediamine). The intact [Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small> is electrostatically adsorbed on the amorphous silicate nanoparticles (the zeolite precursor) and is encapsulated inside the ZSM-22 crystals as these nanoparticles are crystallized. The highly-dispersed and uniform Pt particles embedded inside the ZSM-22 zeolite are successfully obtained by adopting the direct H<small><sub>2</sub></small> reduction to remove the template and reduce the [Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small>. The hydrogenation of furfural to furfuryl alcohol was conducted to evaluate the selective hydrogenation performance of the encapsulated Pt@ZSM-22. The reaction results reveal the furfuryl alcohol selectivity reaches as high as 97.6% at a conversion of 99.5% over the encapsulated Pt@ZSM-22, which is superior to the supported Pt/ZSM-22. The excellent furfuryl alcohol selectivity reflects the shape selectivity conferred by the spatial confinement of the one-dimensional microchannels of ZSM-22. The CO-FT-IR, XPS, XAFS and FT-IR of adsorbed furfural are used to disclose the structure-activity relationship of Pt@ZSM-22. Our work not only successfully realizes the direct hydrothermal synthesis of metal encapsulation in zeolite with 1D straight channels but also demonstrates the great application potentials of such catalysts in selective catalysis.\",\"PeriodicalId\":82,\"journal\":{\"name\":\"Journal of Materials Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.7000,\"publicationDate\":\"2024-11-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Materials Chemistry A\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ta07243j\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Chemistry A","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ta07243j","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Ligand-protected and lowered-temperature hydrothermal synthesis of platinum encapsulated in TON zeolite for shape-selective hydrogenation of furfural to furfuryl alcohol
Encapsulating metal in zeolite is an effective tactic to up-regulate the catalytic selectivity of metal/zeolite catalysts in hydrogenation reaction by virtue of the spatial confinement of the zeolite microchannels. Herein, we present the synthesis of Pt encapsulated in zeolite with TON topology (Pt@ZSM-22) by adopting the ligand-protected and lowered-temperature hydrothermal crystallization. The XRD, SEM, TEM, TG-DSC-MS, and 13C CP/MAS NMR are used to track the hydrothermal process. The experimental results indicate the decomposition and reduction of metal precursor ([Pt(en)2]2+), which usually occurs at the harsh hydrothermal conditions, is effectively restrained at the lowered hydrothermal temperature (140 °C) and with the protection of the ligand (ethylenediamine). The intact [Pt(en)2]2+ is electrostatically adsorbed on the amorphous silicate nanoparticles (the zeolite precursor) and is encapsulated inside the ZSM-22 crystals as these nanoparticles are crystallized. The highly-dispersed and uniform Pt particles embedded inside the ZSM-22 zeolite are successfully obtained by adopting the direct H2 reduction to remove the template and reduce the [Pt(en)2]2+. The hydrogenation of furfural to furfuryl alcohol was conducted to evaluate the selective hydrogenation performance of the encapsulated Pt@ZSM-22. The reaction results reveal the furfuryl alcohol selectivity reaches as high as 97.6% at a conversion of 99.5% over the encapsulated Pt@ZSM-22, which is superior to the supported Pt/ZSM-22. The excellent furfuryl alcohol selectivity reflects the shape selectivity conferred by the spatial confinement of the one-dimensional microchannels of ZSM-22. The CO-FT-IR, XPS, XAFS and FT-IR of adsorbed furfural are used to disclose the structure-activity relationship of Pt@ZSM-22. Our work not only successfully realizes the direct hydrothermal synthesis of metal encapsulation in zeolite with 1D straight channels but also demonstrates the great application potentials of such catalysts in selective catalysis.
期刊介绍:
The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.