A Study on Electron Acceptor of Carbonaceous Materials for Highly Efficient Hydrogen Uptakes

Significant efforts have been directed toward the identification of carbonaceous materials that can be utilized for hydrogen uptake in order to develop on-board automotive systems with a gravimetric capacity of 5.5 wt.%, thus meeting the U.S. Department of Energy technical targets. However, the capacity of hydrogen storage is limited by the weak interaction between hydrogen molecules and the carbon surface. Cigarette butts, which are the most abundant form of primary plastic waste, remain an intractable environmental pollution problem. To transform this source of waste into a valuable adsorbent for hydrogen uptake, we prepared several forms of oxygen-rich cigarette butt-derived porous carbon (CGB-AC, with the activation temperature range of 600 and 900 °C). Our experimental investigation revealed that the specific surface area increased from 600 to 700 °C and then decreased as the temperature rose to 900 °C. In contrast, the oxygen contents gradually decreased with increasing activation temperature. CGB-AC700 had the highest H2 excess uptake () of 8.54 wt.% at 77 K and 20 bar, which was much higher than that of porous carbon reported in the previous studies. We found that the dynamic interaction between the porosity and the oxygen content determined the hydrogen storage capacity. The underlying mechanisms proposed in the present study would be useful in the design of efficient hydrogen storage because they explain the interaction between positive carbonaceous materials and negative hydrogen molecules in quadrupole orbitals.

Upgrading the Hydrogen Storage of MOF-5 by Post-Synthetic Exchange with Divalent Metal Ions

In metal-organic frameworks (MOFs), mixed-metal clusters have the opportunity to adsorb hydrogen molecules due to a greater charge density of the metal. Such interactions may subsequently enhance the gravimetric uptake of hydrogen. However, only a few papers have explored the ability of mixed-metal MOFs to increase hydrogen uptake. The present work reveals the preparation of mixed metal metal-organic frameworks M-MOF-5 (where M = Ni2+, Co2+, and Fe2+) (where MOF-5 designates MOFs such as Zn2+ and 1,4-benzenedicarboxylic acid ligand) using the post-synthetic exchange (PSE) technique. Powder X-ray diffraction patterns and scanning electron microscopy images indicate the presence of crystalline phases after metal exchange, and the inductively coupled plasma–mass spectroscopy analysis confirmed the exchange of metals by means of the PSE technique. The nitrogen adsorption isotherms established the production of microporous M-MOF-5. Although the additional metal ions decreased the surface area, the exchanged materials displayed unique features in the gravimetric uptake of hydrogen. The parent MOF-5 and the metal exchanged materials (Ni-MOF-5, Co-MOF-5, and Fe-MOF-5) demonstrated hydrogen capacities of 1.46, 1.53, 1.53, and 0.99 wt.%, respectively. The metal-exchanged Ni-MOF-5 and Co-MOF-5 revealed slightly higher H2 uptake in comparison with MOF-5; however, the Fe-MOF-5 showed a decrease in uptake due to partial discrete complex formation (discrete complexes with one or more metal ions) with less crystalline nature. The Sips model was found to be excellent in describing the H2 adsorption isotherms with a correlation coefficient ≅ 1. The unique hydrogen uptakes of Ni− and Co-MOF-5 shown in this study pave the way for further improvement in hydrogen uptake.

Hydrogen Diffusion Influence on the Stabilizing Phases Behavior in the Ti-6Al-4V Alloy

For obtaining a unique microstructure in Ti-6Al-4V, hydrogen is utilized as a temporary alloying element; therefore, the mechanism of hydrogen diffusion in α and β phases should be understood. In this study, the electrochemical hydrogenation was applied to the half-length of thin titanium rods, and the diffusion annealing heat treatment was implemented at different temperatures. The hydrogen diffusion coefficient of α phase (Dα) and the hydrogen diffusion coefficient of β phase (Dβ) was determined by employing Abaqus software and C# program for three different homogeneous microstructures. The obtained results showed that Dβ increases, and Dα decreases when the hydrogen concentration in β phase increases. Furthermore, it was observed that each microstructure has a specific temperature in which the maximum hydrogen amount is absorbed. The hydrogen uptake depends more on the volume fraction of β phase than the volume fraction of α phase, which is considered an obstacle to hydrogen diffusion in this alloy.

Biphenyl Hydrogenation with Syngas for Hydrogen Purification and Transportation: Performance of Dispersed Catalytic Systems Based on Transition Metal Sulfides

The feasibility of biphenyl hydrogenation with syngas for hydrogen purification and binding with the aim of its transportation was demonstrated. Specific features of the hydrogenation of biphenyl as a promising organic hydrogen carrier using unsupported Ni–Mo sulfide catalysts were studied. In particular, the influence of temperature, reaction time, presence of water in the system, and Н2/СО gas mixture composition on the substrate conversion and selectivity with respect to products was examined. The highest conversion and the maximal hydrogen uptake are reached at 380°С in 6–8 h. The dispersed catalysts are active in biphenyl hydrogenation at the CO concentration in the Н2/СО gas mixture of up to 50 vol %, and H2O can act in this case as an in situ hydrogen source owing to the occurrence of the water-gas shift reaction.