A graphite sheet modified with reduced graphene oxide-hyper-branched gold nanostructure as a highly efficient electrocatalyst for hydrogen evolution reaction

Hydrogen is considered as the most important energy carrier for the future. Water electrolysis is a green method for hydrogen production and simple technology that produces very clean gases. However, the main problems with this method are that this process possesses slow kinetic, consumes many energies and its common electrocatalyst is platinum (Pt) based which is an expensive and rare substance. The use of accessible electrocatalyst materials with new shape or structure, which can reduce the overpotential for the hydrogen evolution reaction (HER) is one of the ways to increase the efficiency of the electrolyzers. Herein, first, a graphite sheet was modified with graphene oxide (GO) and then a hyperbranched structure of gold was electrodeposited on it by controlling the electrodeposition conditions. The electrode surface was characterized by scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FT-IR). The HER performance of the prepared electrodes was evaluated using linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) methods in 0.5 M H₂SO₄ solution. The as-prepared electrode revealed outstanding HER performance with a near-zero onset overpotential (4.7 mV), overpotential of 44 mV at 10 mA cm⁻², a high current density of 127.9 mA cm⁻² at 200 mV and also satisfactory stability. Such results suggest that this electrocatalyst is promising for generating clean energy on an industrial scale.     

Platinum–rare earth electrodes for hydrogen evolution in alkaline water electrolysis

In the new “Hydrogen Economy” concept, water electrolysis is considered one of the most promising technologies for hydrogen production. Novel electrocatalytic materials for the hydrogen electrode are being actively investigated to improve the energy efficiency of current electrolysers. Platinum (Pt) alloys are known to possess good catalytic activities towards the hydrogen evolution reaction (HER). However, virtually nothing is known about the effects of rare earth (RE) elements on the electrocatalytic behaviour of Pt towards the HER. In this study, the hydrogen discharge is evaluated in three different Pt–RE intermetallic alloy electrodes, namely Pt–Ce, Pt–Sm and Pt–Ho, all having equiatomic composition. The electrodes are tested in 8 M KOH aqueous electrolytes at temperatures ranging from 25 °C to 85 °C. Measurements of the HER by linear scan voltammetry allow the determination of several kinetic parameters, namely the Tafel coefficients, charge-transfer coefficients, and exchange current densities. Activation energies of 46, 59, 39, and 60 kJ mol⁻¹ are calculated for Pt, Pt–Ce, Pt–Sm and Pt–Ho electrodes, respectively. Results show that the addition of REs improves the activity of the Pt electrocatalyst. Studies are in progress to correlate the microstructure of the studied alloys with their performance towards the HER.     

Hydrogenation properties of Hf-Ni intermetallics - Experimental and theoretical investigation

The hydrogenation properties of HfNi and Hf₂Ni₇ intermetallics were investigated at the constant pressure of 1 bar and in the temperature ranges 373-573 K for HfNi and 323-473 K for Hf₂Ni₇. The kinetic parameters, rate constants and activation energies of the absorption processes were determined. Maximal hydrogen absorption, i.e., number of hydrogen atoms absorbed per metal atom, H/M, are 1.05 and 0.04 achieved at 373 K for HfNi and Hf₂Ni₇, respectively. Multiple hydriding/dehydriding was found to influence the improvement of the kinetic parameters. XRD and SEM methods were used to investigate the structural and morphological changes of the samples due to hydrogen absorption. The thermodynamic parameters of hydriding together with the structural properties of the intermetallics and their hydrides, calculated using the full-potential linearized augmented plane waves (FP-LAPW) code based on the density functional theory (DFT), were utilized for the sake of explaining the experimental investigations.     

Ammonia as a hydrogen energy carrier

The gravimetric H₂ densities and the heats of combustion of tanks stored ammonia (ammonia storage tanks) were similar to those of the liquid H₂ tanks at the weight of 20–30ton, although the gravimetric H₂ density of liquid H₂ is 100 wt%. The volumetric H₂ densities and the heats of combustion of ammonia storage tanks were about 2 times higher than those of liquid H₂ tanks at 1–4 × 10⁴ m³. Gray ammonia is synthesized from hydrogen through process known as steam methane reforming, nitrogen separated from air and Haber-Bosch process. Blue ammonia is the same as gray ammonia, but with CO₂ emissions captured and stored. Green ammonia is produced by reacting hydrogen produced by electrolysis of water and nitrogen separated from air with Haber-Bosch process using renewable energies. The energy efficiencies of gray, blue and green ammonia were better than those of liquid hydrogen and methylcyclohexane (MCH) with high H₂ density and similar to the efficiency of H₂ gas. The energy efficiencies of ammonia decreased in the order, gray ammonia > blue ammonia > green ammonia. The production costs of green hydrogen energy carried increased in the order, ammonia < liquid H₂<MCH. The amounts of energy consumption by N₂ production and Haber-Bosch process were below 10% compared with the value of H₂ production from water electrolysis.     

Enhancing the dehydrogenation properties of LiAlH4 using K2NiF6 as additive

Lithium alanate (LiAlH₄) is a material that can be potentially used for solid-state hydrogen storage due to its high hydrogen content (10.5 wt%). Nevertheless, a high desorption temperature, slow desorption kinetic, and irreversibility have restricted the application of LiAlH₄ as a solid-state hydrogen storage material. Hence, to lower the decomposition temperature and to boost the dehydrogenation kinetic, in this study, we applied K₂NiF₆ as an additive to LiAlH₄. The addition of K₂NiF₆ showed an excellent improvement of the LiAlH₄ dehydrogenation properties. After adding 10 wt% K₂NiF₆, the initial decomposition temperature of LiAlH₄ within the first two dehydrogenation steps was lowered to 90 °C and 156 °C, respectively, that is 50 °C and 27 °C lower than that of the аs-milled LiAlH₄. In terms of dehydrogenation kinetics, the dehydrogenation rate of K₂NiF₆-doped LiAlH₄ sample was significantly higher as compared to аs-milled LiAlH₄. The K₂NiF₆-doped LiAlH₄ sample can release 3.07 wt% hydrogen within 90 min, while the milled LiAlH₄ merely release 0.19 wt% hydrogen during the same period. According to the Arrhenius plot, the apparent activation energies for the desorption process of K₂NiF₆-doped LiAlH₄ are 75.0 kJ/mol for the first stage and 88.0 kJ/mol for the second stage. These activation energies are lower compared to the undoped LiAlH₄. The morphology study showed that the LiAlH₄ particles become smaller and less agglomerated when K₂NiF₆ is added. The in situ formation of new phases of AlNi and LiF during the dehydrogenation process, as well as a reduction in particle size, is believed to be essential contributors in improving the LiAlH₄ dehydrogenation characteristics.     

Effects of charging,strain, and doping on the interaction between H2 and nitrogen-rich Penta-CN2 sheet

The development of advanced materials for the safety and efficiency of hydrogen storage media is necessary. We computationally explored the hydrogen storage properties of penta-CN₂ sheet. The hydrogen adsorption properties of neutral, negatively charged, externally strained, and metal-doped penta-CN₂ sheets were investigated in detail. Here, for the first time, the effect of the strain of two-dimensional nonmetallic materials on hydrogen adsorption is investigated. We found that the hydrogen binding energy increases to ?0.20 eV and achieves storage capacities up to 9.00 wt % on the negatively charged substrate, and to ?0.14 eV at 18% stretching. Moreover, metal doping causes hydrogen adsorption energy to increase to ?0.25–0.82 eV. The hydrogen storage capacity of Li-doped defective CN₂ sheet is up to 10.90 wt%. Our study may provide new insights into the search for advanced materials for reversible hydrogen storage.     

Assessing the performance of screw deformed nanotube as potential hydrogen storage material

The hydrogen storage of screw deformed Ti-functionalized (5,2) single walled carbon nanotube is investigated by using the state of the art density functional theory calculations. The single Ti atom prefers to bind at the hollow site of the hexagonal ring with average adsorption energies per hydrogen molecule −0.56 and −0.52 eV for the un-deformed CNT-φ = 0 and deformed CNT-φ = 5 nanotubes, respectively. The hydrogen storage reactions 4H₂ + Ti-CNT-φ = 0,5 are characterized in terms of projected densities of states and statistical thermodynamics. The free energies and enthalpies meet the ultimate targets of the department of energy for minimal and maximal temperatures and pressures. The closest reactions to zero free energy exhibit surface coverage values 0.951 and 0.816 as well as (direct/inverse) rate constant ratios 6.55 and 1.5. The translational term is found to exact a dominant effect on the total entropy change with temperature, and the more promising thermodynamics are assigned to the screw deformed nanotube.     

Synergetic catalyst effect of Ni/Pd dual metal coating accelerating hydrogen storage properties of ZrCo alloy

Aimed at enhancing the hydrogen absorption/desorption performances of ZrCo system, Ni/Pd dual metal coating is employed on ZrCo alloy combined with the electroless plating and displacement plating. The effects of Ni/Pd dual metal coating on the microstructure, hydrogen storage performance of ZrCo alloys were investigated systematically. The results show that Ni/Pd dual metal coating deposits on the surface of ZrCo sample successfully with the thickness of 500 nm. The hydrogen absorption kinetic property is substantially enhanced for ZrCo alloy after Ni/Pd dual metal coating, which is owing to the catalytic effect of Ni/Pd coating. Further, the activation energies (E_a) for hydrogen absorption and desorption are calculated using the Arrhenius Equation and Kissinger method, respectively. Compared with the bare ZrCo, the activation energies of the Ni/Pd coated samples for hydriding/dehydriding process decrease which facilitate the hydrogenation/dehydrogenation reaction. This work introduces a rational approach by building new catalytic coating on the hydrogen storage materials to improve the hydriding/dehydriding kinetic performance.     

Hydrogen absorption kinetics of V4Cr4Ti alloy prepared by aluminothermy

The hydrogen absorption kinetics of V4Cr4Ti alloy, synthesized by aluminothermy process has been investigated in the temperature range of 373–773 K. The obtained hydrogen absorption kinetic curves were linearly fitted using a series of mechanism function to reveal the kinetics parameter and reaction mechanism. Nucleation and growth, one dimensional diffusion and three-dimensional diffusion processes are the intrinsic rate limiting steps of hydrogen absorption at 373 K. It was found that nucleation and growth processes disappear between 413 K–473 K. However at higher temperatures (>473 K), nucleation and growth as well as one dimensional diffusion process disappear. In the temperature ranges investigated (473 K–773 K), three-dimensional diffusion process was the intrinsic rate limiting step. The apparent activation energy was calculated using Arrhenius equation and found to be 6.1 kJ/mol. This value appears to be relatively higher which can be attributed to the presence of aluminium, which has blocked the absorption sites and increased the activation energy.     

Kinetics of hydrogen desorption from Zircaloy-4: Experimental and modelling

Under Pressurized Water Reactor normal operating conditions, the external surface of zirconium alloys cladding absorbs a fraction of the hydrogen produced by water reduction. During spent fuel transport, hydrogen may desorb from the cladding. The study aims to identify and quantify the rate-limiting step in the hydrogen desorption process initially present in the alloy. To better understand this process, the Thermal Desorption Spectrometry (TDS) was used in association with X-ray Photoelectron Spectroscopy analysis. TDS results were analysed with finite elements simulations using the Cast3M code. The optimization of the kinetic constants of hydrogen desorption was performed with CEA (Alternative Energies and Atomic Energy Commission)-tool URANIE. Results showed that hydrogen desorption kinetics from the metal is limited by the surface molecular recombination. Arrhenius-type temperature dependence of kinetic constants allowed to simulate experimental data with a good agreement. The optimized activation energy and the pre-exponential factor for desorption processes were in the range of 290 ± 10 kJ mol⁻¹ and 3 × 10⁷ m⁴ mol⁻¹ s⁻¹ respectively.     

Modeling the kinetic behavior of the Li-RHC system for energy-hydrogen storage: (I) absorption

The Lithium–Boron Reactive Hydride Composite System (Li-RHC) (2 LiH + MgB₂/2 LiBH₄ + MgH₂) is a high-temperature hydrogen storage material suitable for energy storage applications. Herein, a comprehensive gas-solid kinetic model for hydrogenation is developed. Based on thermodynamic measurements under absorption conditions, the system's enthalpy ΔH and entropy ΔS are determined to amount to −34 ± 2 kJ∙mol H₂⁻¹ and −70 ± 3 J∙K⁻¹∙mol H₂⁻¹, respectively. Based on the thermodynamic behavior assessment, the kinetic measurements' conditions are set in the range between 325 °C and 412 °C, as well as between 15 bar and 50 bar. The kinetic analysis shows that the hydrogenation rate-limiting-step is related to a one-dimensional interface-controlled reaction with a driving-force-corrected apparent activation energy of 146 ± 3 kJ∙mol H₂⁻¹. Applying the kinetic model, the dependence of the reaction rate constant as a function of pressure and temperature is calculated, allowing the design of optimized hydrogen/energy storage vessels via finite element method (FEM) simulations.     

Kinetic characterization of flash reduction process of hematite ore fines under hydrogen atmosphere

In order to attain comprehensive utilization of hematite ore fines and reduce carbon dioxide emission, the flash reduction of hematite ore fines under hydrogen atmosphere is studied. The changes of phase composition at 1450 K–1800 K are investigated. A mathematical model is developed to accurately evaluate the reduction kinetic parameters of hematite ore fines based on experiment. The complex flash reduction is accurately described by considering the multiple reaction mechanisms, including hematite thermal decomposition, gas-solid reduction and gas-liquid reduction. The activation energies of the gas-solid reduction and gas-liquid reduction at high temperature are obtained as 223 kJ mol⁻¹ and 180 kJ mol⁻¹, respectively. The developed kinetic model can well describe and predict the flash reduction process of hematite ore fines. The effects of particle size and temperature on the flash reduction process, and the contributions of the thermal decomposition, gas-solid reduction and gas-liquid reduction to the overall reaction process are clarified.     

Electrochemically active biofilm mediated bio-hydrogen production catalyzed by positively charged gold nanoparticles

An electrochemically active biofilm (EAB) was used for the synthesis of positively charged gold nanoparticles [(+)AuNPs] and in-situ hydrogen production without any external energy input. The EAB generate electrons and protons by decomposing sodium acetate (carbon source) in water at 30 °C. These electrons were used initially to reduce Au³⁺ to Au⁰, and later in-situ, these generated electrons and protons were used for hydrogen production. The as-synthesized (+)AuNPs acted as catalyst by providing a charged surface to reduce the protons, leading to the formation of molecular hydrogen according to the Volmer-Heyrovsky mechanism. The hydrogen produced was confirmed and estimated by gas chromatography and a fuel cell test, respectively. The maximum rate of hydrogen production reached ∼105 ± 2 mL/L day. This suggests that hydrogen production is possible in a single chamber reactor using an EAB in the presence of sodium acetate as a substrate and (+)AuNPs as a catalyst.     

Comparative study on bio-hydrogen production from corn stover: Photo-fermentation,dark-fermentation and dark-photo co-fermentation

In this study, three different fermentation methods, such as photo-fermentation (PF), dark-fermentation (DF) and dark-photo co-fermentation (DPCF) for bio-hydrogen production from corn stover were compared in terms of hydrogen production, substrate consumption, by-products formation and energy conversion efficiency. A modified Gompertz model was applied to perform the kinetic analysis of hydrogen production. The maximum cumulative hydrogen yield of 141.42 mL·(g TS)⁻¹ was achieved by PF, DF with the minimum cumulative hydrogen yield of 36.08 mL· (g TS)⁻¹ had the shortest lag time of 4.33 h, and DPCF had the maximum initial hydrogen production rate of 1.88 mL· (g TS)⁻¹·h⁻¹ and maximum initial hydrogen content of 44.40%. The results also indicated PF was an acid-consuming process with a low total VFAs concentration level of 2.90–4.19 g·L⁻¹, DF was a process of VFAs accumulation with a maximum total VFAs concentration of 12.66 g·L⁻¹, and DPCF was a synergistic process in which the total VFAs concentration was significantly reduced and the hydrogen production efficiency was effectively improved compared with DF. The energy conversion efficiency of PF, DF and DPCF were 10.12%, 2.58% and 6.45%, respectively.     

Enhanced hydrogen-storage properties of MgH2 by Fe–Ni catalyst modified three-dimensional graphene

High dehydrogenation temperature and slow dehydrogenation kinetics impede the practical application of magnesium hydride (MgH₂) serving as a potential hydrogen storage medium. In this paper, Fe–Ni catalyst modified three-dimensional graphene was added to MgH₂ by ball milling to optimize the hydrogen storage performance, the impacts and mechanisms of which are systematically investigated based on the thermodynamic and kinetic analysis. The MgH₂+10 wt%Fe–Ni@3DG composite system can absorb 6.35 wt% within 100 s (300 °C, 50 atm H₂ pressure) and release 5.13 wt% within 500 s (300 °C, 0.5 atm H₂ pressure). In addition, it can absorb 6.5 wt% and release 5.7 wt% within 10 min during 7 cycles, exhibiting excellent cycle stability without degradation. The absorption-desorption mechanism of MgH₂ can be changed by the synergistic effects of the two catalyst materials, which significantly promotes the improvement of kinetic performance of dehydrogenation process and reduces the hydrogen desorption temperature.     

Exploration of vacancy defect formation and evolution in low-energy ion implanted pure titanium

Hydrogen behavior and its related property degradation have been long-standing problems for structural materials used in hydrogen energy. The hydrogen atoms can easily interact with vacancy defects, forming hydrogen vacancy complexes which play an important role in the hydrogen-induced structural damage. However, the interaction mechanisms and its evolutions are still unclear. In this work, the hydrogen behavior and the interaction between hydrogen with defects in pure titanium implanted by 30 keV and 50 keV hydrogen ions were studied by positron annihilation spectroscopy. The implantation doses were 5 × 10¹⁶ H/cm², 1 × 10¹⁷ H/cm² and 5 × 10¹⁷ H/cm², respectively. The results show that the structural damage of pure titanium is positively correlated with the ion implantation energy. For the implantation of 50 keV hydrogen ions, a large number of hydrogen atoms are deposited in the samples. With the increase of implantation dose, the formation of hydrogen vacancy complexes (H_mV_n) reduces the effective open-volume of defects and changes the structural features of defects in implanted samples, thus suppressing the formation of vacancy defects and causing the damage range shifting from the peak damage (PD) region to the near surface (NS) region. Eventually, the movement of hydrogen atoms intensifies, and the “hydrogen peak” becomes more obvious. The chemical information related to deposited hydrogen atoms can be easily identified in the processing and analysis of positron annihilation results.     

Oxidation reaction kinetics for the steam-iron process in support of hydrogen production

A hydrogen generation research program is focused on solar-driven hydrogen production by means of reactive metal water splitting. In order to dissociate water molecules at significantly reduced thermal energies as well as providing a practical means for efficient hydrogen and oxygen separation, an intermediary reactive material is introduced to realize water splitting in the form of an oxidation reaction. Elemental iron is used as the reactive material in the process commonly referred to as the steam-iron process. In order to exploit the unique characteristics of highly reactive materials and ultimately achieve the potential efficiency gains at the solar reactor scale, a monolithic laboratory-scale reactor has been designed to explore the fundamental kinetic rates during the iron oxidation reaction at temperatures ranging from about 650 to 900 K. Results show hydrogen production rates on the order of 1E-8 g/cm² s. Micro-Raman spectroscopy is used to access information on the exact iron oxide phase produced, and high resolution SEM and electron dispersion spectroscopy (EDS) are used to assess the oxide morphology and further quantify the oxide state, including spatial distributions.     

Accumulation of hydrogen in titanium exposed to neutron irradiation

Hydrogen saturation of titanium-based materials exposed to irradiation with resonance neutrons with an energy of 0.1 MeV is considered. Radioactive scandium ₂₂Sc⁴⁶, gamma-quanta with energy of 889 and 1120 keV, and hydrogen form during nuclear reactions in titanium. The intensity of the gamma radiation depends on the concentration of hydrogen in titanium pre-saturated with hydrogen. The gamma field likely effects the excitation of the hydrogen subsystem of titanium. Irradiated materials in the presence of gamma radiation are controlled by measuring the thermo-emf. Hydrogenation of titanium exposed to neutron irradiation increases by 10–12%, which changes the thermo-emf by 20%. The temperature of components required to obtain the most hydrogen-saturated titanium corresponds to room temperature. Using this method, the hydrogen saturation time of material decreases and its amount of hydrogen increases. The effective conductivity energy is 0.17/0.5 mV K for unirradiated titanium and 0.122/0.5 mV K for irradiated titanium, change of 30%. The effect of gamma radiation must be considered when producing neutron shields based on titanium borides. Intermetallic compounds used for the accumulation and transportation of hydrogen and exposed to irradiation lose titanium atoms, negating the composition stoichiometry. The quality of commercial titanium saturated with hydrogen under these conditions improves.     

Study of isotope effect on dehydrogenation kinetics of Pd based alloys using differential scanning calorimetry

Owing to the large hydrogen isotope effect, palladium and palladium based alloy are of great technological importance for their application in separation of hydrogen isotopes. The present study deals with the investigation of isotope effect on hydrogen desorption kinetics of Pd, Pd_0.77Ag_0.23 and Pd_0.77Ag_0.10Cu_0.13 alloys, using non-isothermal method by employing Differential Scanning Calorimetry (DSC). Pd_0.77Ag_0.23 and Pd_0.77Ag_0.10Cu_0.13 alloys were prepared by arc melting method and characterised by XRD, TXRF and EDS. Both the alloys are found to have FCC phase similar to Pd lattice. Prior to kinetic measurements, samples were activated by hydriding-dehydriding method. Hydrogen/deuterium desorption kinetic measurements were carried out at four different heating rates (8, 12, 16 and 20 K/min) and Kissinger plots were constructed from peak temperature of DSC curves. Activation energies for hydrogen/deuterium desorption from the corresponding hydride/deuteride were calculated from the slope of Kissinger plot which follows the order; Pd > Pd_0.77Ag_0.23 > Pd_0.77Ag_0.10Cu_0.13. Activation energy for deuterium desorption was found to be lower than that of hydrogen desorption and significant isotope effect was observed for the Pd_0.77Ag_0.10Cu_0.13 alloy which makes it a favorable candidate material for its application in hydrogen isotope separation, employing self-displacement gas chromatography.