Evidence of catalytic production of hot atomic hydrogen in RF generated hydrogen/helium plasmas

A study of the line shapes of hydrogen Balmer series lines in RF generated low pressure He/H₂ plasmas produced results suggesting a catalytic process between helium and hydrogen species results in the generation of ‘hot’ (ca. 28 eV) atomic hydrogen. Even far from the electrodes ‘hot’ atomic hydrogen was predominant in He/H₂ plasmas. Line shapes, relative line areas of cold and hot atomic hydrogen (hot/cold > 2.5), were very similar for areas between the electrodes and far from the electrodes for these plasmas. In contrast, in Xe/H₂ only ‘warm’ (<5 eV) hydrogen (warm/cold < 1.0) was found between the electrodes, and only cold hydrogen away from the electrodes. Earlier postulates that preferential hydrogen line broadening in plasmas results from the acceleration of ionic hydrogen in the vicinity of electrodes, and the special charge exchange characteristics of Ar/H₂+ are clearly belied by the present results that show atomic hydrogen line shape are similar for He/H₂ plasmas throughout the relatively large cylindrical (14 cm ID × 36 cm length) cavity.     

Fast H in hydrogen mixed gas microwave plasmas when an atomic hydrogen supporting surface was present

Atomic hydrogen is heated to temperatures of up to two orders of magnitude greater than the electron temperature or the temperature of any other species in certain hydrogen mixed gas RF or glow discharge plasmas. A crucial test of energetic hydrogen chemistry regarding a resonant energy transfer or rt-mechanism (RTM) versus field acceleration models (FAM) as the basis of this selective isotropic heating of a population of extraordinarily high-kinetic-energy hydrogen atoms is the observation of fast H in microwave cells proven to lack a high field as shown by the complete absence of fast H (∼0.08 eV) by Jovicevic et al. [S. Jovicevic, N. Sakan, M. Ivkovic, N. Konjevic, J. Appl. Phys. 105, 013306-1 (2009)]. The RTM predicts an enhancement in the production of fast H with the presence of a surface to support a high concentration of hydrogen atoms in order to initiate the energetic hot H source reaction that then propagates isotropically throughout the plasma. In contrast to the prior results, extraordinarily fast H of greater than 4 eV (50 times that observed and deemed possible in the Evenson microwave cell by FAM advocate Jovicevic et al.) and 50% fractional population was observed as predicted for RTM using the catalytic reaction systems of He/H₂, Ar/H₂, pure H₂, and water vapor microwave plasmas when an electrically insulating, but atomic hydrogen supporting material was placed in the plasma region. Increasing concentrations of Xe in the non-catalytic Xe/H₂ system results in a significant decrease in the energy and population of fast excited-state H atoms.     

CdSe quantum dots sensitized nanoporous hematite for photoelectrochemical generation of hydrogen

A novel system of CdSe quantum dots (QDs) sensitized porous hematite (α-Fe₂O₃) films has been investigated as a potential photoelectrode for hydrogen generation via photoelectrochemical (PEC) splitting of water. Before sensitization, nanoporous hematite thin films were prepared by spray pyrolysis. Characterizations for crystalline phase formation, crystallite size, absorption spectra, and flatband potential were carried out to analyze PEC data. Loading time of sensitizer to hematite thin films was found to be crucial in affecting its PEC properties. Film having sensitizer loading time as 42 h exhibited best photocurrent density of 550 μA cm⁻² at 1.0 V versus SCE. Current study, for the first time, explores the possibility of using low band gap QDs sensitization on a low band gap film, hematite in PEC splitting of water.     

The decomposition of aromatic hydrocarbons during coal pyrolysis in hydrogen plasma: A density functional theory study

Coal pyrolysis in hydrogen plasma has been proposed to undergo two steps. Volatiles such as aromatic hydrocarbons vaporize from coal and subsequently decompose to produce acetylene and hydrogen. We employed a density functional theory (DFT) to investigate the decomposition pathway of benzene, a model aromatic hydrocarbon, for understanding the coal pyrolysis in hydrogen plasma. The results indicate that there are two low-energy decomposition channels. Active hydrogen atoms in the plasma play an important role in the initiation of benzene decomposition, which leads to the formation of c-C₆H₅ particle and hydrogen molecule. The c-C₆H₅ could further decompose to yield acetylene, hydrogen and carbon soot, which is more favorable based on its lower activation energies. The decomposition makes the primary contribution to acetylene formation, and the dehydrogenation results in the additional hydrogen gas and serious coking. The active hydrogen atoms in plasma can remarkably lessen the energy barriers required for the reactions.     

Irreversible hydrogen quantum dynamics and anomalous scattering behavior in liquids and solids

We report on neutron–proton Compton scattering experiments on various hydrogen containing materials like water, an organic polymer and an ionic metal hydride. Furthermore, results of an electron–proton Compton scattering experiment on the polymer are presented. The results reveal a strong decrease of the scattering integral intensities due to the protons in these materials. Thus far these effects have found no common explanation based on existing condensed matter theories. Rather, they invoke the existence of quantum correlations (also called quantum entanglement—QE) and decoherence between the particles. Of particular importance in the present context is the fact that the interaction time of the probe (i.e. neutron or electron) must be of the same order of magnitude as the decay of the coherence (also called decoherence) of the correlated particles. The found experimental effects and their possible explanations may have far reaching consequences for condensed matter physics and in particular for the theoretical treatment of hydrogen containing materials.     

Selective storage and evolution of hydrogen on nafion/NaCl/graphene quantum dot mixed matrix using tensammetry as power electrochemical technique

Hydrogen storage/evolution behavior of nafion/NaCl/graphene quantum dot (GQD) mixed matrix as selective hydrogen capacitor (power source) was evaluated in detail through an electrochemical process at two independent potential ranges. For this purpose, a three-electrode system included Pt disk as counter electrode, Ag/AgCl as reference electrode and GQD-based mixed matrix-modified Pt disk as working electrode. For hydrogen storage, the deposition potential and time were evaluated to ?1.0 V (vs. Ag/AgCl) and 120 s, respectively under high basic solution generated using NaOH (1.0 M) solution, followed by evolution of hydrogen at +0.8 V (vs. Ag/AgCl) during formation of hydrogen bubbles. The main advantage of this system was the occurrence of hydrogen storage and evolution at two independent potential windows. Both mass transfer and adsorption processes were estimated for the tensammetric peak during the evolution step. The mechanism of hydrogen storage and evolution was obeyed from diffusion and tensammetry, respectively. According to Randles–Sevcik equation using 1.0 mM ${{\text{Fe}\left(\text{CN}\right)}_6}^{3?/4?}$, the active surface area of nafion/NaCl/GQD mixed matrix was ～1906 m²g^?1. Based on the CHN analyses, pressure-concentration temperature as well as hydrogen temperature-programmed desorption, the capacity of the synthesized GQDs for hydrogen storage and evolution was estimated to at least 10.1 and 8.6 wt%, respectively. The stability of the electrode was also estimated during 7000s by chronoamperometry during applying at least 40 cycles in the range from ?1.0 to +1.3 V with reproducible tensammetric peak current (relative standard deviation: 2.54%).     

Optimal cross sections of filament-wound toroidal hydrogen storage vessels based on continuum lamination theory

One of the most important issues for the design of toroidal hydrogen storage vessels reflects on the determination of the most efficient meridional cross sections. In this paper we outline the cross-sectional shape determination for filament-wound toroidal pressure vessels based on the continuum theory and the optimality condition of equal shell strains. With the aid of the geodesic law and the equal-stains condition, the continuum-based optimal cross sections are determined while taking into account the shell thickness build-up along the meridional direction. As an additional option, the influence of the theoretically required axial load on the resulting meridian profile is also evaluated and the results show that the meridian curve returns to zero altitude at a certain magnitude of that axial load and thus forms a closed dome. The cross-sectional shapes and structural performance of classical pressure vessels, circular and continuum-based optimal toroidal pressure vessels are respectively determined and compared to each other. The results reveal that toroidal hydrogen storage vessels designed using the optimal cross sections provide better performance than the circular toroidal vessels and the classical vessels.     

Mechanism of transition metal cluster catalysts for hydrogen evolution reaction

Studying the hydrogen evolution reaction (HER) catalyst is important for the global energy crisis. Clusters have many special characteristics due to quantum size effect and super high specific surface area, including optical performance, catalytic performance, etc. In this work, the structures of transition metal cluster TM_n (TM = Co, Ni, Cu, Pd, Pt, n = 4–10) were searched and optimized by quantum chemistry methods. To search for non-precious metal catalysts, we calculated the Gibbs free energies for HER process on different clusters. Furthermore, the electronic structures of clusters before and after the reaction with H were analyzed, including the molecular surface electron distribution, the frontier molecular orbital, and the charge transfer properties, which dominated the HER processes. The results show that the Cu clusters have excellent HER catalytic properties due to its suitable surface electron distribution and HOMO/LUMO levels, especially Cu₄, Cu₇ and Cu₉, which even comparable to Pt catalysts. These results can help us better understand the mechanism of clusters catalyze HER process.     

Quantum dots as enhancer in photocatalytic hydrogen evolution: A review

Advanced energy conversion processes like photochemical and photoelectrochemical water splitting now a day plays a very important role in challenging the present energy crisis of our world. The successful utilization of this process depends on development of highly efficient, more stable, low cost and outstanding environmental benign semiconductor materials. From recent advancements, it is revealed that quantum dots (QDs) are very outstanding and promising material for the mentioned processes due to their favorable physical and chemical characteristics like high absorption co-efficient, quantum confinement effect, thermal, chemical, mechanical and optical stability, high conductivity and recyclability. In this review article, we have clearly explained the importance of QDs in water splitting along with the general mechanism involved in the process. Following that the enhancement of different materials like metal oxides, layered double hydroxides (LDH), carbonaceous materials (g-C₃N₄, benzene and benzene like materials) by QDs have discussed in the field of water splitting.     

Cobalt sulfide quantum dots modified TiO2 nanoparticles for efficient photocatalytic hydrogen evolution

Cobalt sulfide quantum dots (CoSx QDs) modified TiO₂ nanoparticles are prepared with a precipitation-deposition method using TiO₂, cobalt acetate and sodium sulfide as the precursors. CoSx QD acts as an effective cocatalyst, which accelerates the transfer of the photo-generated electrons and serves as the active site for the reaction between electrons and H₂O, thus enhancing the separation of the e⁻/h⁺ pairs and the photocatalytic H₂ production activity of TiO₂. The amount of CoSx exhibits an optimum value at about 5% (mole ratio to TiO₂), at which the H₂ production rate achieves 838 μmol h⁻¹ g⁻¹ using ethanol as the sacrificial reagent. This exceeds that of the pure TiO₂ by more than 35 times.     

Li decorated penta-silicene as a high capacity hydrogen storage material: A density functional theory study

The H₂ adsorption characteristics of Li decorated single-sided and double-sided penta-silicene are predicted via density functional theory (DFT). The orbital hybridization results in Li atom strongly bind onto the surface of the penta-silicene with a large binding energy and it keeps the decorated Li atoms from aggregation. Moreover, Li decorated double-sided penta-silicene can store up to 12H₂ molecules with the average hydrogen adsorption energy of ?0.220 eV/H₂ and hydrogen uptake capacity of 6.42 wt%, respectively. The ab initio molecular dynamics (AIMD) simulations demonstrate the H₂ molecules are released gradually from the substrate material with the increasing simulation time and the calculated desorption temperature T_D is 281 K in the suitable operating temperature range. Our explorations confirm that Li decorated penta-silicene can be regarded as a promising hydrogen storage candidate for hydrogen storage applications.     

Oxidative pyrolysis reforming of methanol in warm plasma for an on-board hydrogen production

To achieve on-board hydrogen production with high energy efficiency and low energy cost, the oxidative pyrolysis reforming (OPR) of methanol using air as an oxidant in a heat-insulated gliding arc plasma reactor is explored. Effects of dioxygen/methanol (O₂/C) ratio, steam/methanol (S/C) ratio and specific energy input (SEI) on the OPR are investigated. The reaction rate ratio (α) of pyrolysis reforming to oxidative reforming in the OPR is deduced. The OPR of methanol strongly depends on the O₂/C ratio, with which methanol conversion increases rapidly. In the OPR, methanol conversions occur mainly by the oxidative reforming (partial oxidation) at the O₂/C ratios below 0.20, but by the oxidative reforming and the promoted pyrolysis reforming at the O₂/C ratios above 0.20, which is confirmed by the enthalpy change for the overall reaction of OPR. Higher O₂/C ratio results in higher energy efficiency and lower energy cost, however, higher S/C ratio or larger SEI leads to lower energy efficiency and higher energy cost. Under conditions of O₂/C = 0.30, S/C = 0.5, SEI = 24 kJ/mol, energy efficiency of 74% and energy cost of 0.45 kWh/Nm³ with methanol conversion of 88% are achieved.     

Hydrolysis of NH3BH3 and NaBH4 by graphene quantum dots-transition metal nanoparticles for highly effective hydrogen evolution

Recently, effective hydrogen (H₂) evolution upon hydrolysis of different hydrogen storage materials has received much attention. Herein, graphene quantum dots-transition metal nanoparticles (GQDs-TMNPs), with high dispersibility and activity, have been successfully applied in the hydrolysis of both NH₃BH₃ (AB) and NaBH₄ for the first time. GQDs-RhNPs, GQDs-RuNPs, and GQDs-PtNPs are very effective in the hydrolysis of AB and the turnover frequencies (TOFs) can achieve to as high as 656, 384, and 281 mol_H2·mol_cat^?1 min^?1, respectively. Moreover, the synergistic effect between GQDs and TMNPs is explored, and the mechanisms of catalytic hydrolysis of AB and NaBH₄ by GQDs-TMNPs are proposed. This work not only paves the way for the development of GQDs-TMNPs nanocatalysts for the different hydrogen storage materials, but also further advances the understanding of the synergistic effects between GQDs and TMNPs.     

Density functional theory study of reversible hydrogen storage in monolayer beryllium hydride by decoration with boron and lithium

The hydrogen storage capacity of M-decorated (M = Li and B) 2D beryllium hydride is investigated using first-principles calculations based on density functional theory. The Li and B atoms were calculated to be successfully and chemically decorated on the Surface of the α-BeH₂ monolayer with a large binding energy of 2.41 and 4.45eV/atom. The absolute value was higher than the cohesive energy of Li and B bulk (1.68, 5.81eV/atom). Hence, the Li and B atoms are strongly bound on the beryllium hydride monolayer without clustering. Our findings show that the hydrogen molecule interacted weakly with B/α-BeH₂(B-decorated beryllium hydride monolayer) with a low adsorption energy of only 0.0226 eV/H₂ but was strongly adsorbed on the introduced active site of the Li atom in the decorated BeH₂ with an improved adsorption energy of 0.472 eV/H₂. Based on density functional theory, the gravimetric density of 28H₂/8li/α-BeH₂) could reach 14.5 wt.% higher than DOE's target of 6.5 wt. % (the criteria of the United States Department of Energy). Therefore, our research indicates that the Li-decorated beryllium hydride monolayer could be a candidate for further investigation as an alternative material for hydrogen storage.     

Sustainability of hydrogen supply chain. Part II: Prioritizing and classifying the sustainability of hydrogen supply chains based on the combination of extension theory and AHP

The purpose of this study is to develop a method for prioritizing and classifying the sustainability of hydrogen supply chains and assist decision-making for the stakeholders/decision-makers. Multiple criteria for sustainability assessment of hydrogen supply chains are considered and multiple decision-makers are allowed to participate in the decision-making using linguistic terms. In this study, extension theory and analytic hierarchy process are combined to rate the sustainability of hydrogen supply chains. The sustainability of hydrogen supply chains could be identified according to the synthesis correlation degrees to each classical domain. Finally, an illustrative case is studied by the proposed method, and the results show that the proposed method is feasible for prioritizing and classifying the sustainability of hydrogen supply chains.     

Selective deposition of Pd nanoparticles in porous PET membrane for hydrogen separation

Hydrogen purification based on Pd deposition in porous polymeric membranes show promising results for hydrogen permeability and selectivity. It is due to high absorption property of Pd nanoparticles. In this work, gas permeability of carboxylic group functionalized Polyethylene terephthalate (PET) membranes with different time of functionalization have been examined. It has been found that PET membrane having more –COOH group shows higher selectivity for Hydrogen (H₂). Further to improve the selectivity, these carboxylated PET membranes dipped in Pd nanoparticles solution for 6 h and found more selective for H₂ in comparison to Carbon dioxide (CO₂) and Nitrogen (N₂). As the carboxylation increases selectivity of H₂ improves drastically in the beginning and nearly get saturated after 24 h. Similar trend has been observed for these membranes after Pd nanoparticles deposition. Fourier transform infrared spectroscopy (FTIR) spectra of these membranes revealed that intensity of peaks related to –COOH group at 2968 cm^?1 & 1716 cm^?1 increases with functionalization time. Field Emission Scanning Electron Microscopy (FESEM) was used to study the surface morphology of membranes.     

High performance material for hydrogen storage: Graphenelike Si2BN solid

Recently, two dimensional graphenelike i.e. Si₂BN solid monolayer have attracted much attention for the use of hydrogen developments. The work is based on first principles calculations using density functional theory with long range van der Waal (vdW) interactions. The optimized structure is energetically more stable due to high formation energy 45.39 eV with PBE and 50.82 eV with HSE06 functionals, respectively. Our ab-initio studies show that Pd (palladium) adatoms secured graphenelike Si₂BN solid via two types of interactions; physisorption and chemisorptions reactions, which engrossing up to 3H₂ molecules signifying gravimetric limits of ≈6.95–10.21 wt %. The absorption energies vary from ?0.31 eV to ?1.93 eV with Pd-adatom and without Pd-adatom respectively, and it varies up to ?1.24 eV. The work function of pure Si₂BN is 5.36 eV while metal-adatom on monolayer Si₂BN with (1 to 6)H₂ molecules is 3.53 eV–4.99 eV and reaches up to 5.85 eV. The theoretical study suggests that the functionalized graphenelike Si₂BN is efficient for hydrogen storage and propose a possible improvement for advantageous storage of hydrogen at ambient conditions.     

The effect of clay on initial and residual saturation of hydrogen in clay-rich sandstone formation: Implications for underground hydrogen storage

Understanding wettability in rock-brine-hydrogen systems is essential for dependable predictions of capillary/residual trapping in clay-rich sandstone formations. Despite being the most used technique, wettability assessment based on contact angle measurements is confronted with inherent uncertainties that limit its reliability. In contrast, core flooding techniques provide a more direct and realistic picture of wettability and its time evolution. Nuclear Magnetic Resonance (NMR) allows us to evaluate the initial and residual hydrogen saturations and distribution along the core specimen. It is a fast, reliable, and effective way of inferring the impact of wettability on hydrogen migration, and residual trapping in prospective geo-storage rock formations. Recent publications have reported the evaluation of wettability in a brine-hydrogen-rock system where the rock is a clean sandstone (no clays). Here we evaluate the impact of the presence of clays in a sandstone, which has not been reported yet. NMR monitoring was employed to characterize the initial and residual hydrogen saturations in the Bandera Grey (BG) sandstone. To investigate the impact of clay minerals on hydrogen saturation, same rock sample was characterized in its natural state, and after heating it to 700 °C for 12 h in an air environment to burn off clay minerals, During the NMR core flooding experiments, ten pore volumes (PVs) were injected/withdrawn during the drainage/imbibition cycles at a fluid injection rate of 2 mL/min under room temperature and 1000 psi confining pressure. Due to the hydrophilicity of quartz and clay, the tested BG sandstone (clay-rich sandstone) shows a significant residual/trapped saturation (～3.5% can be reproduce); therefore, clay-rich sandstone may not be ideal for hydrogen storage unless cushion gas is used.The results show that initial and residual hydrogen saturations were slightly changed after firing (from 16% to 18% for initial and from 14% to 13% for residual). This also suggests that the wettability of the BG sandstone-brine-hydrogen system is slightly impacted by clay content and type. We also observed that clay firing at 700 °C has little effect on the porosity and gas permeability of the BG sandstone. Moreover, X-ray powder diffraction (XRD) results showed that quartz content increases from 68.1% to 76.2%, Kaolinite transformed into illite and clinochlore disappeared. The disappearance of chlorite after firing suggests that it is transformed into another clay type.