具有桨轮结构SBU的金属有机骨架在水化时的稳定性和水解
Stability and Hydrolyzation of Metal Organic Frameworks with Paddle-Wheel SBUs upon Hydration
摘要：
大多数原型金属有机框架（MOFs）在水分存在下的不稳定性一直是工业规模发展的限制。在这项工作中，我们研究了微孔桨轮框架M（bdc）（ted）0.5 [M=Cu，Zn，Ni，Co; bdc= 1，4-benzenedicarboxylate; ted= triethylenediamine]在受控湿度环境中的解离机制。结合原位红外光谱，拉曼光谱和粉末X-射线衍射测量表明，在暴露于水蒸气后，同构M（BDC）（TED）0.5化合物的稳定性和改性严重依赖于中心金属离子。在Cu（bdc）（ted）0.5的情况下观察到水分子与Cu-O-C的水解反应。ted连接体被水分子的置换反应用Zn（bdc）（ted）0.5和Co（bdc）（ted）0.5鉴定。相比之下，。Ni（bdc）（ted）0.5比其它三种化合物更不易与水蒸气反应。此外，水蒸气冷凝到骨架中是引发解离反应所必需的。这些发现得到了第一性原理理论范德华密度泛函（vdW-DF）计算的支持，为确定具有桨轮二级结构单元的这类MOFs的操作条件提供了必要的信息，并为开发更稳健的单元提供了指导。
英文摘要：
Instability of most prototypical metal organic frameworks (MOFs) in the presence of moisture is always a limita- tion for industrial scale development. In this work, we examine the dissociation mechanism of microporous paddle wheel frameworks M(bdc)(ted)0.5 [M=Cu, Zn, Ni, Co; bdc= 1,4-benzenedicarboxylate; ted= triethylenediamine] in controlled humidity environments. Combined in-situ IR spectroscopy, Raman, and Powder x-ray diffraction measurements show that the stability and modification of isostructual M(bdc)(ted)0.5 compounds upon exposure to water vapor critically depend on the central metal ion. A hydrolysis reaction of water molecules with Cu-O-C is observed in the case of Cu(bdc)(ted)0.5. Displacement reactions of ted linkers by water molecules are identified with Zn(bdc)(ted)0.5 and Co(bdc)(ted)0.5. In contrast,. Ni(bdc)(ted)0.5 is less suscept- ible to reaction with water vapors than the other three compounds. In addition, the condensation of water vapors into the framework is necessary to initiate the dissociation reaction. These findings, supported by supported by first principles theoretical van der Waals density functional (vdW-DF) calculations of overall reaction enthalpies, provide the necessary information for de- termining operation conditions of this class of MOFs with paddle wheel secondary building units and guidance for developing more robust units.
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