title: Gas adsorption properties of highly porous metal-organic frameworks containing functionalized naphthalene dicarboxylate linkers.
abstract: Three functionalized metal-organic frameworks (MOFs), MOF-205-NH2, MOF-205-NO2, and MOF-205-OBn, formulated as Zn4O(BTB)4/3(L), where BTB is benzene-1,3,5-tribenzoate and L is 1-aminonaphthalene-3,7-dicarboxylate (NDC-NH2), 1-nitronaphthalene-3,7-dicarboxylate (NDC-NO2) or 1,5-dibenzyloxy-2,6-naphthalenedicarboxylate (NDC-(OBn)2), were synthesized and their gas (H2, CO2, or CH4) adsorption properties were compared to those of the un-functionalized, parent MOF-205. Ordered structural models for MOF-205 and its derivatives were built based on the crystal structures and were subsequently used for predicting porosity properties. Although the Brunauer-Emmett-Teller (BET) surface areas of the three MOF-205 derivatives were reduced (MOF-205, 4460; MOF-205-NH2, 4330; MOF-205-NO2, 3980; MOF-205-OBn, 3470 m(2) g(-1)), all three derivatives were shown to have enhanced H2 adsorption capacities at 77 K and CO2 uptakes at 253, 273, and 298 K respectively at 1 bar in comparison with MOF-205. The results indicate the following trend in H2 adsorption: MOF-205 < MOF-205-NO2 < MOF-205-NH2 < MOF-205-OBn. MOF-205-OBn showed good ideal adsorbed solution theory (IAST) selectivity values of 6.5 for CO2/N2 (15/85 in v/v) and 2.7 for CO2/CH4 (50/50 in v/v) at 298 K. Despite the large reduction (-22%) in the surface area, MOF-205-OBn displayed comparable total volumetric CO2 (at 48 bar) and CH4 (at 35 bar) storage capacities with those of MOF-205 at 298 K: MOF-205-OBn, 305 (CO2) and 112 (CH4) cm(3) cm(-3), and for MOF-205, 307 (CO2) and 120 (CH4) cm(3) cm(-3), respectively.
authors.affiliation: Department of Chemistry, Soongsil University, 369 Sangdo-Ro, Dongjak-Gu, Seoul 156-743, Republic of Korea. parkhyejeong83@gmail.com jaheon@ssu.ac.kr.
authors.forename: Jaeung
authors.initials: J
authors.lastname: Sim
authors.forename: Haneul
authors.initials: H
authors.lastname: Yim
authors.forename: Nakeun
authors.initials: N
authors.lastname: Ko
authors.forename: Sang Beom
authors.initials: SB
authors.lastname: Choi
authors.forename: Youjin
authors.initials: Y
authors.lastname: Oh
authors.forename: Hye Jeong
authors.initials: HJ
authors.lastname: Park
authors.forename: SangYoun
authors.initials: S
authors.lastname: Park
authors.forename: Jaheon
authors.initials: J
authors.lastname: Kim
mesh_terms: D000327:Adsorption; D002245:Carbon Dioxide / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005740:Gases / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D008697:Methane / Q000737:chemistry; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D016062:Porosity
chemical_list: D002264:Carboxylic Acids; D005740:Gases; D009281:Naphthalenes; D009942:Organometallic Compounds; D002245:Carbon Dioxide; C031721:naphthalene; D006859:Hydrogen; D008697:Methane