Dr. Feifei Zhang, Zhiwei Zhao, Yating Wang, Xiaomin Li, Xiaowei Bai, Mengyue Lu, Yanjie Wang, Dr. Xiaoqing Wang, Prof. Libo Li, Prof. Jinping Li, Prof. Jiangfeng Yang
{"title":"低极化率氮吸附点用于N2/CH4分离","authors":"Dr. Feifei Zhang, Zhiwei Zhao, Yating Wang, Xiaomin Li, Xiaowei Bai, Mengyue Lu, Yanjie Wang, Dr. Xiaoqing Wang, Prof. Libo Li, Prof. Jinping Li, Prof. Jiangfeng Yang","doi":"10.1002/anie.202510242","DOIUrl":null,"url":null,"abstract":"<p>Selective adsorption of N<sub>2</sub> from CH<sub>4</sub> is an industrially promising but challenging process given their similar sizes and physicochemical properties. Herein, we report a robust metal-organic framework (Cu-MFU-4l) featuring open Cu(I) sites of low polarizability for benchmark N<sub>2</sub>/CH<sub>4</sub> separation. The presence of open Cu(I) sites in the framework was confirmed by X-ray absorption spectroscopy (XAS), in situ CO-adsorbed infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Gas sorption isotherms revealed that Cu-MFU-4l exhibited a significant difference between N<sub>2</sub> and CH<sub>4</sub> uptakes, resulting in a high N<sub>2</sub>/CH<sub>4</sub> uptake ratio (1.94) and kinetic selectivity (2.20), of which the N<sub>2</sub>/CH<sub>4</sub> uptake ratio was the highest among all MOFs reported to date. Breakthrough experiments confirmed Cu-MFU-4l as the best porous adsorbent hitherto reported for binary N<sub>2</sub>/CH<sub>4</sub> separation, based on the record-high breakthrough selectivity (2.43) and CH<sub>4</sub> productivity (0.47 mmol g<sup>−1</sup>). High-purity CH<sub>4</sub> (99.99%) could also be obtained from ternary and even six-component CH<sub>4</sub> mixtures by a one-step separation process. In situ infrared spectroscopy and computational modeling studies revealed that the open Cu(I) sites could better distinguish N<sub>2</sub> and CH<sub>4</sub>.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 36","pages":""},"PeriodicalIF":16.9000,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Nitrogen Adsorption Sites with Low Polarizability for Benchmark N2/CH4 Separation\",\"authors\":\"Dr. Feifei Zhang, Zhiwei Zhao, Yating Wang, Xiaomin Li, Xiaowei Bai, Mengyue Lu, Yanjie Wang, Dr. Xiaoqing Wang, Prof. Libo Li, Prof. Jinping Li, Prof. Jiangfeng Yang\",\"doi\":\"10.1002/anie.202510242\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Selective adsorption of N<sub>2</sub> from CH<sub>4</sub> is an industrially promising but challenging process given their similar sizes and physicochemical properties. Herein, we report a robust metal-organic framework (Cu-MFU-4l) featuring open Cu(I) sites of low polarizability for benchmark N<sub>2</sub>/CH<sub>4</sub> separation. The presence of open Cu(I) sites in the framework was confirmed by X-ray absorption spectroscopy (XAS), in situ CO-adsorbed infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Gas sorption isotherms revealed that Cu-MFU-4l exhibited a significant difference between N<sub>2</sub> and CH<sub>4</sub> uptakes, resulting in a high N<sub>2</sub>/CH<sub>4</sub> uptake ratio (1.94) and kinetic selectivity (2.20), of which the N<sub>2</sub>/CH<sub>4</sub> uptake ratio was the highest among all MOFs reported to date. Breakthrough experiments confirmed Cu-MFU-4l as the best porous adsorbent hitherto reported for binary N<sub>2</sub>/CH<sub>4</sub> separation, based on the record-high breakthrough selectivity (2.43) and CH<sub>4</sub> productivity (0.47 mmol g<sup>−1</sup>). High-purity CH<sub>4</sub> (99.99%) could also be obtained from ternary and even six-component CH<sub>4</sub> mixtures by a one-step separation process. In situ infrared spectroscopy and computational modeling studies revealed that the open Cu(I) sites could better distinguish N<sub>2</sub> and CH<sub>4</sub>.</p>\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":\"64 36\",\"pages\":\"\"},\"PeriodicalIF\":16.9000,\"publicationDate\":\"2025-07-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Angewandte Chemie International Edition\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/anie.202510242\",\"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":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/anie.202510242","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Nitrogen Adsorption Sites with Low Polarizability for Benchmark N2/CH4 Separation
Selective adsorption of N2 from CH4 is an industrially promising but challenging process given their similar sizes and physicochemical properties. Herein, we report a robust metal-organic framework (Cu-MFU-4l) featuring open Cu(I) sites of low polarizability for benchmark N2/CH4 separation. The presence of open Cu(I) sites in the framework was confirmed by X-ray absorption spectroscopy (XAS), in situ CO-adsorbed infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Gas sorption isotherms revealed that Cu-MFU-4l exhibited a significant difference between N2 and CH4 uptakes, resulting in a high N2/CH4 uptake ratio (1.94) and kinetic selectivity (2.20), of which the N2/CH4 uptake ratio was the highest among all MOFs reported to date. Breakthrough experiments confirmed Cu-MFU-4l as the best porous adsorbent hitherto reported for binary N2/CH4 separation, based on the record-high breakthrough selectivity (2.43) and CH4 productivity (0.47 mmol g−1). High-purity CH4 (99.99%) could also be obtained from ternary and even six-component CH4 mixtures by a one-step separation process. In situ infrared spectroscopy and computational modeling studies revealed that the open Cu(I) sites could better distinguish N2 and CH4.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.