Breathing Behaviour Modification of Gallium MIL-53 Metal-Organic Frameworks Induced by the Bridging Framework Inorganic Anion
Breathing Behaviour Modification of Gallium MIL-53 Metal-Organic Frameworks Induced by the Bridging Framework Inorganic Anion
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DOI：
10.1002/chem.202203773
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发表时间：
2023-03-13
影响因子：
4.3
通讯作者：
Attfield，Martin P.
中科院分区：
文献类型：
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作者：
Lutton-Gething，A. R. Bonity J.;Nangkam，Lynda T.;Attfield，Martin P.
金属有机框架Ga-MIL-53 [GaX（bdc）]（X−=（OH）−或F−，bdc=1，4-benzenedicarboxylate）中μ2-X−桥接阴离子的控制方面被证明可以指导该框架发生热诱导呼吸转变的温度。原位单晶X射线衍射研究表明，在[Ga（OH）（bdc）]（1）中用20%的（OH）−取代F−以产生[Ga（OH）0.8F0.2（bdc）]（2）相对于窄孔（np）形式稳定了大孔（lp）形式，导致在较高温度下lp到np转变的开始明确减少，以及氮在较低温度下通过NP到LP到中间（INT）孔转变的吸附/解吸。这些原位衍射研究也产生了一个更合理的晶体结构的int-[GaX（bdc）] nH 2 O相，并表明，增加加热速率到闪速加热制度可以使int-[GaX（bdc）] nH 2 O到lp-[GaX（bdc）]的转变发生在一个比np-[GaX（bdc）]更低的温度下，通过一个未报道的途径。
Controlling aspects of the μ2‐X−bridging anion in the metal–organic framework Ga‐MIL‐53 [GaX(bdc)] (X−=(OH)−or F−, bdc=1, 4‐benzenedicarboxylate) is shown to direct the temperature at which thermally induced breathing transitions of this framework occur. In situ single crystal X‐ray diffraction studies reveal that substituting 20 % of (OH)−in [Ga(OH)(bdc)] (1) for F−to produce [Ga(OH)0.8F0.2(bdc)] (2) stabilises the large pore (lp) form relative to the narrow pore (np) form, causing a well‐defined decrease in the onset of the lp to np transition at higher temperatures, and the adsorption/desorption of nitrogen at lower temperatures through np to lp to intermediate (int) pore transitions. These in situ diffraction studies have also yielded a more plausible crystal structure of the int‐[GaX(bdc)] ⋅ H2O phases and shown that increasing the heating rate to a flash heating regime can enable the int‐[GaX(bdc)] ⋅ H2O to lp‐[GaX(bdc)] transition to occur at a lower temperature than np‐[GaX(bdc)] via an unreported pathway.