Zhang Yuanbin, Hu Jianbo, Krishna Rajamani, Wang Lingyao, Yang Lifeng, Cui Xili, Duttwyler Simon, Xing Huabin
Key laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China.
Institute of Zhejiang University-Quzhou, 78 Jiuhua Boulevard North, Quzhou, 324000, P. R. China.
Angew Chem Int Ed Engl. 2020 Sep 28;59(40):17664-17669. doi: 10.1002/anie.202007681. Epub 2020 Aug 6.
Separation of acetylene (C H ) from carbon dioxide (CO ) or ethylene (C H ) is important in industry but limited by the low capacity and selectivity owing to their similar molecular sizes and physical properties. Herein, we report two novel dodecaborate-hybrid metal-organic frameworks, MB H (dpb) (termed as BSF-3 and BSF-3-Co for M=Cu and Co), for highly selective capture of C H . The high C H capacity and remarkable C H /CO selectivity resulted from the unique anionic boron cluster functionality as well as the suitable pore size with cooperative proton-hydride dihydrogen bonding sites (B-H ⋅⋅⋅H -C≡C-H ⋅⋅⋅H -B). This new type of C H -specific functional sites represents a fresh paradigm distinct from those in previous leading materials based on open metal sites, strong electrostatics, or hydrogen bonding.
从二氧化碳（CO₂）或乙烯（C₂H₄）中分离乙炔（C₂H₂）在工业上具有重要意义，但由于它们相似的分子尺寸和物理性质，其容量和选择性较低，受到限制。在此，我们报道了两种新型的十二硼酸盐杂化金属有机框架，MB₁₂H₁₂(dpb)（当M = Cu和Co时分别称为BSF - 3和BSF - 3 - Co），用于高选择性捕获C₂H₂。高的C₂H₂容量和显著的C₂H₂/CO₂选择性源于独特的阴离子硼簇官能团以及具有协同质子 - 氢化物 - 二氢键合位点（B - H∙∙∙H - C≡C - H∙∙∙H - B）的合适孔径。这种新型的C₂H₂特异性功能位点代表了一种与先前基于开放金属位点、强静电作用或氢键的领先材料不同的全新范例。
