A hydrothermally stable Zn(II)-based metal-organic framework: structural modulation and gas adsorption
A hydrothermally stable Zn(II)-based metal-organic framework: structural modulation and gas adsorption
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水热稳定的Zn(II)基金属有机骨架：结构调节和气体吸附
DOI：
10.1039/c5dt01770j
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发表时间：
2015
影响因子：
4
通讯作者：
Jianrong Li
中科院分区：
文献类型：
--
作者：
Xiuling Zhang;Yongzheng Zhang;Dashua Zhang;Baoyong Zhu;Jianrong Li
在N，N′-二甲基乙酰胺/乙腈/水（v/v/v = 1：1：1）混合溶剂中，通过三角形配体2，4，6-三（4-羧基苯氧基）-1，3，5-三嗪（H3 tcpt）与Zn（NO3）2·6 H2O的溶剂热反应 ，合成了一种双层、互穿、三维（3D）多孔金属有机骨架[Zn 2（tcpt）OH]·（1·溶剂），与罕见的，桨轮二级结构单元（SBU），锌2（COO）3，合成和表征。结果发现，当通过与叶轮SBU的tcpt 3 −键合构建的二维层通过-OH基团沿着SBU的轴向位点连接时，形成1的单一3D结构。与所报道的具有该配体的基于Zn（II）的伙伴相比，合成条件，特别是所使用的溶剂，显然在形成不同SBU中起关键作用，从而导致具有相同配体的不同MOF。特别是，1具有良好的水稳定性和热稳定性，并且可以耐受pH值为5至12的酸性水溶液。此外，1显示出良好的吸附能力对H2（2.21重量%，在77 K和1大气压），可以选择性地吸附CO2从CH 4和N2，尽管其相对较低的空隙体积（36.8%），这表明在气体储存和分离的潜在应用。
By the solvothermal reaction of a triangular ligand, 2,4,6-tris-(4-carboxyphenoxy)-1,3,5-triazine (H3tcpt) with Zn(NO3)2·6H2O in N,N′-dimethylacetamide/acetonitrile/H2O (v/v/v = 1 : 1 : 1) mixed solvents, a two-fold, interpenetrated, three-dimensional (3D), porous metal–organic framework, [Zn2(tcpt)OH]·solvents (1·solvents), with a rare, paddlewheel secondary building unit (SBU), Zn2(COO)3, was synthesized and characterized. It was found that a single 3D structure of 1 forms when two-dimensional layers, which are constructed by tcpt3− bonding with the paddlewheel SBUs, are linked by –OH groups along the axial sites of the SBUs. Compared with the reported Zn(II)-based partners with this ligand, synthesis conditions, particularly the solvents used, clearly played a key role in the formation of different SBUs, thereby resulting in distinct MOFs with the same ligand. In particular, 1 features good water and thermal stability and can withstand acidic aqueous solutions with pH values ranging from 5 to 12. In addition, 1 displays good adsorption ability towards H2 (2.21 wt% at 77 K and 1 atm) and can selectively adsorb CO2 from CH4 and N2, in spite of its relatively low void volume (36.8%), suggesting potential applications in gas storage and separation.