title: Quantum sieving effect of three-dimensional Cu-based organic framework for H2 and D2.
abstract: 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.
authors.affiliation: Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.
authors.forename: Daisuke
authors.initials: D
authors.lastname: Noguchi
authors.forename: Hideki
authors.initials: H
authors.lastname: Tanaka
authors.forename: Atsushi
authors.initials: A
authors.lastname: Kondo
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Kajiro
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Noguchi
authors.forename: Tomonori
authors.initials: T
authors.lastname: Ohba
authors.forename: Hirofumi
authors.initials: H
authors.lastname: Kanoh
authors.forename: Katsumi
authors.initials: K
authors.lastname: Kaneko
mesh_terms: D000327:Adsorption; D001555:Benzene Derivatives / Q000737:chemistry; D002850:Chromatography, Gel; D003300:Copper / Q000737:chemistry*; D003903:Deuterium / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D009010:Monte Carlo Method; D009942:Organometallic Compounds / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D011789:Quantum Theory; D013816:Thermodynamics; D014961:X-Ray Diffraction
chemical_list: D001555:Benzene Derivatives; D009942:Organometallic Compounds; D011725:Pyridines; D003300:Copper; D006859:Hydrogen; D003903:Deuterium; C034306:4,4'-bipyridyl