Department of Chemistry, Seoul National University, Seoul 151-747, Republic of Korea.
Chemistry. 2010 Dec 17;16(47):14043-50. doi: 10.1002/chem.201002135.
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) (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.
金属-有机骨架（MOFs），{[Cu(2)(bdcppi)(dmf)(2)]·10DMF·2H(2)O}(n)（SNU-50）和{[Zn(2)(bdcppi)(dmf)(3)]·6DMF·4H(2)O}(n)（SNU-51），是通过 N,N'-双（3,5-二羧基苯基）均苯四酸二酰亚胺（H(4)BDCPPI）与 Cu(NO(3))(2)和 Zn(NO(3))(2)的溶剂热反应分别制备的。骨架 SNU-50 具有 NbO 型网络结构，而 SNU-51 具有 PtS 型网络结构。通过 SNU-50 与丙酮的客体交换，然后在 170°C 下抽真空制备的脱溶剂固体Cu(2)(bdcppi)（SNU-50'），由于每个金属离子上都有空位配位位和配体中的酰亚胺基团，因此可以吸附大量的 N(2)、H(2)、O(2)、CO(2)和 CH(4)气体。Langmuir 比表面积为 2450 m(2) g(-1)。它在 1 大气压和 77 K 下可吸附高达 2.10wt%的 H(2)气体，零覆盖等离解热为 7.1 kJ mol(-1)，在 77 K 和 60 bar 下总共可吸附 7.85wt%。在 298 K 时，其 CO(2)和 CH(4)吸附容量分别为 55 bar 时为 77wt%和 60 bar 时为 17wt%。特别值得注意的是 SNU-50'（在 77 K 和 0.2 atm 下的 O(2)吸附容量为 118wt%），这是迄今为止报道的任何 MOF 中最高的。通过 SNU-51 与 Cu(II)的金属离子交换，制备了具有 PtS 型网络的{[Cu(2)(bdcppi)(dmf)(3)]·7DMF·5H(2)O}(n)（SNU-51-Cu(DMF)），这是不能通过直接溶剂热反应合成的。
