H2 Reaction Research Articles

Kinetic study of reverse water-gas shift chemical looping on La-based perovskite

This was a kinetic study on the reduction reaction with H2(g) and subsequent oxidation reaction with CO2(g) involved in a chemical looping reverse water-gas shift cycle (RWGS-CL) on lanthanum-based perovskites. The influence of particle size, gas flow rate, initial sample mass, temperature, and reactant gas partial pressure were analyzed for each reaction. The kinetic parameters of reduction reactions for LaCoO3 and LaCo0.50Fe0.50O3 were determined through isothermal reactions between 275 and 400 °C and hydrogen partial pressure between 1.67 and 5 pct. These reactions are well described by a contracting volume model. The activation energies found were 90.3 ± 2 and 71.6 ± 4 kJ mol−1, and for ln(A) 10.4 ± 0.4 and 8.3 ± 0.9, for LaCoO3 and LaCo0.50Fe0.50O3 reductions, respectively. Two kinetic regimes were identified for the reaction between reduced LaCo0.50Fe0.50O3 and CO2(g) with formation of CO(g), depending on particle size. The surfaces of the solid reactants serve as potential sites for initiating the conversion reaction due to their higher energy levels compared to those of the bulk material. This accounts for higher conversion rates observed in smaller particle sizes, where the surface-to-bulk ratio is higher. The second stage kinetics was analyzed, and the activation energy was determined to be 148.6 ± 9 kJ mol−1. For LaCo0.50Fe0.50O3, XPS measurements show that only Co changes its oxidation state during the redox reactions.

Numerical investigation of nanosecond plasma-assisted ignition in blast furnace gas

The ignition delay of blast furnace gas (BFG) and air mixtures is numerically investigated in a constant-pressure reactor employing plasma-assisted ignition. Given the absence of a well-established chemical kinetic mechanism for plasma-assisted ignition in BFG and air mixtures, this study develops a mechanism by integrating well-validated plasma kinetics reactions involving CO2 with CO and H2, along with pre-existing plasma kinetics for air. The study explores the influence of various factors on ignition delay time, including the reduced electric field, the number of nanosecond pulses, equivalence ratio, and molar fraction of hydrogen. It is found that the utilization of nanosecond pulsed plasma results in a notable enhancement of the ignition delay time in BFG. Under lower reduced electric field conditions, the vibrational states of N2 predominantly contribute to the generation of O radicals. Increasing the number of nanosecond pulses facilitates the ignition in BFG and air mixtures while maintaining the same overall deposition energy. Ignition occurs more rapidly in fuel-rich mixtures due to the elevated accumulation of O, H, OH radicals during the final nanosecond pulse in rich mixtures. When the H2 concentration is elevated to 3 %, the electron impact reaction H2 + e → e + H + H becomes a more significant source of H radicals during the nanosecond pulse, in contrast to the 1 % H2 case. Additionally, this study investigate the effect of species at the last nanosecond pulse on ignition delay time of BFG. The results indicate that the impact of nanosecond plasma on the ignition delay time of BFG can be captured by considering the concentration of the primitive BFG/air species (CO, CO2, H2, O2, N2) and key radicals (O, H, OH) at the last nanosecond pulse.

Coupled 3D (J ≥ 0) Time-Dependent Wave Packet Calculation for the F + H2 Reaction on Accurate Ab Initio Multi-State Diabatic Potential Energy Surfaces.

We had calculated adiabatic potential energy surfaces (PESs), nonadiabatic, and spin-orbit (SO) coupling terms among the lowest three electronic states (12A', 22A', and 12A″) of the F + H2 system using the multireference configuration interaction (MRCI) level of theory, and the adiabatic-to-diabatic transformation equations were solved to formulate the diabatic Hamiltonian matrix [J. Chem. Phys. 2020, 153, 174301] for the entire region of the nuclear configuration space. The accuracy of such diabatic PESs is explored by performing scattering calculations to evaluate integral cross sections (ICSs) and rate constants. The nonadiabatic and SO effects are studied by utilizing coupled 3D time-dependent wave packet formalism with zero and nonzero total angular momentum on multiple adiabatic/diabatic surfaces calculation. We depict the convergence profiles of reaction probabilities for the reactive as well as nonreactive processes on various electronic states at different collision energies with respect to total angular momentum including all helicity quantum numbers. Finally, total ICSs are calculated as functions of collision energies for the initial rovibrational state (v = 0, j = 0) of the H2 molecule along with the temperature-dependent rate coefficient, where those quantities are compared with previous theoretical and experimental results.

Distinct Site Motifs Activate O2 and H2 on Supported Au Nanoparticles in Liquid Water.

Au nanoparticles catalyze the activation and conversion of small molecules with rates and kinetic barriers that depend on the dimensions of the nanoparticle, composition of the support, and presence of catalytically culpable water molecules that solvate these interfaces. Here, molecular interpretations of steady-state rate measurements, kinetic isotope effects, and structural characterizations reveal how the interface of Au nanoparticles, liquid water, and metal oxide supports mediate the kinetically relevant activation of H2 and sequential reduction of O2-derived intermediates during the formation of H2O2 and H2O. Rates of H2 consumption are 10-100 fold greater on Au nanoparticles supported on metal oxides (e.g., titania) compared to more inert and hydrophobic materials (carbon, boron nitride). Similarly, Au nanoparticles on reducible and Lewis acidic supports (e.g., lanthana) bind dioxygen intermediates more strongly and present lower barriers (<22 kJ mol-1) for O-O bond dissociation than inert interfaces formed with silica (>70 kJ mol-1). Selectivities for H2O2 formation increase significantly as the diameters of the Au nanoparticles increase because differences in nanoparticle size change the relative fractions of exposed sites that exist at Au-support interfaces. In contrast, site-normalized rates and barriers for H2 activation depend weakly on the size of Au nanoparticles and the associated differences in active site motifs. These findings suggest that H2O aids the activation of H2 at sites present across all surface Au atoms when nanoparticles are solvated by water. However, molecular O2 preferentially binds and dissociates at Au-support interfaces, leading to greater structure sensitivity for barriers of O-O dissociation across different support identities and sizes of Au nanoparticles. These insights differ from prior knowledge from studies of gas-phase reactions of H2 and O2 upon Au nanoparticle catalysts within dilute vapor pressures of water (10-4 to 0.1 kPa H2O), in which catalysis occurs at the perimeter of the Au-support interface. In contrast, contacting Au catalysts with liquid water (55.5 M H2O) expands catalysis to all surface Au atoms and enables appreciable H2O2 formation.

Improvement of an enzymatic cascade synthesis of nicotinamide mononucleotide via protein engineering and reaction-process reinforcement.

Enzymatic synthesis of β-nicotinamide mononucleotide (NMN) from D-ribose has garnered widespread attention due to its cheap material, the use of mild reaction conditions, and the ability to produce highly pure products with the desired optical properties. However, the overall NMN yield of this method is impeded by the low activity of rate-limiting enzymes. The ribose-phosphate diphosphokinase (PRS) and nicotinamide phosphoribosyltransferase (NAMPT), that control the rate of the reaction, were engineered to improve the reaction efficacy. The actives of mutants PRS-H150Q and NAMPT-Y15S were 334% and 57% higher than that of their corresponding wild-type enzymes, respectively. Furthermore, by adding pyrophosphatase, the byproduct pyrophosphate which can inhibit the activity of NAMPT was degraded, leading to a 6.72% increase in NMN yield. Following with reaction-process reinforcement, a high yield of 8.10gL-1 NMN was obtained after 3h of reaction, which was 56.86-fold higher than that of the stepwise reaction synthesis (0.14gL-1 ), indicating that the in vitro enzymatic synthesis of NMN from D-ribose and niacinamide is an economical and feasible route.

Remotely Bonded Bridging Dioxygen Ligands Enhance Hydrogen Transfer in a Silica-Supported Tetrairidium Cluster Catalyst.

A longstanding challenge in catalysis by noble metals has been to understand the origin of enhancements of rates of hydrogen transfer that result from the bonding of oxygen near metal sites. We investigated structurally well-defined catalysts consisting of supported tetrairidium carbonyl clusters with single-atom (apical iridium) catalytic sites for ethylene hydrogenation. Reaction of the clusters with ethylene and H2 followed by O2 led to the onset of catalytic activity as a terminal CO ligand at each apical Ir atom was removed and bridging dioxygen ligands replaced CO ligands at neighboring (basal-plane) sites. The presence of the dioxygen ligands caused a 6-fold increase in the catalytic reaction rate, which is explained by the electron-withdrawing capability induced by the bridging dioxygen ligands, consistent with the inference that reductive elimination is rate-determining. Electronic-structure calculations demonstrate an additional role of the dioxygen ligands, changing the mechanism of hydrogen transfer from one involving equatorial hydride ligands to that involving bridging hydride ligands. This mechanism is made evident by an inverse kinetic isotope effect observed in ethylene hydrogenation reactions with H2 and, alternatively, with D2 on the cluster incorporating the dioxygen ligands and is a consequence of quasi-equilibrated hydrogen transfer in this catalyst. The same mechanism accounts for rate enhancements induced by the bridging dioxygen ligands for the catalytic reaction of H2 with D2 to give HD. We posit that the mechanism involving bridging hydride ligands facilitated by oxygen ligands remote from the catalytic site may have some generality in catalysis by oxide-supported noble metals.

Research on V2O3 preparation by stepwise catalysis solution-phase hydrogen reduction from shale V-rich solution

Solution-phase hydrogen reduction reaction (SpHR) was introduced to overcome the problems of ammonia nitrogen pollution, high energy consumption, and long production flow of traditional reduction roasting. From φ-pH diagram, the increase of reaction temperature, vanadium concentration and H2 partial pressure is beneficial to the preparation of V2O3. High purity V2O3 could not be prepared by single addition catalysis and synchronous catalysis in SpHR process, and the Ni + NiSO4 stepwise catalysis can effectively eliminate the problem of nickel wrapped in vanadium precipitates during the precipitation process. Under the optimal conditions of Ni + NiSO4 stepwise catalysis of nickel powder dosage 5 g/L, NiSO4 dosage 8 g/L, nickel powder catalytic time 90 min, NiSO4 catalytic time 30 min, the precipitate with nickel content 11.15 % was obtained, and Ni catalyst can be separated by magnetic separation with nickel recovery ratio of 99.52 %. Ni2+ in SpHR precipitates to Ni(OH)2 and then disintegrates and reduces to Ni, and Ni + NiSO4 stepwise catalysis includes two steps of pre-catalysis and secondary catalysis. After fourth cyclic experiment, the vanadium content of V2O3 product obtained was 67.46 % (i.e. 99.21 % V2O3 purity met the requirements of GB 40301–2021), the total recovery was 98.68 %, and the vanadium loss ratio was stable at 1.22 %. The process of SpHR has no ammonia nitrogen wastewater or waste gas discharge, and the price of V2O3 with purity more than 99 % on the market is about 260,000 ¥/t. The stepwise catalysis SpHR has remarkable environmental benefits and economic benefits.

Theoretical Development of the Interaction-Asymptotic Region Decomposition Method for Tetratomic Reactive Scattering.

An accurate and efficient time-dependent wave packet method is proposed for solving the product state-resolved reaction probabilities of the tetratomic reactive system. In this method, the entire scattering process is divided into the interaction region and multiple asymptotic regions, sharing the same spirit as the interaction-asymptotic region decomposition (IARD) approach in a triatomic reactive scattering process. The hyperspherical coordinate is adopted in the interaction region, while the corresponding Jacobi coordinate is employed in each asymptotic region. Therefore, in this IARD method, the "coordinate problem", the difficulty of expressing the wave function in the entire region using a single coordinate system, can be effectively avoided, and only a very small number of the grid points (or the basis functions) are required. For the numerical illustration, the typical tetratomic reaction H2 + OH with zero total angular momentum is calculated, and compared with other quantum wave packet methods. Our proposed IARD method for the tetratomic reactive system is much more efficient and accurate.

OME[formula omitted]/air mixtures: The structure and propagation mechanism of their laminar premixed flames

Oxymethylene dimethyl ethers (CH3O(CH2O)xCH3 or OMEx) are synthetic substitutes of diesel and jet fuel. They can achieve soot-less combustion and have been shown to exhibit favourable ignition characteristics. With the aim to explore their combustion physics, the structure of their flames is analysed using the algorithmic tools of the Computational Singular Perturbation (CSP) method. It is demonstrated that the flame structure and the mechanism for its propagation is encapsulated in the fastest explosive mode, introduced by chemical dynamics in a narrow region of the flame front. This narrow region extends around the point where the maximum heat release rate (MHRR) is recorded. CSP diagnostics identify (i) reactions H + O2→ O + OH and CO + OH → CO2 + H beyond MHRR as initiating an upstream diffusion of heat and H radicals, both of which are generated by the exothermic reaction H2 + OH → H2O + H, (ii) a downstream convective motion that ensues and (iii) chemical activity that is initiated ahead of MHRR and sustained by the convective transport of fuel and oxygen. CSP also identifies differences in the action of the upstream diffusion of heat and H radicals and of the downstream transport of fuel and oxidiser. It is also shown that the fastest explosive mode far from the neighbourhood of MHRR has no influence on the structure and propagation of the flame front. Although OME2−4/air mixtures exhibit drastically different dynamics in the context of homogeneous autoignition, very small differences are recorded in terms of flame structure and propagation. The findings suggests that, since practically all major processes driving the flame front propagation are similar to those of hydrocarbons, OMEx fuels can be used as “drop-in” fuels in currently employed burners.

Dynamics and energetics of the K([formula omitted]) + H[formula omitted] ([formula omitted]) reaction: Significance of orientational and (ro)vibrational contribution

The significance of orientational and (ro)vibrational excitations on the K(2S) + H2 (X1Σg+) reaction dynamics is presented here by performing the exact time-dependent wavepacket calculations using the Coriolis coupling (CC) approach. Employing the new accurate ab initio ground electronic surface 1 2A′ reported by Yuan et al. (2018), the dynamical quantities such as integral cross sections and thermal rate constants are computed within the CC and CS (centrifugal sudden) methods. All partial wave contributions of J (total angular momentum) up to 90 are required to get the convergence in dynamical results up to the collision energy of 3.5 eV. The present study attests that the ground and first vibrational level dynamics is insignificant. For v=2, the reaction probability is monotonically increasing, followed by the onset noted near 1.25 eV, as a function of collision energy up to 3.5 eV. Further, the kinematic effects (replacing H by D atom) on the title system is also performed and found that the KH product formation is more favored than the KD product via HD depletion path.

Reaction path model of the formation of abiotic immiscible hydrocarbon fluids in subducted carbonated serpentinites, Lanzo Massif (Western Italian Alps)

Fluids generated from subducted slabs participate in the cycling of deep carbon in the crust and upper mantle. In these fluids, aqueous carbon species vary in oxidation state between +IV and -IV depending on whether the fluids are oxidizing or reducing, respectively. Most studies of subduction-zone fluids have focused on oxidized carbon species. However, recent studies of natural samples have demonstrated the occurrence of deep, reducing fluids, generated in both subducted oceanic upper mantle and crustal rocks. CH4-H2-rich fluid inclusions in subducted carbonated serpentinites have demonstrated the existence of abiotic, immiscible, hydrocarbon fluids at upper mantle conditions. To investigate the formation of such immiscible hydrocarbon fluids during the evolution of subducted carbonated serpentinites, we used equilibrium constants from the Deep Earth Water model to carry out predictive chemical mass transfer modeling to simulate the alteration reactions. A novel feature of the models was the inclusion of an immiscible hydrocarbon fluid containing six components (CH4,f,C2H6,f,C3H8,f,isoC4H10,f,CO2,f,H2,f). This feature enabled prediction of the formation of a separate immiscible fluid in equilibrium with aqueous species and minerals.We developed a predictive reaction path model of invasive H2,f reacting with carbonated serpentinites and interstitial aqueous fluids for comparison with the natural samples from the Lanzo Massif, western Italian Alps. Over a range of temperatures and pressures, immiscible hydrocarbon fluids formed in association with altered mineral assemblages. Reaction progress caused the transformation of carbonated serpentinites and the formation of clinopyroxene, brucite, graphite, and hydrocarbon fluids, along with changes of pH, logfO2, and aqueous species. CH4,f was the most abundant hydrocarbon species in all the models. The overall results at 2.0 GPa and 400 to 450 °C were consistent with the natural samples from the Lanzo Massif. Interestingly, large amounts of H2O formed due to oxidation of H2. More hydrocarbons and H2O formed in models with lower fluid/rock mass ratios or with more reactant H2. Models at different pressure and temperature conditions showed similar results with some variation in the relative stabilities of aragonite, graphite and olivine solid solution, and associated differences in mineral sequences, hydrocarbon fluids, values of aqueous species, and the final logfO2 and pH. Our models strongly support the laboratory and field evidence that reduction of carbonated serpentinites by infiltrating H2 fluids can cause the formation of immiscible, abiotic hydrocarbon fluids in subduction zones.

Unveiling Quantum Interference in the D+ + H2 Nonadiabatic Reaction Dynamics at Low Collision Energies.

Fully converged nonadiabatic dynamics calculations of the D+ + H2 → H+ + HD reaction are performed at low temperatures using the time-dependent wave packet approach based on a set of precise 3 × 3 diabatic potential energy surfaces (PESs) ( Phys. Chem. Chem. Phys., 2021, 23, 7735-7747, DOI: 10.1039/D0CP04100A). The D+ + H2 reaction is mediated by a dense manifold of resonances associated with the deep potential well on the ground-state PES. The calculated results show that the nonadiabatic coupling can affect the resonance positions, deviating from the expectation based solely on adiabatic considerations. Furthermore, significant forward-backward asymmetry in total differential cross sections (DCSs) is revealed, which is markedly influenced by nonadiabatic effects. The nonadiabatic effects not only affect the contribution of partial waves in the reaction but also make the interference patterns in the DCSs change significantly.

Unconventional Error Cancellation Explains the Success of Hartree-Fock Density Functional Theory for Barrier Heights.

Energy barriers, which control the rates of chemical reactions, are seriously underestimated by computationally efficient semilocal approximations for the exchange-correlation energy. The accuracy of a semilocal density functional approximation is strongly boosted for reaction barrier heights by evaluating that approximation non-self-consistently on Hartree-Fock electron densities, which has been known for ∼30 years. The conventional explanation is that the Hartree-Fock theory yields the more accurate density. This work presents a benchmark Kohn-Sham inversion of accurate coupled-cluster densities for the reaction H2 + F → HHF → H + HF and finds a strong, understandable cancellation between positive (excessively overcorrected) density-driven and large negative functional-driven errors (expected from stretched radical bonds in the transition state) within this Hartree-Fock density functional theory. This confirms earlier conclusions (Kaplan, A. D., et al. J. Chem. Theory Comput. 2023, 19, 532-543) based on 76 barrier heights and three less reliable, but less expensive, fully nonlocal density functional proxies for the exact density.

A comparative study of fibrous silica-based catalysts for improving methane production via CO2 methanation

The process of utilizing the greenhouse gas carbon dioxide (CO2) is crucial in addressing and reducing the impact of climate change. The CO2 methanation process, also known as the Sabatier reaction, is considered one of the appealing approaches since it provides synthetic natural gas (SNG), fulfilling the present needs. However, the CO2 methanation reaction demands an exceptionally effective catalyst capable of surpassing the energy barrier associated with eight proton-electron transfers from H2 molecules. Herein, the application of fibrous silica nanospheres along with the fibrous modification of mesostructured silica nanoparticles (MSN) towards CO2 methanation, called the Centre of Hydrogen energy silica (CHE-Si) and CHE-SM was reported. Both catalysts were successfully synthesized by utilizing micro-emulsion techniques and subsequently were characterized with x-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, and N2 adsorption-desorption. FTIR results revealed that CHE-SM possessed superior Si-OH and Si-O species than CHE-Si despite displaying low surface area and pore volume. Consequently, CHE-SM achieved above 50% CO2 conversion and CH4 yield at 500 °C while CHE-Si exhibited lower performance. This discrepancy in catalytic performance was due to the fact that CHE-SM was comprised of more active sites that could adsorb and dissociate CO2 and H2 reactants.

Atomic layer deposition of Pt nanoparticles using dimethyl (N, N–dimethyl-3-butene-1-amine−N) platinum and H2 reactant and its application to 2D WS2 photodetectors

2D transition metal dichalcogenides (2D TMDCs) have thin and flexible structures and can be widely applied to nanoelectronics technology as a representative of 2D materials. Research studies on the surface functionalization of 2D TMDCs with nanoparticles have been actively conducted for fabrication of high-performance devices. Specifically, platinum (Pt) has attracted significant attention as a surface functionalization material in various applications, including photosensors, biosensors, and gas sensors due to its effective catalytic effect and excellent corrosion resistance. However, solution-based methods and PVD technologies, widely used for Pt nanoparticle synthesis, have difficulties forming fine particles dispersed on nanomaterials. Atomic layer deposition (ALD) is emerging as an advantageous method for forming nanoparticles, and dimethyl (N,N-dimethyl-3-buten-1-amine-N) platinum (DDAP) can overcome disadvantages of conventional ALD Pt precursors. In this study, we successfully synthesized Pt films using hydrogen as a new reactant in the DDAP-based ALD Pt process and evaluated formation of nanoparticles on SiO2/Si substrates. Subsequently, the ALD Pt-functionalized photodetector was fabricated with 2D WS2, a representative visible-light photodetector material, and improvement of photocurrent was confirmed by providing additional carriers via the localized surface plasmon resonance phenomenon. Furthermore, preferentially growing at high surface energy points, such as defects on WS2 nanosheets, can suppress the capture of photoexcited electrons by defects, consequently extending the carrier lifetime and preventing surface oxidation of the device. In the wavelength range of 500–1200 nm, the photoresponsivity of the ALD Pt-functionalized WS2 photodetector was improved more than 10–20 times compared to pristine WS2, and the response time was also noticeably improved. This study presents a novel approach to Pt functionalization using ALD, opening new possibilities for advanced nanodevice applications.

A single resonance Regge pole dominates the forward-angle scattering of the state-to-state F + H2 → FH + H reaction at Etrans = 62.09 meV.

The aim of the present paper is to bring clarity, through simplicity, to the important and long-standing problem: does a resonance contribute to the forward-angle scattering of the F + H2 reaction? We reduce the problem to its essentials and present a well-defined, yet rigorous and unambiguous, investigation of structure in the differential cross sections (DCSs) of the following three state-to-state reactions at a translational energy of 62.09 meV: F + H2(vi = 0, ji = 0, mi = 0) → FH(vf = 3, jf = 0, 1, 2, mf = 0) + H, where vi, ji, mi and vf, jf, mf are the initial and final vibrational, rotational and helicity quantum numbers respectively. Firstly, we carry out quantum-scattering calculations for the Fu-Xu-Zhang potential energy surface, obtaining accurate numerical scattering matrix elements for indistinguishable H2. The calculations use a time-independent method, with hyperspherical coordinates and an enhanced Numerov method. Secondly, the following theoretical techniques are employed to analyse structures in the DCSs: (a) full and Nearside-Farside (NF) partial wave series (PWS) and local angular momentum theory, including resummations of the full PWS up to second order. (b) The recently introduced "CoroGlo" test, which lets us distinguish between glory and corona scattering at forward angles for a Legendre PWS. (c) Six asymptotic (semiclassical) forward-angle glory theories and three asymptotic farside rainbow theories, valid for rainbows at sideward-scattering angles. (d) Complex angular momentum (CAM) theories of forward and backward scattering, with the Regge pole positions and residues computed by Thiele rational interpolation. Thirdly, our conclusions for the three PWS DCSs are: (a) the forward-angle peaks arise from glory scattering. (b) A broad (hidden) farside rainbow is present at sideward angles. (c) A single Regge pole contributes to the DCS across the whole angular range, being most prominent at forward angles. This proves that a resonance contributes to the DCSs for the three transitions. (d) The diffraction oscillations in the DCSs arise from NF interference, in particular, interference between the Regge pole and direct subamplitudes.

NiGraf: a new nickel-based molecularly doped metal for enhanced water electrolysis

Graphene oxide 3D entrapped in Ni-based nanoparticles establishes a new class of catalytic materials highly promising towards enhanced alkaline water electrolysis as NiGraf can be used to mediate both H2 and O2 evolution reactions at room temperature.

First-principles study of molecular hydrogen binding to heme in competition with O2, NO and CO.

Molecular hydrogen shows antioxidant activity and distinct efficacy towards vascular diseases, but the understanding of this is not yet satisfactory at the atomic level. In this work, we study the binding properties of H2 to the heme group in relation with other diatomic molecules (DMs), including O2, NO and CO, and their displacement reactions, using first-principles calculations. We carry out molecular modeling of the heme group, using iron-porphyrin with the imidazole ligand, i.e., FePIm, and smaller models of Fe(CnHn+2N2)2NH3 with n = 3 and 1, and of molecular complexes of heme-DM and -H. Through analysis of optimized geometries and energetics, it is found that the order of binding strength of DMs or H to the Fe of heme is NO > O2 > CO > H > H2 for FePIm-based systems, while it is H > O2 > NO > CO > H2 for model-based systems. We calculate the activation energies for displacement reactions of H2 and H by other DMs, revealing that the H2 displacements occur spontaneously while the H displacements require a large amount of energy. Finally, our calculations corroborate that the rate constants increase with increasing temperature according to the Arrhenius relation.

Sorption-enhanced glycerol steam reforming over lithium cuprate-based bifunctional material for the production of high-purity hydrogen

We investigated the production of high-purity H2 through sorption-enhanced glycerol steam reforming (SEGSR) using lab-made bifunctional materials consisting of nickel, Al2O3, and Li2CuO2. Different bifunctional materials were prepared with 10 wt % Ni loading but varying wt % of Al2O3 and Li2CuO2, and their catalytic activity was evaluated in a continuous fixed-bed down-flow reactor. HM-50, which had an equal wt % of Al2O3 and Li2CuO2, showed the highest performance. The conversion of glycerol and the purity of H2 were examined with respect to temperature, feed flow rate, and steam-to-carbon molar ratio (S/C). At the optimum reaction conditions (temperature = 700 °C, feed flow rate = 0.5 ml/min, and S/C = 6), glycerol conversion and H2 purity were 100 % and 94 mol %, respectively. The adsorption capacity of HM-50 was found to be 3.9 mmol CO2 per gram. With a breakthrough time of 15 min, the substance was stable for 13 adsorption-desorption cycles. The material was regenerated by substituting the feed with a N2 and steam mixture heated to 700 °C for 30 min. A most likely reaction mechanism suggested that glycerol was catalytically converted to acetaldehyde, which was then quickly decomposed to CO and CH4. We are the first research team to investigate the use of Li2CuO2 in any steam reforming process.

A CFD analysis of the rotating target holder of the 14-MeV neutron generator

An accelerator based 14-MeV neutron generator is installed at Institute for Plasma Research, Gandhinagar to generate high energy neutrons by using a water-cooled rotating tritium target. In this device, neutrons would be generated from the nuclear reaction 3H(D, n)4He by bombarding accelerated deuterium ions on a solid tritium target. The rotating target holder mainly consists of a rotating copper disc water-cooled case mounted on the rotating shaft. The high-energy deuterium ion beam impacted on solid TiT target fitted on the copper case imparting its energy to the case. This energy is taken away from the system through the water passing through the annulus cavity of the shaft. This paper presents details of the engineering CFD (computed fluid dynamics) analysis carried out for optimizing two important parameters of the rotating target. Firstly optimization of the location of flow parameters of the water as mass flow rate and Secondly optimization of speed of the rotating target and the design of fins inside the copper case.