Highly Effective H2/D2 Separation within the Stable Cu(I)Cu(II)-BTC: The Effect of Cu(I) Structure on Quantum Sieving

被引:20
作者
Hu, Xiaoyu [1 ,2 ]
Ding, Fengyun [3 ,4 ]
Xiong, Renjin [3 ]
An, Yongtao [3 ]
Feng, Xingwen [3 ]
Song, Jiangfeng [3 ]
Zhou, Linsen [3 ]
Li, Peilong [3 ]
Chen, Changlun [1 ,5 ]
机构
[1] Chinese Acad Sci, Inst Plasma Phys, HFIPS, R China, Hefei 230031, Peoples R China
[2] Univ Sci & Technol China, P, R China, Hefei 230026, Peoples R China
[3] China Acad Engn Phys, Inst Mat, Mianyang 621907, Peoples R China
[4] Sichuan Univ, Inst Atom & Mol Phys, Chengdu 610065, Sichuan, Peoples R China
[5] Soochow Univ, Collaborat Innovat Ctr Radiat Med, Jiangsu Higher Educ Inst, Suzhou 215123, Peoples R China
基金
中国国家自然科学基金;
关键词
hydrogen isotope separation; Cu(I) ions; quantum sieving; thermal desorption spectroscopy; DFT calculation; METAL-ORGANIC FRAMEWORKS; HYDROGEN ISOTOPE-SEPARATION; SELECTIVE ADSORPTION; CO2; ADSORPTION; HKUST-1; H-2/D-2; D-2; ENERGY; H-2; DESORPTION;
D O I
10.1021/acsami.2c18221
中图分类号
TB3 [工程材料学];
学科分类号
0805 ; 080502 ;
摘要
Realizing ideal deuterium separation from isotopic mixtures remains a daunting challenge because of their almost identical sizes, shapes, and physicochemical properties. Using the quantum sieving effect in porous materials with suitable pore size and open metal sites (OMSs) enables efficient hydrogen isotope separation. Herein, synthetic HKUST-1-derived microporous mixed-valence Cu(I)Cu(II)-BTC (BTC = benzene-1,3,5-tricarboxylate), featuring a unique network of distinct Cu(I) and Cu(II) coordination sites, can remarkably boost the D2/H2 isotope separation, which has a high selectivity (SD2/H2) of 37.9 at 30 K, in comparison with HKUST-1 and other porous materials. Density functional theory (DFT) calculations indicate that the introduction of Cu(I) macrocycles in the framework decreases the pore size and further leads to relatively enhanced interaction of H2/D2 molecules on Cu(II) sites. The significantly enhanced selectivity of Cu(I)Cu(II)-BTC at 30 K can be mainly attributed to the synergistic effect of kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS). The results reveal that Cu(I) OMSs exhibit counterintuitive behaviors and play a crucial role in tuning quantum sieving without a complex structural design, which provides a deeper insight into quantum sieving mechanisms and a new strategy for the intelligent design of highly efficient isotope systems.
引用
收藏
页码:3941 / 3952
页数:12
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