Enhance Hydrogen Isotopes Separation by Alkali Earth Metal Dopant in Metal-Organic Framework
Enhance Hydrogen Isotopes Separation by Alkali Earth Metal Dopant in Metal-Organic Framework
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DOI：
10.1021/acs.jpclett.2c03657
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发表时间：
2023-01-30
影响因子：
5.7
通讯作者：
Chen，Wei
中科院分区：
文献类型：
--
作者：
Dong，Wenjun;Yuan，Jiamin;Chen，Wei
基于孔径的动力学量子筛分和基于吸附位的化学亲和量子筛分是多孔材料分离氢同位素混合物的两种途径。将碱土金属（Be、Mg和Ca）掺杂到UiO-67中以探索这些金属位点是否可以促进H2/D2分离。基于密度泛函理论计算的零点能和吸附焓，Be掺杂剂表现出比其他碱土金属掺杂剂更好的H2/D2分离性能，并且在基于CAQS的金属-有机骨架中具有不饱和金属位.轨道相互作用与化学亲和力密切相关，并进一步影响D2/H2选择性。此外，在77 K下Be掺杂位点的预测D2/H2选择性（49.4）甚至大于最佳实验结果（26）。最后，通过对H2和D2在Be掺杂UiO-67上的不同动力学行为的研究，表明其具有较强的KQS分离H2/D2的性能。
Kinetic quantum sieving (KQS) based on pore size and chemical affinity quantum sieving (CAQS) based on adsorption site are two routes of porous materials to separate hydrogen isotope mixtures. Alkali earth metals (Be, Mg, and Ca) were doped into UiO-67 to explore whether these metal sites can promote H2/D2separation. Based on the zero-point energy and adsorption enthalpy calculated by density functional theory calculations, the Be dopant shows better H2/D2separation performance than other alkali earth metal dopants and unsaturated metal sites in metal–organic frameworks based on CAQS. Orbital interaction strongly relates to the chemical affinity and further influences the D2/H2selectivity. Moreover, the predicted D2/H2selectivity of Be-doped sites (49.4) at 77 K is even larger than the best experimental result (26). Finally, the different dynamic behaviors of H2and D2on Be-doped UiO-67 indicate its strong H2/D2separation performance via KQS.