Hydrogen Storage in Metal-Organic Frameworks
The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H 2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H 2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H 2 adsorption measurements, to provide a comprehensive picture of H 2 adsorption at all relevant pressures. A rigorous understanding of experimental findings was further achieved via first-principles electronic structure calculations, which also supported synthetic efforts through predictions of additional novel frameworks with promising properties for vehicular H 2 storage. The results of the computational efforts also helped to elucidate the fundamental principles governing the interaction of H 2 with the frameworks, and in particular with exposed metal sites in the pores of these materials. Significant accomplishments from this project include the discovery of a metal-organic framework with a high H 2 binding enthalpy and volumetric capacity at 25 °C and 100 bar, which surpasses the metrics of any other known metal-organic framework. Additionally this material was designed to be extremely cost effective compared to most comparable adsorbents, which is imperative for eventual real-world applications. Progress toward synthesizing new frameworks containing multiple open coordination sites is also discussed, and appears to be the most promising future direction for hydrogen storage in these porous materials.