Unusually Large Band Gap Changes in Breathing Metal-Organic Framework Materials
Unusually Large Band Gap Changes in Breathing Metal-Organic Framework Materials
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DOI：
10.1021/acs.jpcc.5b04050
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发表时间：
2015-07-23
影响因子：
3.7
通讯作者：
Slater, Ben
中科院分区：
文献类型：
--
作者：
Ling, Sanliang;Slater, Ben
金属有机框架（mof）的许多潜在应用集中在利用其孔隙度进行分子存储、释放和分离，其中功能行为由主客体相互作用的微妙平衡控制。一般来说，主人的结构相对来说不会因为客人的出现而受到干扰；然而，mof的一个子集表现出由客体吸附或其他刺激引发的戏剧性相变行为，其中MIL-53材料是一个原型。在这项工作中，我们使用密度泛函方法来研究与相和密度变化相关的电子结构变化，并发现对于已知的mil -53型材料和担保结构，带隙的相关变化可能大于1 eV。此外，我们还表明，内部压力（通过客体分子）和外部压力对带隙大小和带隙状态有重要影响。mof的电子特性对呼吸跃迁的巨大响应可以在电阻开关、相变存储器、压阻、气敏和热致变色材料的未来应用中得到利用。
Many of the potential applications for metal-organic frameworks (MOFs) focus on exploiting their porosity for molecular storage, release, and separation, where the functional behavior is controlled by a subtle balance of host-guest interactions. Typically, the host structure is relatively unperturbed by the presence of guests; however, a subset of MOFs exhibit dramatic phase-change behavior triggered by the adsorption of guests or other stimuli, for which the MIL-53 material is an archetype. In this work, we use density functional approaches to examine the electronic structure changes associated with changes of phase and density and find the associated change in band gaps can be larger than 1 eV for known MIL-53-type materials and hypothecated structures. Moreover, we show that internal pressure (via guest molecules) and external pressure can exert a major influence on the band gap size and gap states. The large response in electronic properties to breathing transitions in MOFs could be exploitable in future applications in resistive switching, phase-change memory, piezoresistor, gas-sensing and thermochromic materials.