{"title":"具有杂原子功能化纳米通道的铝基金属有机框架吸附剂用于分离己烷异构体","authors":"Jingxian Hua, Yawei Gu, Zemin Li, Luogang Wu, Haiqian Lian, Lixiong Zhang, Rujing Hou, Yichang Pan, Weihong Xing","doi":"10.1021/acs.iecr.4c02953","DOIUrl":null,"url":null,"abstract":"Metal–organic frameworks (MOFs) have emerged as attractive options for the nonthermal separation of hexane isomers due to their variable channel environments and structural diversity. Here, we report three robust Al-MOFs, KMF-1, MIL-160, and CAU-23, which have nanochannels functionalized with heteroatoms (N, O, and S) for the adsorptive separation of hexane isomers. The adsorption isotherms reveal that these three Al-MOFs can simultaneously adsorb linear, mono-, and dibranched isomers due to their relatively large pore sizes, while showing distinct thermodynamic adsorption behaviors. Significantly, CAU-23, constructed with “S”-atom-functionalized ligands, boasts a notable <i>n</i>-hexane uptake of 3.4 mmol·g<sup>–1</sup>, coupled with <i>n</i>-hexane/3-methylpentane and <i>n</i>-hexane/2,2-dimethylbutane uptake ratios of 1.2 and 1.7 at 298 K and a pressure of 19 kPa, respectively, surpassing those of most reported thermodynamically separated MOF materials. Breakthrough measurements demonstrate that CAU-23 effectively separates an <i>n</i>-hexane/3-methylpentane/2,2-dimethylbutane mixture system into linear, mono-, and dibranched components, achieving <i>n</i>-hexane purity levels of up to 99.9%, while providing sufficient retention time between <i>n</i>-hexane, 3-methylpentane, and 2,2-dimethylbutane. The configurational bias Monte Carlo and density functional theory calculations confirmed atomic-scale interactions between heteroatom sites within Al-MOF nanochannels and various isomers, leading to distinct distributions and adsorption characteristics. Moreover, CAU-23 offers a benchmark balance among separation performance, regeneration ability, cost of production, and scalability, highlighting its potential for further research in industrial adsorptive separation of hexane isomers.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"14 1","pages":""},"PeriodicalIF":3.8000,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Robust Aluminum-Based Metal–Organic Framework Adsorbents with Heteroatom-Functionalized Nanochannels for Hexane Isomer Separation\",\"authors\":\"Jingxian Hua, Yawei Gu, Zemin Li, Luogang Wu, Haiqian Lian, Lixiong Zhang, Rujing Hou, Yichang Pan, Weihong Xing\",\"doi\":\"10.1021/acs.iecr.4c02953\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Metal–organic frameworks (MOFs) have emerged as attractive options for the nonthermal separation of hexane isomers due to their variable channel environments and structural diversity. Here, we report three robust Al-MOFs, KMF-1, MIL-160, and CAU-23, which have nanochannels functionalized with heteroatoms (N, O, and S) for the adsorptive separation of hexane isomers. The adsorption isotherms reveal that these three Al-MOFs can simultaneously adsorb linear, mono-, and dibranched isomers due to their relatively large pore sizes, while showing distinct thermodynamic adsorption behaviors. Significantly, CAU-23, constructed with “S”-atom-functionalized ligands, boasts a notable <i>n</i>-hexane uptake of 3.4 mmol·g<sup>–1</sup>, coupled with <i>n</i>-hexane/3-methylpentane and <i>n</i>-hexane/2,2-dimethylbutane uptake ratios of 1.2 and 1.7 at 298 K and a pressure of 19 kPa, respectively, surpassing those of most reported thermodynamically separated MOF materials. Breakthrough measurements demonstrate that CAU-23 effectively separates an <i>n</i>-hexane/3-methylpentane/2,2-dimethylbutane mixture system into linear, mono-, and dibranched components, achieving <i>n</i>-hexane purity levels of up to 99.9%, while providing sufficient retention time between <i>n</i>-hexane, 3-methylpentane, and 2,2-dimethylbutane. The configurational bias Monte Carlo and density functional theory calculations confirmed atomic-scale interactions between heteroatom sites within Al-MOF nanochannels and various isomers, leading to distinct distributions and adsorption characteristics. Moreover, CAU-23 offers a benchmark balance among separation performance, regeneration ability, cost of production, and scalability, highlighting its potential for further research in industrial adsorptive separation of hexane isomers.\",\"PeriodicalId\":39,\"journal\":{\"name\":\"Industrial & Engineering Chemistry Research\",\"volume\":\"14 1\",\"pages\":\"\"},\"PeriodicalIF\":3.8000,\"publicationDate\":\"2025-01-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Industrial & Engineering Chemistry Research\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.iecr.4c02953\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Industrial & Engineering Chemistry Research","FirstCategoryId":"5","ListUrlMain":"https://doi.org/10.1021/acs.iecr.4c02953","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
Robust Aluminum-Based Metal–Organic Framework Adsorbents with Heteroatom-Functionalized Nanochannels for Hexane Isomer Separation
Metal–organic frameworks (MOFs) have emerged as attractive options for the nonthermal separation of hexane isomers due to their variable channel environments and structural diversity. Here, we report three robust Al-MOFs, KMF-1, MIL-160, and CAU-23, which have nanochannels functionalized with heteroatoms (N, O, and S) for the adsorptive separation of hexane isomers. The adsorption isotherms reveal that these three Al-MOFs can simultaneously adsorb linear, mono-, and dibranched isomers due to their relatively large pore sizes, while showing distinct thermodynamic adsorption behaviors. Significantly, CAU-23, constructed with “S”-atom-functionalized ligands, boasts a notable n-hexane uptake of 3.4 mmol·g–1, coupled with n-hexane/3-methylpentane and n-hexane/2,2-dimethylbutane uptake ratios of 1.2 and 1.7 at 298 K and a pressure of 19 kPa, respectively, surpassing those of most reported thermodynamically separated MOF materials. Breakthrough measurements demonstrate that CAU-23 effectively separates an n-hexane/3-methylpentane/2,2-dimethylbutane mixture system into linear, mono-, and dibranched components, achieving n-hexane purity levels of up to 99.9%, while providing sufficient retention time between n-hexane, 3-methylpentane, and 2,2-dimethylbutane. The configurational bias Monte Carlo and density functional theory calculations confirmed atomic-scale interactions between heteroatom sites within Al-MOF nanochannels and various isomers, leading to distinct distributions and adsorption characteristics. Moreover, CAU-23 offers a benchmark balance among separation performance, regeneration ability, cost of production, and scalability, highlighting its potential for further research in industrial adsorptive separation of hexane isomers.
期刊介绍:
ndustrial & Engineering Chemistry, with variations in title and format, has been published since 1909 by the American Chemical Society. Industrial & Engineering Chemistry Research is a weekly publication that reports industrial and academic research in the broad fields of applied chemistry and chemical engineering with special focus on fundamentals, processes, and products.