Formation Of Molecular Hydrogen Research Articles

Borohydride Electrooxidation on Carbon-Supported Noble Metal Nanoparticles: Insights into Hydrogen and Hydroxyborane Formation

Borohydride anions (BH4–) are interesting as fuel for low-temperature alkaline fuel cells, owing to their high hydrogen content and low theoretical potential of oxidation. However, the borohydride electrooxidation mechanism and the potential dependence of the undesirable parallel hydrolysis pathway are not completely understood. In this study, by using a dual thin-layer flow-cell online coupled with a mass spectrometer and a rotating ring-disk electrode, the electrocatalytic activity and the dependence of the molecular hydrogen and hydroxiborane (BH3OH–) formation were investigated for carbon-supported Au, Ag, Pt, and Pd nanoparticles. For Au/C and Ag/C, the H2 and BH3OH– production presented a peak in the potential region of the first branch of the BOR wave and another increase in the metal oxide region. Pt/C and Pd/C showed accentuated H2 detection at the OCP, with a sharp decrease to practically zero after the BOR onset. Interestingly, and contrarily to what was observed for Au/C and Ag/C, the RRDE measurements showed BH3OH– production only at higher potentials (Pt- or Pd-oxides). These results were explained on the basis of the higher reactivity of Pt/C and Pd/C for the BOR, in which BHx-like species remain adsorbed and hydrogen is consumed via electrooxidation on their surfaces, at low potentials. On the other hand, Au/C and Ag/C, possessing lower reactivity (lower d-band center), the BH3-like species, produced in the first BOR steps, desorb from their surfaces and are detected at the ring. Concomitantly, at the BOR onset, H2 is formed, via recombination of adsorbed hydrogen atoms and can be detected by the mass spectrometer because these materials are relatively inactive for the hydrogen oxidation reaction.

Monte Carlo simulation to investigate the formation of molecular hydrogen and its deuterated forms

H2 is the most abundant interstellar species, and its deuterated forms (HD and D2) are also present in high abundance. The high abundance of these molecules could be explained by considering the chemistry that occurs on interstellar dust. Because of its simplicity, the rate equation method is widely used to study the formation of grain-surface species. However, because the recombination efficiency for the formation of any surface species is highly dependent on various physical and chemical parameters, the Monte Carlo method is best suited for addressing the randomness of the processes. We perform Monte Carlo simulations to study the formation of H2,HD and D2 on interstellar ice. The adsorption energies of surface species are the key inputs for the formation of any species on interstellar dusts, but the binding energies of deuterated species have yet to be determined with certainty. A zero-point energy correction exists between hydrogenated and deuterated species, which should be considered during modeling of the chemistry on interstellar dusts. Following some previous studies, we consider various sets of adsorption energies to investigate the formation of these species under diverse physical conditions. As expected, notable differences in these two approaches (rate equation method and Monte Carlo method) are observed for the production of these simple molecules on interstellar ice. We introduce two factors, namely, Sf and β, to explain these discrepancies: Sf is a scaling factor, which can be used to correlate the discrepancies between the rate equation and Monte Carlo methods, and β indicates the formation efficiency under various conditions. Higher values of β indicate a lower production efficiency. We observed that β increases with a decrease in the rate of accretion from the gas phase to the grain phase.

Microstructure from joint analysis of experimental data and ab initio interactions: Hydrogenated amorphous silicon

A study of the formation of voids and molecular hydrogen in hydrogenated amorphous silicon is presented based upon a hybrid approach that involves inversion of experimental nuclear magnetic resonance data in conjunction with ab initio total-energy relaxations in an augmented solution space. The novelty of this approach is that the voids and molecular hydrogen appear naturally in the model networks unlike conventional approaches, where voids are created artificially by removing silicon atoms from the networks. Two representative models with 16 and 18 at. % of hydrogen are studied in this work. The result shows that the microstructure of the a-Si:H network consists of several microvoids and few molecular hydrogen for concentration above 15 at. % H. The microvoids are highly irregular in shape and size, and have a linear dimension of 5–7 Å. The internal surface of a microvoid is found to be decorated with 4–9 hydrogen atoms in the form of monohydride Si–H configurations as observed in nuclear magnetic resonance experiments. The microstructure consists of (0.9–1.4)% hydrogen molecules of total hydrogen in the networks. These observations are consistent with the outcome of infrared spectroscopy, nuclear magnetic resonance, and calorimetry experiments.

Role of hydrogen formation and silver phase for methanol-SCR over silver/alumina

Formation of reaction products over silver/alumina during lean NOx reduction with methanol was studied, with and without addition of hydrogen to the feed. The silver phase in silver/alumina was analyzed by UV–vis spectroscopy in order to elucidate the influence of silver loading and different gas environments. Formation of molecular hydrogen and reduction of supported silver species were observed during selective catalytic reduction (SCR) with methanol, without hydrogen in the feed. This availability of hydrogen and the reduction of silver are suggested to contribute to the high low-temperature activity connected to oxygenates (like alcohols) as reducing agents for NOx.

Molecular hydrogen formation during water radiolysis in the presence of zirconium dioxide

The presence of zirconium dioxide (ZrO2) greatly increases H2 yields in water radiolysis, an inevitable process which takes place in nuclear power plants. The aim of this review is to compile available knowledge about ZrO2 effect on H2 yields. The following parameters taken into consideration include: (i) LET of radiation, (ii) form of the adsorbed water, (iii) presence of oxygen, (iv) surface area, (v) crystalline structure, (vi) size of particles, (vii) doping with other oxides, (viii) grafting, and (ix) catalytic decomposition of H2O2.

Revised rate coefficients for H2 and H− destruction by realistic stellar spectra

Understanding the processes that can destroy H$_2$ and H$^-$ species is quintessential in governing the formation of the first stars, black holes and galaxies. In this study we compute the reaction rate coefficients for H$_2$ photo--dissociation by Lyman--Werner photons ($11.2 - 13.6$ eV), and H$^-$ photo--detachment by 0.76 eV photons emanating from self-consistent stellar populations that we model using publicly available stellar synthesis codes. So far studies that include chemical networks for the formation of molecular hydrogen take these processes into account by assuming that the source spectra can be approximated by a power-law dependency or a black-body spectrum at 10$^4$ or $10^5$ K. We show that using spectra generated from realistic stellar population models can alter the reaction rates for photo-dissociation, $\rm k_{\rm{di}}$, and photo-detachment, $\rm k_{\rm{de}}$, significantly. In particular, $\rm k_{\rm{de}}$ can be up to $\sim 2-4$ orders of magnitude lower in the case of realistic stellar spectra suggesting that previous calculations have over-estimated the impact that radiation has on lowering H$_2$ abundances. In contrast to burst modes of star formation, we find that models with continuous star formation predict increasing $\rm k_{\rm{de}}$ and $\rm k_{\rm{di}}$, which makes it necessary to include the star formation history of sources to derive self-consistent reaction rates, and that it is not enough to just calculate J$_{21}$ for the background. For models with constant star formation rate the change in shape of the spectral energy distribution leads to a non-negligible late-time contribution to $\rm k_{\rm{de}}$ and $\rm k_{\rm{di}}$, and we present self-consistently derived cosmological reaction rates based on star formation rates consistent with observations of the high redshift Universe.

Damped Lyman α absorbers as a probe of stellar feedback

We examine the abundance, clustering and metallicity of Damped Lyman-alpha Absorbers (DLAs) in a suite of hydrodynamic cosmological simulations using the moving mesh code AREPO. We incorporate models of supernova and AGN feedback, as well as molecular hydrogen formation. We compare our simulations to the column density distribution function at $z=3$, the total DLA abundance at $z=2-4$, the measured DLA bias at $z=2.3$ and the DLA metallicity distribution at $z=2-4$. Our preferred models produce populations of DLAs in good agreement with most of these observations. The exception is the DLA abundance at $z < 3$, which we show requires stronger feedback in $10^{11-12} \, h^{-1} M_\odot$ mass halos. While the DLA population probes a wide range of halo masses, we find the cross-section is dominated by halos of mass $10^{10} - 10^{11} \, h^{-1} M_\odot$ and virial velocities $50 - 100 \;\mathrm{km/s}$. The simulated DLA population has a linear theory bias of $1.7$, whereas the observations require $2.17 \pm 0.2$. We show that non-linear growth increases the bias in our simulations to $2.3$ at $k=1\; \mathrm{Mpc/}h$, the smallest scale observed. The scale-dependence of the bias is, however, very different in the simulations compared against the observations. We show that, of the observations we consider, the DLA abundance and column density function provide the strongest constraints on the feedback model.

Formation and evolution of molecular hydrogen in disc galaxies with different masses and Hubble types

We investigate the physical properties of molecular hydrogen (H2) in isolated and interacting disk galaxies with different masses and Hubble types by using chemodynamical simulations with H2 formation on dust grains and dust growth and destruction in interstellar medium (ISM). We particularly focus on the dependences of H2 gas mass fractions (f_H2), spatial distributions of HI and H2, and local H2-scaling relations on initial halo masses (M_h), baryonic fractions (f_bary), gas mass fractions (f_g), and Hubble types. The principal results are as follows. The final f_H2 can be larger in disk galaxies with higher M_h, f_bary, and f_g. Some low-mass disk models with M_h smaller than 10^10 M_sun show extremely low f_H2 and thus no/little star formation, even if initial f_g is quite large (>0.9). Big galactic bulges can severely suppress the formation of H2 from HI on dust grains whereas strong stellar bars can not only enhance f_H2 but also be responsible for the formation of H2-dominated central rings. The projected radial distributions of H2 are significantly more compact than those of HI and the simulated radial profiles of H2-to-HI-ratios (R_mol) follow roughly R^-1.5 in MW-type disk models. Galaxy interaction can significantly increase f_H2 and total H2 mass in disk galaxies. The local surface mass densities of H2 can be correlated with those of dust in a galaxy. The observed correlation between R_mol and gas pressure (R_mol ~ P_g^0.92) can be well reproduced in the simulated disk galaxies.

Light-driven hydrogen production from aqueous protons using molybdenum catalysts.

Homogeneous light-driven systems employing molecular molybdenum catalysts for hydrogen production are described. The specific Mo complexes studied are six-coordinate bis(benzenedithiolate) derivatives having two additional isocyanide or phosphine ligands to complete the coordination sphere. Each of the complexes possesses a trigonal prismatic coordination geometry. The complexes were investigated as proton reduction catalysts in the presence of [Ru(bpy)3](2+), ascorbic acid, and visible light. Over 500 TON are obtained over 24 h. Electrocatalysis occurs between the Mo(IV)/Mo(III) and Mo(III)/Mo(II) redox couples, around 1.0 V vs SCE. Mechanistic studies by (1)H NMR spectroscopy show that upon two-electron reduction the Mo(CNR)2(bdt)2 complex dissociates the isocyanide ligands, followed by addition of acid to result in the formation of molecular hydrogen and the Mo(bdt)2 complex.

THE FORMATION OF MASSIVE PRIMORDIAL STARS IN THE PRESENCE OF MODERATE UV BACKGROUNDS

Radiative feedback from populations II stars played a vital role in early structure formation. Particularly, photons below the Lyman limit can escape the star forming regions and produce a background ultraviolet (UV) flux which consequently may influence the pristine halos far away from the radiation sources. These photons can quench the formation of molecular hydrogen by photo-detachment of $\rm H^{-}$. In this study, we explore the impact of such UV radiation on fragmentation in massive primordial halos of a few times $\rm 10^{7}$~M${_\odot}$. To accomplish this goal, we perform high resolution cosmological simulations for two distinct halos and vary the strength of the impinging background UV field in units of $\rm J_{21}$. We further make use of sink particles to follow the evolution for 10,000 years after reaching the maximum refinement level. No vigorous fragmentation is observed in UV illuminated halos while the accretion rate changes according to the thermal properties. Our findings show that a few 100-10, 000 solar mass protostars are formed when halos are irradiated by $\rm J_{21}=10-500$ at $\rm z>10$ and suggest a strong relation between the strength of UV flux and mass of a protostar. This mode of star formation is quite different from minihalos, as higher accretion rates of about $\rm 0.01-0.1$ M$_{\odot}$/yr are observed by the end of our simulations. The resulting massive stars are the potential cradles for the formation of intermediate mass black holes at earlier cosmic times and contribute to the formation of a global X-ray background.

A UV flux constraint on the formation of direct collapse black holes

The ability of metal free gas to cool by molecular hydrogen in primordial halos is strongly associated with the strength of ultraviolet (UV) flux produced by the stellar populations in the first galaxies. Depending on the stellar spectrum, these UV photons can either dissociate $\rm H_{2}$ molecules directly or indirectly by photo-detachment of $\rm H^{-}$ as the latter provides the main pathway for $\rm H_{2}$ formation in the early universe. In this study, we aim to determine the critical strength of the UV flux above which the formation of molecular hydrogen remains suppressed for a sample of five distinct halos at $z>10$ by employing a higher order chemical solver and a Jeans resolution of 32 cells. We presume that such flux is emitted by PopII stars implying atmospheric temperatures of $\rm 10^{4}$~K. We performed three-dimensional cosmological simulations and varied the strength of the UV flux below the Lyman limit in units of $\rm J_{21}$. Our findings show that the value of $\rm J_{21}^{crit}$ varies from halo to halo and is sensitive to the local thermal conditions of the gas. For the simulated halos it varies from 400-700 with the exception of one halo where $\rm J_{21}^{crit} \geq 1500$. This has important implications for the formation of direct collapse black holes and their estimated population at z > 6. It reduces the number density of direct collapse black holes by almost three orders of magnitude compared to the previous estimates.

Non-equilibrium chemistry and cooling in the diffuse interstellar medium – II. Shielded gas

We extend the non-equilibrium model for the chemical and thermal evolution of diffuse interstellar gas presented in Richings et al. (2014) to account for shielding from the UV radiation field. We attenuate the photochemical rates by dust and by gas, including absorption by HI, H2, HeI, HeII and CO where appropriate. We then use this model to investigate the dominant cooling and heating processes in interstellar gas as it becomes shielded from the UV radiation. We consider a one-dimensional plane-parallel slab of gas irradiated by the interstellar radiation field, either at constant density and temperature or in thermal and pressure equilibrium. The dominant thermal processes tend to form three distinct regions in the clouds. At low column densities cooling is dominated by ionised metals such as SiII, FeII, FeIII and CII, which are balanced by photoheating, primarily from HI. Once the hydrogen-ionising radiation becomes attenuated by neutral hydrogen, photoelectric dust heating dominates, while CII becomes dominant for cooling. Finally, dust shielding triggers the formation of CO and suppresses photoelectric heating. The dominant coolants in this fully shielded region are H2 and CO. The column density of the HI-H2 transition predicted by our model is lower at higher density (or at higher pressure for gas clouds in pressure equilibrium) and at higher metallicity, in agreement with previous PDR models. We also compare the HI-H2 transition in our model to two prescriptions for molecular hydrogen formation that have been implemented in hydrodynamic simulations.

A no-go theorem for direct collapse black holes without a strong ultraviolet background

Abstract Explaining the existence of supermassive black holes larger than ∼109 M⊙ at redshifts z ≳ 6 remains an open theoretical question. One possibility is that gas collapsing rapidly in pristine atomic cooling haloes (Tvir ≳ 104 K) produces 104–106 M⊙ black holes. Previous studies have shown that the formation of such a black hole requires a strong UV background to prevent molecular hydrogen cooling and gas fragmentation. Recently, it has been proposed that a high UV background may not be required for haloes that accrete material extremely rapidly or for haloes where gas cooling is delayed due to a high baryon-dark matter streaming velocity. In this work, we point out that building up a halo with Tvir ≳ 104 K before molecular cooling becomes efficient is not sufficient for forming a direct collapse black hole (DCBH). Though molecular hydrogen formation may be delayed, it will eventually form at high densities leading to efficient cooling and fragmentation. The only obvious way that molecular cooling could be avoided in the absence of strong UV radiation, is for gas to reach high enough density to cause collisional dissociation of molecular hydrogen (∼104 cm−3) before cooling occurs. However, we argue that the minimum core entropy, set by the entropy of the intergalactic medium when it decouples from the cosmic microwave background, prevents this from occurring for realistic halo masses. This is confirmed by hydrodynamical cosmological simulations without radiative cooling. We explain the maximum density versus halo mass in these simulations with simple entropy arguments. The low densities found suggest that DCBH formation indeed requires a strong UV background.

Transfer Hydrogenation of Cellulose‐based Oligomers over Carbon‐supported Ruthenium Catalyst in a Fixed‐bed Reactor

AbstractRu supported on activated carbon was found to be active for the transfer hydrogenation of cellulose oligomers, which were produced by the milling of acidulated microcrystalline cellulose. A C6 sugar alcohol yield of 85 % was obtained in less than 1 h reaction time in a batch reactor. Optimum reaction conditions for transfer hydrogenation were determined as 180 °C and a pH above 2.2 using glucose as a substrate. Use of deuterium as a marker established that direct transfer of hydride species from 2‐propanol to glucose occurs through the dihydride mechanism. Formation of molecular hydrogen from 2‐propanol dehydrogenation was found to be a side reaction, with little influence on the glucose hydrogenation step. Conversion of cellulose oligomers to hexitols was also achieved in a continuous flow fixed‐bed reactor with 36.4 % yield at a liquid hourly space velocity of 4.7 h−1. The catalytic activity did not decrease even after 12 h of the onstream reaction.

Scattering properties of dark atoms and molecules

There has been renewed interest in the possibility that dark matter exists in the form of atoms, analogous to those of the visible world. An important input for understanding the cosmological consequences of dark atoms is their self-scattering. Making use of results from atomic physics for the potentials between hydrogen atoms, we compute the low-energy elastic scattering cross sections for dark atoms. We find an intricate dependence upon the ratio of the dark proton to electron mass, allowing for the possibility to "design" low-energy features in the cross section. Dependences upon other parameters, namely the gauge coupling and reduced mass, scale out of the problem by using atomic units. We derive constraints on the parameter space of dark atoms by demanding that their scattering cross section does not exceed bounds from dark matter halo shapes. We discuss the formation of molecular dark hydrogen in the universe, and determine the analogous constraints on the model when the dark matter is predominantly in molecular form.

THE FORMATION OF MOLECULAR HYDROGEN ON SILICATE DUST ANALOGS: THE ROTATIONAL DISTRIBUTION

Our laboratory experiments continue to explore how the formation of molecular hydrogen is influenced by dust and how dust thereby affects hydrogen molecules adsorbed on its surface. In Sabri et al., we present the preparation of nanometer-sized silicate grain analogs via laser ablation. These analogs illustrate extremes in structure (fully crystalline or fully amorphous grains), and stoichiometry (the forsterite and fayalite end-members of the olivine family). These were inserted in FORMOLISM, an ultra-high vacuum setup where they can be cooled down to ~5 K. Atomic beams are directed at these surfaces and the formation of new molecules is studied via REMPI(2+1) spectroscopy. We explored the rotational distribution (0 ≤ J'' ≤ 5) of v'' = 0 of the ground electronic state of H2. The results of these measurements are reported here. Surprisingly, molecules formed and ejected from crystalline silicates have a cold (T rot ~ 120 K) rotational energy distribution, while for molecules formed on and ejected from amorphous silicate films, the rotational temperature is ~310 K. These results are compared to previous experiments on metallic surfaces and theoretical simulations. Solid-state surface analysis suggests that flatter grains could hinder the cartwheel rotation mode. A search for hot hydrogen, predicted as a result of H2 formation, hints at its production. For the first time, the rotational distribution of hydrogen molecules formed on silicate dust is reported. These results are essential to understanding the chemistry of astrophysical media containing bare dust grains.

Polycyclic aromatic hydrocarbons – catalysts for molecular hydrogen formation

Polycyclic aromatic hydrocarbons (PAHs) have been shown to catalyse molecular hydrogen formation. The process occurs via atomic hydrogen addition reactions leading to the formation of super-hydrogenated PAH species, followed by molecular hydrogen forming abstraction reactions. Here, we combine quadrupole mass spectrometry data with kinetic simulations to follow the addition of deuterium atoms to the PAH molecule coronene. When exposed to sufficiently large D atom fluences, coronene is observed to be driven towards the completely deuterated state (C24D36) with the mass distribution peaking at 358 amu, just below the peak mass of 360 amu. Kinetic models reproduce the experimental observations for an abstraction cross-section of sigma(abs) = 0.01 angstroms2 per excess H/D atom, and addition cross-sections in the range of sigma(add) = 0.55-2.0 angstroms2 for all degrees of hydrogenation. These findings indicate that the cross-section for addition does not scale with the number of sites available for addition on the molecule, but rather has a fairly constant value over a large interval of super-hydrogenation levels.

Utilizing cellulase as a hydrogen peroxide stabilizer to combine the biopolishing and bleaching procedures of cotton cellulose in one bath

In this research, the stabilization effect of cellulase on the decomposition of hydrogen peroxide was investigated for the first time. It was concluded that, regardless of the decomposition mechanism, the cellulase protein could contribute significantly to peroxide stability. This effect stems from the formation of molecular hydrogen bonding between peroxide and cellulase protein or direct sequestering of free metal ions by amino acids in cellulase. Furthermore, based on this stability, a combined biopolishing and peroxide bleaching protocol was developed to improve cotton quality more efficiently. Afterwards, physicochemical properties such as the weight and strength loss, water absorbency, and carbonyl and carboxyl group content of treated cotton cellulose were measured to show the feasibility of the new method. Fourier-transform infrared (FT-IR) and X-ray diffraction (XRD) analyses indicated that the crystallinity index of cotton was increased due to the preferential hydrolysis of amorphous cellulose by cellulase.

The impact of different physical processes on the statistics of Lyman-limit and damped Lyman α absorbers

We compute the z = 3 neutral hydrogen column density distribution function f(NHI) for 19 simulations drawn from the OWLS project using a post-processing correction for self-shielding calculated with full radiative transfer of the ionising background radiation. We investigate how different physical processes and parameters affect the abundance of Lyman-limit systems (LLSs) and damped Lyman-alpha absorbers (DLAs) including: i) metal-line cooling; ii) the efficiency of feedback from SNe and AGN; iii) the effective equation of state for the ISM; iv) cosmological parameters; v) the assumed star formation law and; vi) the timing of hydrogen reionization . We find that the normalisation and slope, D = d log10 f /d log10 NHI, of f(NHI) in the LLS regime are robust to changes in these physical processes. Among physically plausible models, f(NHI) varies by less than 0.2 dex and D varies by less than 0.18 for LLSs. This is primarily due to the fact that these uncertain physical processes mostly affect star-forming gas which contributes less than 10% to f(NHI) in the the LLS column density range. At higher column densities, variations in f(NHI) become larger (approximately 0.5 dex at NHI = 10^22 cm^-2 and 1.0 dex at NHI = 10^23 cm^-2) and molecular hydrogen formation also becomes important. Many of these changes can be explained in the context of self-regulated star formation in which the amount of star forming gas in a galaxy will adjust such that outflows driven by feedback balance inflows due to accretion. Data and code to reproduce all figures can be found at the following url: https://bitbucket.org/galtay/hi-cddf-owls-1

The formation of molecular hydrogen from water ice in the lunar regolith by energetic charged particles

On 9 October 2009, the Lunar Crater Observation and Sensing Satellite (LCROSS) mission impacted a spent Centaur rocket into the permanently shadowed region (PSR) within Cabeus crater and detected water vapor and ice, as well as other volatiles, in the ejecta plume. The Lyman Alpha Mapping Project (LAMP), a far ultraviolet (FUV) imaging spectrograph on board the Lunar Reconnaissance Orbiter (LRO), observed this plume as FUV emissions from the fluorescence of sunlight by molecular hydrogen (H2) and other constituents. Energetic charged particles, such as galactic cosmic rays (GCRs) and solar energetic particles (SEPs), can dissociate the molecules in water ice to form H2. We examine how much H2can be formed by these types of particle radiation interacting with water ice sequestered in the regolith within PSRs, and we assess whether it can account for the H2 observed by LAMP. To estimate H2formation, we use the GCR and SEP radiation dose rates measured by the LRO Cosmic Ray Telescope for the Effects of Radiation (CRaTER). The exposure time of the ice is calculated by considering meteoritic gardening and the penetration depth of the energetic particles. We find that GCRs and SEPs could convert at least 1–7% of the original water molecules into H2. Therefore, given the amount of water detected by LCROSS, such particle radiation‒induced dissociation of water ice could likely account for a significant percentage (10–100%) of the H2measured by LAMP.