Publications

We will describe how novel nanoporous framework materials (NFM) such as metal-organic frameworks (MOFs) can be interfaced with common mechanical sensors, such as surface acoustic wave (SAW), microcantilever array, and quartz crystal microbalance (QCM) devices, and subsequently be used to provide selectivity and sensitivity to a broad range of analytes including explosives, nerve agents, and volatile organic compounds (VOCs). NFM are highly ordered, crystalline materials with considerable synthetic flexibility resulting from the presence of both organic and inorganic components within their structure. Chemical detection using micro-electro-mechanical-systems (MEMS) devices (i.e. SAWs, microcantilevers) requires the use of recognition layers to impart selectivity. Unlike traditional organic polymers, which are dense, the nanoporosity and ultrahigh surface areas of NFM allow for greater analyte uptake and enhance transport into and out of the sensing layer. This enhancement over traditional coatings leads to improved response times and greater sensitivity, while their ordered structure allows chemical tuning to impart selectivity. We describe here experiments and modeling aimed at creating NFM layers tailored to the detection of water vapor, explosives, CWMD, and volatile organic compound (VOCs), and their integration with the surfaces of MEMS devices. Molecular simulation shows that a high degree of chemical selectivity is feasible. For example, a suite of MOFs can select for strongly interacting organics (explosives, CWMD) vs. lighter volatile organics at trace concentrations. At higher gas pressures, the CWMD are deselected in favor of the volatile organics. We will also demonstrate the integration of various NFM on the surface of microcantiliver arrays, QCM crystals, and SAW devices, and describe new synthetic methods developed to improve the quality of NFM coatings. Finally, MOF-coated MEMS devices show how temperature changes can be tuned to improve response times, selectivity, and sensitivity.

Abstract not provided.

The objective of this project is to lay the foundation for using ordered nanoporous materials known as metal-organic frameworks (MOFs) to create devices and sensors whose properties are determined by the dimensions of the MOF lattice. Our hypothesis is that because of the very short (tens of angstroms) distances between pores within the unit cell of these materials, enhanced electro-optical properties will be obtained when the nanopores are infiltrated to create nanoclusters of metals and other materials. Synthetic methods used to produce metal nanoparticles in disordered templates or in solution typically lead to a distribution of particle sizes. In addition, creation of the smallest clusters, with sizes of a few to tens of atoms, remains very challenging. Nanoporous metal-organic frameworks (MOFs) are a promising solution to these problems, since their long-range crystalline order creates completely uniform pore sizes with potential for both steric and chemical stabilization. We report results of synthetic efforts. First, we describe a systematic investigation of silver nanocluster formation within MOFs using three representative MOF templates. The as-synthesized clusters are spectroscopically consistent with dimensions {le} 1 nm, with a significant fraction existing as Ag{sub 3} clusters, as shown by electron paramagnetic resonance. Importantly, we show conclusively that very rapid TEM-induced MOF degradation leads to agglomeration and stable, easily imaged particles, explaining prior reports of particles larger than MOF pores. These results solve an important riddle concerning MOF-based templates and suggest that heterostructures composed of highly uniform arrays of nanoparticles within MOFs are feasible. Second, a preliminary study of methods to incorporate fulleride (K{sub 3}C{sub 60}) guest molecules within MOF pores that will impart electrical conductivity is described.

In this work we demonstrate the concept of stress-induced chemical detection using metal-organic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N2 or O2. The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO2. Finally, we report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes. Copyright © 2008 American Chemical Society.

Abstract not provided.