Ping Enming, Chen Xiaoxiao, Zhou Yunshan, Zhang Lijuan, Kong Lingyun, Chen Nan
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing100029, P. R. China.
Inorg Chem. 2023 Jan 30;62(4):1591-1601. doi: 10.1021/acs.inorgchem.2c03795. Epub 2023 Jan 19.
In this work, CAU-10-H@γ-AlOOH is prepared, and then UTSA-16 is loaded on CAU-10-H@γ-AlOOH to obtain UTSA-16@CAU-10-H@γ-AlOOH. Using the as-prepared composites as stationary materials by cryogenic gas chromatography at 77 K, while CAU-10-H@γ-AlOOH achieves the complete separation of -H (-H) and D with a resolution of 1.66 and a separation time of 9.52 min, UTSA-16@CAU-10-H@γ-AlOOH achieves higher efficiency separation of hydrogen isotopes in a shorter separation time (4.56 min) with = 1.7. Molecular simulation results show that CAU-10-H has both chemical affinity quantum sieving and kinetic sieving effects for H/D at 77 K, and UTSA-16 can only exert the kinetic sieving effect. UTSA-16's load on CAU-10-H@γ-AlOOH weakens the adsorption of hydrogen isotopes, and the presence of Co in UTSA-16 promotes the conversion of -H to -H. In gas chromatography, H was preferentially desorbed from the system due to strong D adsorption caused by the chemical affinity quantum sieving effect and faster H diffusion caused by the kinetic sieving effect. These additive effects achieved efficient hydrogen isotope separation at 77 K.
在本工作中，制备了CAU-10-H@γ-AlOOH，然后将UTSA-16负载在CAU-10-H@γ-AlOOH上，得到UTSA-16@CAU-10-H@γ-AlOOH。在77 K下，通过低温气相色谱法将所制备的复合材料用作固定相材料，CAU-10-H@γ-AlOOH实现了-H (-H) 和D的完全分离，分离度为1.66，分离时间为9.52分钟，而UTSA-16@CAU-10-H@γ-AlOOH在更短的分离时间（4.56分钟）内以1.7的分离度实现了更高效率的氢同位素分离。分子模拟结果表明，CAU-10-H在77 K时对H/D同时具有化学亲和量子筛分和动力学筛分效应，而UTSA-16仅发挥动力学筛分效应。UTSA-16负载在CAU-10-H@γ-AlOOH上会削弱氢同位素的吸附，UTSA-16中Co的存在促进了-H向-H的转化。在气相色谱中，由于化学亲和量子筛分效应导致D的强吸附以及动力学筛分效应导致H更快扩散，H优先从系统中解吸。这些加和效应实现了77 K下高效的氢同位素分离。
