Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), 76344, Eggenstein-Leopoldshafen, Germany.
Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), 76344, Eggenstein-Leopoldshafen, Germany.
Adv Mater. 2018 Feb;30(8). doi: 10.1002/adma.201706551. Epub 2018 Jan 8.
Proton conducting nanoporous materials attract substantial attention with respect to applications in fuel cells, supercapacitors, chemical sensors, and information processing devices inspired by biological systems. Here, a crystalline, nanoporous material which offers dynamic remote-control over the proton conduction is presented. This is realized by using surface-mounted metal-organic frameworks (SURMOFs) with azobenzene side groups that can undergo light-induced reversible isomerization between the stable trans and cis states. The trans-cis photoisomerization results in the modulation of the interaction between MOF and guest molecules, 1,4-butanediol and 1,2,3-triazole; enabling the switching between the states with significantly increased (trans) and reduced (cis) conductivity. Quantum chemical calculations show that the trans-to-cis isomerization results in the formation of stronger hydrogen bridges of the guest molecules with the azo groups, causing stronger bonding of the guest molecules and, as a result, smaller proton conductivity. It is foreseen that photoswitchable proton-conducting materials may find its application in advanced, remote-controllable chemical sensors, and a variety of devices based on the conductivity of protons or other charged molecules, which can be interfaced with biological systems.
质子传导纳米多孔材料在燃料电池、超级电容器、化学传感器和受生物系统启发的信息处理设备等方面的应用引起了广泛关注。本文提出了一种具有动态远程控制质子传导能力的结晶纳米多孔材料。这是通过使用带有偶氮苯侧基的表面安装型金属有机骨架(SURMOF)来实现的,偶氮苯侧基可以在稳定的反式和顺式之间发生光诱导可逆异构化。反式-顺式光致异构化导致 MOF 和客体分子(1,4-丁二醇和 1,2,3-三唑)之间的相互作用发生调制,从而实现了具有显著增加(反式)和降低(顺式)电导率的状态之间的切换。量子化学计算表明,顺式-反式异构化导致客体分子与偶氮基团形成更强的氢键,使客体分子的结合更强,从而导致质子电导率更小。预计光致开关质子传导材料可能在先进的、远程可控的化学传感器以及基于质子或其他带电分子的导电性的各种设备中得到应用,这些设备可以与生物系统接口。