Han Yang, Ming Xu, Min Mao, Lei Gao, Hao Zhang, Sha-Sha Meng, Wen-Qi Tang, Yu-Hao Gu, Shuai Yuan, Ling-Mei Liu and Zhi-Yuan Gu*,
{"title":"超稳定羧酸铜金属有机骨架。","authors":"Han Yang, Ming Xu, Min Mao, Lei Gao, Hao Zhang, Sha-Sha Meng, Wen-Qi Tang, Yu-Hao Gu, Shuai Yuan, Ling-Mei Liu and Zhi-Yuan Gu*, ","doi":"10.1021/jacs.5c05507","DOIUrl":null,"url":null,"abstract":"<p >Direct synthesis of acid–base-stable copper carboxylate metal–organic frameworks (MOFs) is of great significance but faces substantial challenges. Herein, a nanoenvelope strategy was proposed to protect the copper paddle-wheel cluster in the assembly between Cu(II) and 4,4′,4″,4‴-(1,3,6,8-pyrenetetrayl)tetrakis-benzoic acid (H<sub>4</sub>TBAPy) through AB stacking. This structure unexpectedly restricted the access of water to the Cu–O bonds, creating one of the most stable MOFs in water (240 days, RT) as well as in acid and base solutions (pH from 0 to 13). Water vapor adsorption experiments, density functional theory (DFT) calculations, and radial distribution function (RDF) analyses further confirmed the high water resistance of Cu<sub>2</sub>TBAPy. Moreover, excellent separation for xylene isomers was achieved, with a resolution of 18.2 (meta-xylene/para-xylene) and a durability of 31 months, which surpassed all previous materials. Xylene isomer impurities were separated with a detection limit as low as 1.33 pg. The remarkable stability of Cu<sub>2</sub>TBAPy offers valuable guidance for the design and synthesis of highly water-stable copper carboxylate MOFs.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 25","pages":"21961–21972"},"PeriodicalIF":15.6000,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ultrastable Copper Carboxylate Metal–Organic Frameworks\",\"authors\":\"Han Yang, Ming Xu, Min Mao, Lei Gao, Hao Zhang, Sha-Sha Meng, Wen-Qi Tang, Yu-Hao Gu, Shuai Yuan, Ling-Mei Liu and Zhi-Yuan Gu*, \",\"doi\":\"10.1021/jacs.5c05507\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Direct synthesis of acid–base-stable copper carboxylate metal–organic frameworks (MOFs) is of great significance but faces substantial challenges. Herein, a nanoenvelope strategy was proposed to protect the copper paddle-wheel cluster in the assembly between Cu(II) and 4,4′,4″,4‴-(1,3,6,8-pyrenetetrayl)tetrakis-benzoic acid (H<sub>4</sub>TBAPy) through AB stacking. This structure unexpectedly restricted the access of water to the Cu–O bonds, creating one of the most stable MOFs in water (240 days, RT) as well as in acid and base solutions (pH from 0 to 13). Water vapor adsorption experiments, density functional theory (DFT) calculations, and radial distribution function (RDF) analyses further confirmed the high water resistance of Cu<sub>2</sub>TBAPy. Moreover, excellent separation for xylene isomers was achieved, with a resolution of 18.2 (meta-xylene/para-xylene) and a durability of 31 months, which surpassed all previous materials. Xylene isomer impurities were separated with a detection limit as low as 1.33 pg. The remarkable stability of Cu<sub>2</sub>TBAPy offers valuable guidance for the design and synthesis of highly water-stable copper carboxylate MOFs.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"147 25\",\"pages\":\"21961–21972\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2025-06-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.5c05507\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.5c05507","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Direct synthesis of acid–base-stable copper carboxylate metal–organic frameworks (MOFs) is of great significance but faces substantial challenges. Herein, a nanoenvelope strategy was proposed to protect the copper paddle-wheel cluster in the assembly between Cu(II) and 4,4′,4″,4‴-(1,3,6,8-pyrenetetrayl)tetrakis-benzoic acid (H4TBAPy) through AB stacking. This structure unexpectedly restricted the access of water to the Cu–O bonds, creating one of the most stable MOFs in water (240 days, RT) as well as in acid and base solutions (pH from 0 to 13). Water vapor adsorption experiments, density functional theory (DFT) calculations, and radial distribution function (RDF) analyses further confirmed the high water resistance of Cu2TBAPy. Moreover, excellent separation for xylene isomers was achieved, with a resolution of 18.2 (meta-xylene/para-xylene) and a durability of 31 months, which surpassed all previous materials. Xylene isomer impurities were separated with a detection limit as low as 1.33 pg. The remarkable stability of Cu2TBAPy offers valuable guidance for the design and synthesis of highly water-stable copper carboxylate MOFs.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.