High Gas Sorption and Metal‐Ion Exchange of Microporous Metal–Organic Frameworks with Incorporated Imide Groups

Abstract

Metal-organic frameworks (MOFs), {[Cu(2)(bdcppi)(dmf)(2)]·10DMF·2H(2)O}(n) (SNU-50) and {[Zn(2)(bdcppi)(dmf)(3)]·6DMF·4H(2)O}(n) (SNU-51), have been prepared by the solvothermal reactions of N,N'-bis(3,5-dicarboxyphenyl)pyromellitic diimide (H(4)BDCPPI) with Cu(NO(3))(2) and Zn(NO(3))(2), respectively. Framework SNU-50 has an NbO-type net structure, whereas SNU-51 has a PtS-type net structure. Desolvated solid [Cu(2)(bdcppi)](n) (SNU-50'), which was prepared by guest exchange of SNU-50 with acetone followed by evacuation at 170 °C, adsorbs high amounts of N(2), H(2), O(2), CO(2), and CH(4) gases due to the presence of a vacant coordination site at every metal ion, and to the presence of imide groups in the ligand. The Langmuir surface area is 2450 m(2) g(-1). It adsorbs H(2) gas up to 2.10 wt% at 1 atm and 77 K, with zero coverage isosteric heat of 7.1 kJ mol(-1), up to a total of 7.85 wt% at 77 K and 60 bar. Its CO(2) and CH(4) adsorption capacities at 298 K are 77 wt% at 55 bar and 17 wt% at 60 bar, respectively. Of particular note is the O(2) adsorption capacity of SNU-50' (118 wt% at 77 K and 0.2 atm), which is the highest reported so far for any MOF. By metal-ion exchange of SNU-51 with Cu(II), {[Cu(2)(bdcppi)(dmf)(3)]·7DMF·5H(2)O}(n) (SNU-51-Cu(DMF)) with a PtS-type net was prepared, which could not be synthesized by a direct solvothermal reaction.