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Porous 10-and 12-vertex (bi)-p-dicarba-closo-boranedicarboxylates of cobalt and their gas adsorptive properties
Autoři: Boldog István | Dusek Michal | Jelinek Tomas | Švec Petr | De Oliveira Ramos Francisca Solanea | Růžička Aleš | Bulánek Roman
Rok: 2018
Druh publikace: článek v odborném periodiku
Název zdroje: Microporous and Mesoporous Materials
Název nakladatele: Elsevier Science BV
Místo vydání: Amsterdam
Strana od-do: 284-294
Tituly:
Jazyk Název Abstrakt Klíčová slova
cze Porézní 10-ti a 12-ti vrcholové deriváty karboranu s kobaltem a jejich vlastnosti pro adsorpci plynů Dva nové porézní koordinační polymery, [Co-3(mu(3)-OH)(Bcb10DC)(2.5)(DEF)(3)(EtOH)(1.5)(H2O)(0.5) .DEF.EtOH (3b) a [Co-2(Bcb12DC)(2)(DMF)(4)(EtOH)].2EtOH (4) byly syntetizovány. Jejich vlastnosti byly porovnány se dvěma známými analogy. Dále byly testovány pro adsorpci plynů. MOF; porézní; koordinační polymer; karboran; adsorpce plynů
eng Porous 10-and 12-vertex (bi)-p-dicarba-closo-boranedicarboxylates of cobalt and their gas adsorptive properties Two new porous coordination polymers, [Co-3(mu(3)-OH)(Bcb10DC)(2.5)(DEF)(3)(EtOH)(1.5)(H2O)(0.5)] center dot DEF center dot EtOH (3b) and [Co-2(Bcb12DC)(2)(DMF)(4)(EtOH)] center dot 2EtOH (4) based on 10- and 12-vertex p-bicarboranedicarboxylic acids, 1,1'-bi-(1,10-dicarba-closo-decaborane)-10,10'-dicarboxylic acid (H(2)Bcb10DC) and 1,1'-bi-(1,12-dicarba-closo-decaborane)-12,12'-dicarboxylic acid (H(2)Bcb12DC) were synthesized. Their properties were compared with the two known analogues based on shorter ligand-homologues, [Co(cb10DC)(DMF)] (1) and [Co-4(OH)(2)(cb12DC)(3)(DMF)(2)(H2O)(4)] center dot 3DMF center dot EtOH (2). The structure of 3b is based on a trinuclear cluster and has a 3D structure with a 5-c bnn underlying net, while 4 is based on a binuclear cluster and composed of stacked 2D sql layers. Activated 3' with altered structure has S-BET(N-2) of 1012 m(2) g(-1) and 4' with mostly retained structure 920 m(2) g(-1). Gas adsorption by 3' and 4' at 1 bar is: 80.1 cm(3) g(-1) (0.72%(wt)) and 81.3 cm(3) g(-1) (0.73%(wt)) H-2 at 77 K; 16.7 and 21.9 cm(3) g(-1) CO2 at 273 K; 6.2 and 10.0 cm(3) g(-1) of CH4 at 273 K. The isosteric heat of adsorption Q(st) at zero coverage are respectively: 5.0 and 4.5 kJ mol(-1) for H-2, 16.7 and 21.9 for CO2; 6.2 and 10.0 for CH4. 2' with similar to 645 m(2) g(-1) (calc. 883 m(2) g(-1)) has the highest mass-specific H-2 adsorption, > 30% than other compounds, while Q(st) is close to 1' and slightly higher than for 3' and 4'. Adsorption of CO2 and CH4 and Q(st) are similar to 1.5-2 times lower for 3' and 4' compared to 1' and 2'. The surface area specific adsorption of H-2, CO2 and CH4 is the highest for 1'. The CO2/CH4 LAST selectivities (0.15/0.85; 1 bar, 298 K) are in 2-4.5 range. 3' and 4' retain a significant part of porosity after soaking in water unlike 1' and 2'. MOF; Porous; Coordination polymer; Carborane; Gas adsorption