Li, Jialuo (2020-09). Metal-Organic Frameworks (MOFs) Based Nano-Materials in the Applications as Sensors and Catalysts. Doctoral Dissertation. Thesis uri icon

abstract

  • This dissertation begins with an introduction into the development of MOFs, particularly nano-sized MOFs and MOFs based metal nano-particles. (Chapter I) The reported synthetic strategies as well as their application in bio-related and catalyst field are discussed and perspectives on the promising future direction of this field are also presented. Chapter II demonstrates that "turn-on" fluorescent sensors can be assembled by combining a fluorophore and a recognition moiety within a complex cavity of a multicomponent MOF. The selective binding of CN- to recognition moieties inhibited the energy transfer between the two moieties, resulting in a fluorescence "turn on" effect. The optimized MOF-sensor had a CN- detection limit of 0.05 uM, which is much lower than traditional CN- molecular fluorescent sensors (~0.2 uM). Chapter III demonstrates that aggregation caused quenching of perylenes can be minimalized by molecular incorporation into metal-organic frameworks (MOFs). The average distance between perylene moieties was tuned by changing the linker ratios, thus controlling the fluorescence intensity, emission wavelength, and quantum yield. Taking advantage of the tunable fluorescence, inherent porosity, and high chemical stability of the parent MOF, utilization of the framework was able to be applied as a fluorescent sensor for oxygen detection in the gas phase. Ultimately, this work showed fast response times and good recyclability of the material. Chapter IV demonstrates that the utility of a coordination cage as a nanoparticle container to encapsulate ruthenium nanoparticles and tune their crystalline structures. Using this method, a rare fcc crystalline structure was able to be formed. This nanoparticle-cage composite exhibited record-high catalytic activity toward ammonia borane dehydrogenation. In addition, it provided a strategy for the encapsulation of metal nanocrystals within a soluble molecular cage, forming homogeneous catalysts with unprecedented activity. The main purpose of the work presented in this dissertation is to (1) explore the application of MOFs in the field of fluorescence sensors; (2) establish synthetic strategies for nano-sized MOFs; and (3) improve the catalytically performance of PCC supported metal nanoparticles. Building up on this work and the rapid development by others in this field, promising applications of MOFs in fluorescence sensors, bio-sensing, and clean energy generation are anticipated.

publication date

  • September 2020