Benchmark C 2 H 2 /CO 2 Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry
| Autor: | Kai Shao, Enlai Hu, Yu Yang, Ling Zhang, Huabin Xing, Ling Yang, Yuanjing Cui, Bin Li, Banglin Chen, Guodong Qian, Ke Jiang, Lifeng Yang, Libo Li |
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| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Chemistry chemistry.chemical_element General Chemistry Microporous material General Medicine 010402 general chemistry 01 natural sciences Copper Catalysis 0104 chemical sciences chemistry.chemical_compound Adsorption Acetylene Chemical engineering Molecule Metal-organic framework Gas separation Selectivity |
| Zdroj: | Angewandte Chemie. 133:16131-16138 |
| ISSN: | 1521-3757 0044-8249 |
| Popis: | Separation of acetylene from carbon dioxide remains a daunting challenge because of their very similar molecular sizes and physical properties. We herein report the first example of using copper(I)-alkynyl chemistry within an ultra-microporous MOF (CuI @UiO-66-(COOH)2 ) to achieve ultrahigh C2 H2 /CO2 separation selectivity. The anchored CuI ions on the pore surfaces can specifically and strongly interact with C2 H2 molecule through copper(I)-alkynyl π-complexation and thus rapidly adsorb large amount of C2 H2 at low-pressure region, while effectively reduce CO2 uptake due to the small pore sizes. This material thus exhibits the record high C2 H2 /CO2 selectivity of 185 at ambient conditions, significantly higher than the previous benchmark ZJU-74a (36.5) and ATC-Cu (53.6). Theoretical calculations reveal that the unique π-complexation between CuI and C2 H2 mainly contributes to the ultra-strong C2 H2 binding affinity and record selectivity. The exceptional separation performance was evidenced by breakthrough experiments for C2 H2 /CO2 gas mixtures. This work suggests a new perspective to functionalizing MOFs with copper(I)-alkynyl chemistry for highly selective separation of C2 H2 over CO2 . |
| Databáze: | OpenAIRE |
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