Novel Carbon (C)-Boron (B)-Nitrogen (N)-Containing H2 Storage Materials
- Boston College, Chestnut Hill, MA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Univ. of Alabama, Tuscaloosa, AL (United States)
- Protonex Technology Corporation, Southborough, MA (United States)
The following summarizes the research conducted for DOE project DE-EE0005658 “Novel Carbon(C)-Boron(B)-Nitrogen(N)-Containing H2 Storage Materials”. This work focused in part on the continued study of two materials identified from the preceding project DE-FG360GO18143 (“Hydrogen Storage by Novel CBN Heterocycle Materials”) as lead candidates to meet the DOE technical targets for either vehicular or non-automotive hydrogen storage applications. Specifically, a room-temperature liquid, 3-methyl-1,2-cyclopentane (B), and a high H2 capacity solid, 1,2-BN-cyclohexane (J), were selected for further characterization and performance optimization. In addition to these compounds, the current project also aimed to prepare several new materials predicted to be disposed towards direct reversibility of H2 release and uptake, a feature deemed critical to achieving efficient recycling of spent fuel end products. To assist in the rational design of these and other next-generation materials, this project undertook to investigate the mechanism of hydrogen release from established compounds (mainly B and J) using a combined experimental/computational approach. Among this project’s signature accomplishments, the preliminary synthetic route to B was optimized for production on decagram scale. With such quantities of material available, its performance in powering an actual 30 W proton exchange membrane (PEM) fuel cell stack was tested and found to be identical to that of facility H2. Despite this positive proof-of-concept achievement, however, further consideration of neat B as a potential hydrogen storage material was abandoned due to evidence of thermal instability. Specifically, mass spectrometry-coupled thermogravimetric analysis (TGA-MS) revealed significant H2 release from B to initiate at 50 °C, well below the 60 °C minimum threshold set by the DOE. This result prompted a more extensive investigation in the decomposition mechanism of B vis-à-vis that of J, which exhibited in neat form a substantially higher onset temperature for spontaneous H2 release (70 °C). Solution-phase kinetic experiments using ReactIR established a second-order dependence for the initial loss of H2 from both B and J; Arrhenius analysis, however, revealed the activation barrier for this reaction was lower for B than for J, which presumably contributes to the diminished thermal stability of the former. On the basis of these and other experimental results, extensive computational efforts yielded a reasonable mechanistic model for the dehydrogenation of 1,2-BN-cycloalkane materials. While the prospect of neat B as a suitable hydrogen storage material was discarded, it was proposed that the combination of B with more thermally stable amine-borane-based materials might afford mixtures with improved properties. Indeed, when B was combined with ammonia borane (AB) in a 2:1 molar ratio, the two materials formed a liquid. More significantly, this mixture remained liquid even after complete dehydrogenation, thus establishing the potential for a single-phase fuel cycle. (In contrast, the dehydrogenation product of neat B is a low melting solid (mp = 28-30 °C).) Another advantage conferred by the blend formulation was a dramatic reduction in the amount of borazine produced by AB. Borazine is a well-known contaminant of H2 produced by the thermal decomposition of neat AB, and exerts deleterious effects on fuel cell performance. Residual gas analysis (RGA) of the gas stream generated from the B-AB blend, however, detected just 0.01% borazine content when a Pt-Ni nanoparticle dehydrogenation catalyst was used. In all ii then, the 2:1 B-AB blend marks a major achievement in the effort to develop a suitable liquid amine-borane hydrogen storage material, and merits further investigation into the optimization for practical adoption. Similar realization of the potential of J as a high % wt. H2 material required a method to dehydrogenate the carbonaceous components of the molecule without the use of a sacrificial hydrogen acceptor, as had been reported in the previous project. Ultimately, this reaction was achieved for a B,N-disubstituted BN-cyclohexene model substrate using a gas flow system with a fixed Pd/C catalyst bed. Considerable work remains, however, to translate these initial results into a general protocol for complete dehydrogenation of fully saturated BN-cycloalkane materials such as J. With concrete confirmation of the possibility to perform both BN and CC dehydrogenation on a single theoretical substrate, COMSOL modeling was used to evaluate the effects of thermodynamically coupling the two reactions. It was hypothesized that the heat generated from exothermic BN dehydrogenation would partially drive the endothermic CC dehydrogenation reaction; this additional heat consumption was expected to in turn confer the benefit of lowering the maximum reactor temperature. A two-dimensional model of an axisymmetric reactor including experimental kinetic and calculated thermodynamic parameters for both reactions did indeed predict these outcomes. The extent to which the effects of thermodynamic coupling actually manifested, however, were also revealed to depend strongly on the relative rates of the two reactions, as well as the magnitude of the equilibrium constant governing the progress of the endothermic process. Given the evident complexity of attaining high effective % wt. H2 capacity with J, alternative systems were investigated for greater facility of extensive H2 release. Among those studied, 1,2,4,5-bis-BN-cyclohexane (H) demonstrated the most favorable properties, particularly with respect to thermal stability: rather than decompose, a neat sample instead sublimed when heated above 150 °C. Nevertheless, two commercially available catalytic systems were identified to effect release of two H2 equivalents from H. Release of further equivalents were apparently impeded by the formation of either polymeric material or one of two dimeric cage compounds depending on the catalyst used. Notably, a method to regenerate H from these product mixtures remains to be developed. Thus, while H may prove useful for certain long-term energy storage needs, it is currently less suited applications involving frequent fuel consumption. Similar difficulties were also encountered in attempts to realize the complete fuel cycle of 1,3-BN-cyclohexane (E) and B,N-substituted derivatives thereof. It had been initially proposed that E would provide for readily reversible BN dehydrogenation through a measure of frustrated Lewis pair-type character. Indeed, computations predicted this reaction would be essentially thermoneutral in solution. In the course of attempts to fully hydrogenate the spent fuel, however, dimeric species formed and proved resistant to further BN reduction. While a number of monomeric cyclic compounds were also successfully synthesized as formal boron-nitrogen frustrated Lewis pairs, none demonstrated any capacity to split H2 across the BN unit. The challenge of developing a practical amine-borane-based material for readily reversible hydrogen storage thus remains unresolved at this time. As such, it deserves consideration as a major objective of any future work.
- Research Organization:
- Boston College, Chestnut Hill, MA (United States)
- Sponsoring Organization:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office
- DOE Contract Number:
- EE0005658
- OSTI ID:
- 1393260
- Report Number(s):
- DE-EE0005658
- Country of Publication:
- United States
- Language:
- English
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