Quantum sieving effect of three-dimensional Cu-based organic framework for H2 and D2.
Quantum sieving effect of three-dimensional Cu-based organic framework for H2 and D2.
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DOI：
10.1021/ja077469f
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发表时间：
2008-04
影响因子：
15
通讯作者：
D. Noguchi;Hideki Tanaka;A. Kondo;H. Kajiro;H. Noguchi;T. Ohba;H. Kanoh;K. Kaneko
中科院分区：
文献类型：
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作者：
D. Noguchi;Hideki Tanaka;A. Kondo;H. Kajiro;H. Noguchi;T. Ohba;H. Kanoh;K. Kaneko
采用同步x射线粉末衍射法测定了383 K预抽真空后一维孔网[Cu（4,4′-联吡啶）2(CF 3so3) 2] n金属有机骨架（CuBOTf）的晶体结构。用氮气吸附法测定了预真空CuBOTf的有效纳米孔隙度。测定了CuBOTf在40和77 K下的h2和d2吸附等温线，并利用有效纳米孔隙度与gcmc模拟等温线进行了比较。利用Feynman-Hibbs有效势模拟的77 K下的h2和d2等温线与实验结果吻合，为CuBOTf吸附h2和d2的量子分子筛分效应提供了直接证据。而对1:1的h2和d2混合气的选择性为1.2。相反，实验h2和d2等温线在40 K下有明显的吸附滞后，这是由于测量吸附分支时存在明显的孔阻塞效应。量子h2的阻滞效应比量子d2的阻滞效应更明显；在40 K时，对h2的选择性在2.6 ~ 5.8之间。在77 K的条件下，还研究了三维孔隙网络中[Cu 3（苯-1,3,5-三羧酸盐）2(h2o) 3] n吸附h2和d2的量子分子筛分效应。
The crystal structure of [Cu(4,4'-bipyridine) 2(CF 3SO 3) 2] n metal-organic framework (CuBOTf) of one-dimensional pore networks after pre-evacuation at 383 K was determined with synchrotron X-ray powder diffraction measurement. Effective nanoporosity of the pre-evacuated CuBOTf was determined with N 2 adsorption at 77 K. The experimental H 2 and D 2 adsorption isotherms of CuBOTf at 40 and 77 K were measured and then compared with GCMC-simulated isotherms using the effective nanoporosity. The quantum-simulated H 2 and D 2 isotherms at 77 K using the Feynman-Hibbs effective potential coincided with the experimental ones, giving a direct evidence on the quantum molecular sieving effect for adsorption of H 2 and D 2 on CuBOTf. However, the selectivity for the 1:1 mixed gas of H 2 and D 2 was 1.2. On the contrary, experimental H 2 and D 2 isotherms at 40 K had an explicit adsorption hysteresis, originating from the marked pore blocking effect on measuring the adsorption branch. The blocking effect for quantum H 2 is more prominent than that for quantum D 2; the selectivity for D 2 over H 2 at 40 K was in the range of 2.6 to 5.8. The possibility of the quantum molecular sieving effect for H 2 and D 2 adsorption on [Cu 3(benzene-1,3,5-tricarboxylate) 2(H 2O) 3] n of three-dimensional pore networks was also shown at 77 K.