Dihydrogen, methane, and carbon dioxide isotherm measurements were performed at 1−85 bar and 77−298 K on the evacuated forms of seven porous covalent organic frameworks (COFs). The uptake behavior and capacity of the COFs is best described by classifying them into three groups based on their structural dimensions and corresponding pore sizes. Group 1 consists of 2D structures with 1D small pores (9 A for each of COF-1 and COF-6), group 2 includes 2D structures with large 1D pores (27, 16, and 32 A for COF-5, COF-8, and COF-10, respectively), and group 3 is comprised of 3D structures with 3D medium-sized pores (12 A for each of COF-102 and COF-103). Group 3 COFs outperform group 1 and 2 COFs, and rival the best metal−organic frameworks and other porous materials in their uptake capacities. This is exemplified by the excess gas uptake of COF-102 at 35 bar (72 mg g−1 at 77 K for hydrogen, 187 mg g−1 at 298 K for methane, and 1180 mg g−1 at 298 K for carbon dioxide), which is similar to the performance of COF...

http://yaghi.berkeley.edu/pdfPublications/Furukawa09.pdf

Storage of Hydrogen, Methane, and Carbon Dioxide in Highly Porous Covalent Organic Frameworks for Clean Energy Applications

Hydrogen is a promising energy carrier in future energy systems. However, storage of hydrogen is a substantial challenge, especially for applications in vehicles with fuel cells that use proton-exchange membranes (PEMs). Different methods for hydrogen storage are discussed, including high-pressure and cryogenic-liquid storage, adsorptive storage on high-surface-area adsorbents, chemical storage in metal hydrides and complex hydrides, and storage in boranes. For the latter chemical solutions, reversible options and hydrolytic release of hydrogen with off-board regeneration are both possible. Reforming of liquid hydrogen-containing compounds is also a possible means of hydrogen generation. The advantages and disadvantages of the different systems are compared.

Chemical and Physical Solutions for Hydrogen Storage

The storage of gases in porous adsorbents, such as activated carbon and carbon nanotubes, is examined here thermodynamically from a systems viewpoint, considering the entire adsorption-desorption cycle. The results provide concrete objective criteria to guide the search for the "Holy Grail" adsorbent, for which the adsorptive delivery is maximized. It is shown that, for ambient temperature storage of hydrogen and delivery between 30 and 1.5 bar pressure, for the optimum adsorbent the adsorption enthalpy change is 15.1 kJ/mol. For carbons, for which the average enthalpy change is typically 5.8 kJ/mol, an optimum operating temperature of about 115 K is predicted. For methane, an optimum enthalpy change of 18.8 kJ/mol is found, with the optimum temperature for carbons being 254 K. It is also demonstrated that for maximum delivery of the gas the optimum adsorbent must be homogeneous, and that introduction of heterogeneity, such as by ball milling, irradiation, and other means, can only provide small increases in physisorption-related delivery for hydrogen. For methane, heterogeneity is always detrimental, at any value of average adsorption enthalpy change. These results are confirmed with the help of experimental data from the literature, as well as extensive Monte Carlo simulations conducted here using slit pore models of activated carbons as well as atomistic models of carbon nanotubes. The simulations also demonstrate that carbon nanotubes offer little or no advantage over activated carbons in terms of enhanced delivery, when used as storage media for either hydrogen or methane.

/pdf/optimum-conditions-for-adsorptive-storage-26opq4h9wj.pdf

Optimum conditions for adsorptive storage.

Asphaltenes, the most aromatic of the heaviest components of crude oil, are critical to all aspects of petroleum use, including production, transportation, refining, upgrading, and heavy-end use in paving and coating materials. As such, efficiency in these diverse disciplines mandates proper chemical accounting of structure−function relations of crude oils and asphaltenes, the vision of petroleomics (Asphaltenes, Heavy Oils and Petroleomics; Mullins, O. C., Sheu, E. Y., Hammami, A., Marshall, A. G., Eds.; Springer: New York, 2007). Indeed, the molecular characterization of asphaltenes is required as well as the detailed understanding of the hierarchical colloidal structures of asphaltenes and petroleum. With great prescience, Professor Teh Fu Yen and co-workers proposed a hierarchical model of asphaltenes to account for many of their characteristics known at that time (Dickie, J. P.; Yen, T. F. Macrostrucutres of asphaltic fractions by various instrumental methods. Anal. Chem. 1967, 39, 1847−1852). This m...

The Modified Yen Model

The Yen–Mullins model, also known as the modified Yen model, specifies the predominant molecular and colloidal structure of asphaltenes in crude oils and laboratory solvents and consists of the following: The most probable asphaltene molecular weight is ∼750 g/mol, with the island molecular architecture dominant. At sufficient concentration, asphaltene molecules form nanoaggregates with an aggregation number less than 10. At higher concentrations, nanoaggregates form clusters again with small aggregation numbers. The Yen–Mullins model is consistent with numerous molecular and colloidal studies employing a broad array of methodologies. Moreover, the Yen–Mullins model provides a foundation for the development of the first asphaltene equation of state for predicting asphaltene gradients in oil reservoirs, the Flory–Huggins–Zuo equation of state (FHZ EoS). In turn, the FHZ EoS has proven applicability in oil reservoirs containing condensates, black oils, and heavy oils. While the development of the Yen–Mullin...

Advances in Asphaltene Science and the Yen–Mullins Model

The storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy. Previous strategies--where hydrogen has been bound chemically, adsorbed in materials with permanent void space or stored in hybrid materials that combine these elements--have problems arising from either technical considerations or materials cost. A recently reported clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures (approximately 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to approximately 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.

Tuning clathrate hydrates for hydrogen storage

The inhibition activities of two antifreeze proteins (AFPs) on the formation of tetrahydrofuran (THF) clathrate hydrate have been tested. AFPs from fish (wfAFP) and insect (CfAFP) changed the morphology of growing THF hydrate crystals. Also, both AFPs showed higher activities in inhibiting the formation THF hydrate than a commercial kinetic inhibitor, poly(vinylpyrrolidone) (PVP). Strikingly, both AFPs also showed the ability to eliminate the "memory effect" in which the crystallization of hydrate occurs more quickly after the initial formation. This is the first report of molecules that can inhibit the memory effect. Since the homogeneous nucleation temperature for THF hydrate was measured to be 237 K, close to that observed for ice itself, the action of kinetic inhibitors must involve heterogeneous nucleation. On the basis of our results, we postulate a mechanism for heterogeneous nucleation, the memory effect and its elimination by antifreeze proteins.

Effect of antifreeze proteins on the nucleation, growth, and the memory effect during tetrahydrofuran clathrate hydrate formation.

On the formation and properties of asphaltene nanoaggregates and clusters by DC-conductivity and centrifugation

The critical nanoaggregate concentration (CNAC) of asphaltenes in toluene has been studied by a variety of methods recently. Here, we explore low-frequency electrical impedance measurements to detect and quantify nanoaggregate formation of asphaltenes. The Nyquist and Bode plots confirm the frequency range necessary for the dominance of (organic) ion conduction as opposed to reactive impedance. Impedance measurements are made as a function of the asphaltene concentration in toluene. We perform ionic conduction measurements at low frequency to avoid electrode polarization effects and then extrapolate to obtain direct-current (DC) conductivity. In a plot of DC conductivity versus asphaltene concentration, we see a clear break between two linear regions that is attributed to nanoaggregate formation. Very close agreement with high-Q ultrasonic measurements is shown for two petroleum asphaltenes with different CNACs. In addition, this work is shown to be consistent with previous alternating-current (AC) conduc...

Critical Nanoaggregate Concentration of Asphaltenes by Direct-Current (DC) Electrical Conductivity†

The effect of Type I antifreeze protein (AFP) from winter flounder on the formation of propane hydrate and methane hydrate was studied. We show that the formation of both hydrates is inhibited significantly, with both nucleation and crystal growth being affected. Also, AFP showed the so-far unique ability to eliminate the "memory effect" in the reformation of gas hydrate. We have proposed a mechanism involving the interference of AFP with heterogeneous nucleation and subsequent growth of the hydrates. It is also shown that a number of samples must be studied in order to obtain meaningful statistics, and that magnetic resonance imaging provides a novel way of studying the nucleation and growth of hydrate in multiple droplets.

Huang Zeng

Papers

Tuning clathrate hydrates for hydrogen storage

Effect of antifreeze proteins on the nucleation, growth, and the memory effect during tetrahydrofuran clathrate hydrate formation.

On the formation and properties of asphaltene nanoaggregates and clusters by DC-conductivity and centrifugation

Critical Nanoaggregate Concentration of Asphaltenes by Direct-Current (DC) Electrical Conductivity†

Effect of antifreeze protein on nucleation, growth and memory of gas hydrates