Reactivation of Promoted Nickel Catalysts for Deuterium Exchange between Hydrogen and Water in the Vapour Phase

Binary promoted nickel – chromium oxide and ternary promoted nickel – chromium oxide – aluminium oxide mixed catalysts were prepared for use in the present study. The catalysts were prepared by co-precipitation of the corresponding metal nitrates as carbonates followed by calcination in nitrogen atmosphere at 350 °C and reduction in hydrogen atmosphere at 320 °C. To prevent spontaneous oxidation of the catalysts, bidistilled water was added followed by heating of the catalyst mixtures at about 110 °C in hydrogen atmosphere for few hours. Deactivation of catalysts was studied by measurements of the variation of their activities with the time of contact of the reacting gas mixtures with the catalyst surface in the reaction chamber. It was found that while the catalytic activity of ternary catalysts for the isotopic exchange of deuterium between hydrogen and water vapour was higher than that of the binary one, the loss in activity of the former teas faster than the latter. Reactivation of the catalysts were carried out at different temperatures between 110–160°C in hydrogen atmosphere. Catalytic activity measurements indicated that higher temperatures are better for the reactivation process.     

Hydrogen-Water Deuterium Exchange Reaction Over Mixed Oxide Supported Nickel Catalysts

Three series of catalysts, Ni/Al₂O₃-SiO₂, Ni/Al₂O₃-Cr₂O₃ and Ni/SiO₂-Cr₂O₃, were prepared by co-precipitation. In all samples the nickel content was kept constant at 70 at.% Ni, while the support composition was varied. The nickel surface areas, which are required to measure the specific catalytic activities, were determined by hydrogen chemisorption. In the case of the single oxide supported nickel catalysts, the order of the specific catalytic activity values was: Ni/Cr₂O₃<Ni/Al₂O₃<Ni/SiO₂. The specific catalytic activity of the Ni/Al₂O₃-SiO₂ samples, as a function of the support composition, follows approximately the weighted sum of the specific activities of the single oxide supported nickel catalysts. The specific catalytic activity value of the Ni/Al₂O₃-Cr₂O₃ and Ni/SiO₂-Cr₂O₃ samples more closely resembled that of Ni/Cr₂O₃ catalyst. The presence on chromia surface of the chromic anhydride and its tendency to spread onto are supposed to be the cause of this behaviour. Due to their enhanced activity, the Ni/Al₂O₃-Cr₂O₃ catalysts can be used for the production and detritiation of heavy water.     

Separation of Deuterium Isotope by Chemical Exchange between Hydrogen and Water Vapour

The separation factor of deuterium (α) for the exchange reaction between hydrogen and water vapour at 100 °C has been measured and was found to be equals to 2.52 and 2.50, depending on the used experimental technique.

An empirical equation relating the variation of the separation factor with temperature for such isotopic exchange reaction has been deduced. The values of α were calculated from 0–800 °C and indicated close agreement with those calculated from spectroscopic data.

Comparison of the deduced empirical equation with the general equation relating the separation factor with temperature for such reaction, allowed the calculation of the zero point energy, as well as the free energy as a function of temperature.     

Nickel/Chromium oxide/Zirconium oxide Catalysts for Hydrogen/Deuterium Isotopic Exchange

Catalysts composed of nickel and promoted with different metal oxides proved to be suitable for H/D isotropic exchange between hydrogen and water vapour. They loss their activity due to water condensation on their surfaces. Several nickel/chromium oxide/zirconium oxide catalysts of different composition were prepared by the coprecipitation technique. The liquid phase activity of these catalysts were followed using the hydrogen peroxide decomposition on their surfaces at different temperatures. The surface characteristics of the examined catalysts were followed by applying the BET method. The results were discussed and lead to the required catalyst composition which resists the water condensation on its surface during operation and has relatively high activity in the vapour phase H/D isotopic exchange reaction between hydrogen and water.     

H/D Isotopic Exchange between Hydrogen and Water Vapour on Ni/Cr2O3/ThO2 Catalysts

Thoriumdioxide was selected as a second promoter for nickel catalyst in addition to chromium oxide which was proved to be suitable to accelerate the H/D isotopic exchange reaction between hydrogen and water vapour. A series of Ni/Cr₂O₃/ThO₂ catalysts were prepared by the co-precipitation technique. The amount of Ni was 70 … 90 mol%, while that of Cr₂O₃ was 0 … 20 mol% and that of ThO₂ ranges from 0 … 30 mol%. This type of catalysts is sensitive for water condensation on its surface. The total surface area, total pore volume and pore radius of the catalysts were calculated from nitrogen adsorption on their surfaces at 77 K and application of the BET-equation.     

Hydrophobic Bimetallic Catalysts for H/D Exchange Reaction between Hydrogen and Water

Hydrophobic bimetallic catalysts of Pt-M on styrenedivinylbenzene were prepared, where M represents successively: Ir, Rh, Pd, Cu and Ag. The total metal loading was 0.5 wt% and the weight fractions of the metal M were: 0.0,0.05,0.1,0.25,0.5,0.75 and 1.0. For each sample, the catalytic activity for H/D exchange between hydrogen and water vapor was measured. In case of monometallic catalysts, no activity was detected for M = Cu and M = Ag, and the order of the activity values for the other metals was: Pt < Ir < Rh < Pd. For each bimetallic catalyst, the activity measurements indicated a clear interaction between the platinum and the second metal, thus the activity was significantly increased for M = Ir, increased for M = Rh, decreased for M = Pd, drastically decreased for M = Cu and M = Ag.     

Isotopic Exchange of Hydrogen between the Fluids of the Hydrocarbon Fields

It is presented the isotopic exchange of hydrogen in natural gas, crude oil, and underground water. The general behaviour of the isotopic exchange occuring in a system with a large number of components is given. A good agreement between the calculated and the experimental isotopic distribution factors is obtained in the case of the isotopic exchange of hydrogen between methane and underground water. The deuterium concentration of the crude oil samples inserts between the values obtained for methane and underground water. This fact is due to the presence of the isotopic exchange between these fluids.     

Liquid Phase Kinetic and Thermodynamic Studies on Promoted Nickel Catalysts used for H/D Exchange

Successful choice of the suitable catalyst composition for hydrogen/deuterium exchange reaction between hydrogen and water requires understanding of chemical kinetics as well as surface properties and activity in both liquid- and vapour phases. The present study deals with the thermodynamic and kinetic behaviour of a simple liquid phase reaction on the surface of nickel catalyst promoted with zirconium oxide used for the H/D exchange. This study helps understand the condensation of water on the catalyst surface during operation which leads to its poisoning. In this specific case water molecules are responsible for selective poisoning of this type of catalysts. The reaction rate constant, the increase in Gibb,s free energy, the enthalpy, the entropy of activation and the energy of activation were calculated.     

1H NMR Study of Hydrogen Bonding and Hydrogen to Deuterium Isotope Exchange in Ureido Sugars

Abstract

The acidic properties of ureido NH protons in two new derivatives of methyl 3,4,6-triacetyl-2-deoxy-β-D-glucopyranoside and i-butylamine (1) and L-leucine (2) were studied by ¹H NMR. Stronger influence of polar aprotic solvents, more effective interaction with nitroxyl radical and faster H/D exchange indicate that N1'-H proton which is proximate to the glucopyranose ring is more acidic than N3'-H one in both ureido sugars, this conclusion was supported by semi-empirical AM1 calculation. Hydrogen to deuterium exchange rates are 1.2 x 10^?2 to 5.5x 10^?3 M^?1 min^?l. Significantly slower exchange of N3'-H proton standing by Leu residue in 2 can be explained by the existence of internal H-bonds.     

Body Water,Lean Body and Fat Mass of Healthy Children as Measured by Deuterium Oxide Dilution

Abstract

Body composition of 165 healthy children was measured using the well-established method of deuterium oxide (²H₂O) dilution. After distribution of an oral load of 2.0 ml ²H₂O/kg body weight body water was estimated from the ²H₂O concentration in urine. Lean body mass was then calculated from body water using previously published age dependent ratios of the water content of the lean body mass. Fat mass was calculated as the difference of body weight and lean body mass. A good correlation was found between body water and body weight. Linear regression revealed TBW = 0.589 BW + 0.728 (r = 0.99). Body water, lean body mass and fat mass were found to change with age. The fat content of the body increases during the first six months of life. It then decreases until four to five years then rising again until 15 years of age.     

Hochwirksame ternäre Ni-Cr2O3-Al2O3-Mischkatalysatoren für den Deuteriumaustausch zwischen Wasserstoff und Wasserdampf

Die vorliegenden Untersuchungen basieren auf der Hypothese, daβ die spezifische Aktivität eines binären Ni-Cr₂O₃-Mischkatalysators für den Deuteriumaustausch in System Wasserstoff/Wasserdampf durch Zusatz einer geeeigeneten Drittkomponente durch Synergese gesteigert werden kann. Entsprechend den Anforderungen, die an die Drittkomponente zu stellen sind, erweist sich Al₂O₃ als besonders geeingent. Die gemessenen spezifischen Aktivitälen der untersuchten ternären Mischkatalysatoren zeigen, daβ entsprechend der angenommenen Hypothese ein bemerkenswerter synergetischer Effekt durch Zusatz von Al₂O₃ als Drittkomponente zu dem binären Ni-Cr₂O₃-Mischkatalysator innerhalb bestimmter Konzentrationsverhältnisse (80–85 Mol.% Ni, 5–15 Mol-% Cr₂O₃ und 5–15 Mol-% Al₂O₃) auftritt.     

NiWO3 Nanoparticles Grown on Graphitic Carbon Nitride (g‐C3N4) Supported Toray Carbon as an Efficient Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions

Catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are at the heart of water oxidation reactions. Despite continuous efforts, the development of OER/HER electrocatalysts with high activity at low cost remains a big challenge. Herein, a composite material consisting of TC@WO₃@g‐C₃N₄@Ni‐NiO complex matrix as a bifunctional electrocatalyst for the OER and HER is described. Though the catalyst has modest activity for HER, it exhibits high OER activity thereby making it a better nonprecious electrocatalyst for both OER and HER and is further improved by g‐C₃N₄. The catalytic activity arises from the synergetic effects between WO₃, Ni‐NiO, and g‐C₃N₄. A Ni‐NiO alloy and WO₃ nanoparticles decorated on the g‐C₃N₄ surface supported toray carbon (TC) matrix (TC@WO₃@g‐C₃N₄@Ni‐NiO) by a facile route that show an excellent and durable bifunctional catalytic activity for OER and HER in the alkaline medium are developed. This carbon nitride with binary metal/metal‐oxide matrix supported with TC exhibit an overpotential of 0.385 and 0.535 V versus RHE at a current density of 10 mA cm^?2 (Tafel slopes of 0.057 and 0.246 V dec^?1 for OER and HER, respectively), in 0.1 m NaOH . The catalyst is tested in water electrolysis for 17 h.     

A Facile Strategy to Synthesize Cobalt‐Based Self‐Supported Material for Electrocatalytic Water Splitting

Designing and developing active, robust, and noble‐metal‐free catalysts with superior stability for electrocatalytic water splitting is of critical importance but remains a grand challenge. Here, a facile strategy is provided to synthesize a series of Co‐based self‐supported electrode materials by combining electrospinning and chemical vapor deposition (CVD) technologies. The Co, Co₃O₄, Co₉S₈ nanoparticles (NPs) are formed in situ simultaneously with the formation of carbon nanofibers (CNFs) during the CVD process, respectively. The Co‐based NPs are uniformly distributed through the CNFs and they can be directly used as the electrode materials for hydrogen evolution reaction (HER) in acid and oxygen evolution reaction (OER) in alkaline. The Co₉S₈/CNFs membrane exhibits the best HER activity with overpotential of 165 mV at j = 10 mA cm^?2 and Tafel slope of 83 mV dec^?1 and OER activity with overpotential of 230 mV at j = 10 mA cm^?2 and Tafel slope of 72 mV dec^?1. The onion‐like graphitic layers formed around the NPs not only improve the electrical conductivity of the electrode but also prevent the separation of the NPs from the carbon matrix as well as the aggregation.     

Review of Laser-Induced Plasma,Its Mechanism,and Application to Quantitative Analysis of Hydrogen and Deuterium

Abstract

A comprehensive review of important progress achieved over the last 30 years regarding knowledge of laser-induced plasmas generated by CO₂ and Nd:YAG lasers in a variety of ambient gases is presented in this article, as well as research results on the extension of laser-induced breakdown spectroscopy (LIBS) for quantitative analysis of light elements, especially hydrogen and deuterium. First, the formation of shock wave–induced expanding secondary plasma in low-pressure ambient gases is discussed along with the dynamic characteristics of the secondary plasma expansion process. The unique advantages of low-pressure gas plasma are explained in relation to the successful detection of the sharp H and D emission lines. The experimental results using helium ambient gas are presented with emphasis on the role of He gas plasma in introducing an additional delayed excitation mechanism involving the helium metastable excited state, which resulted in the complete resolution of H and D emission lines, separated by only 0.18 nm. The development of a laser precleaning treatment and special double-pulse techniques further produced a linear calibration line with zero intercept applicable to quantitative H and D analyses of zircaloy sample, with either low- or high-pressure ambient He gas. More recent use of a transversely excited atmospheric (TEA) CO₂ laser in place of an Nd:YAG laser has demonstrated the much desired larger excited helium plasma and thereby resulted in significant emission enhancement and improved detection sensitivity.     

The Origin and Evolution of Some Mineral Water Sources Estimated from Their Deuterium Content

In this paper are discussed the origin and the evolution of several mineral water sources from some places of Romania, on the basis of deuterium content variations of water which take place in time and their correlation with the total salt content.     

Deuterium,Oxygen-18 and Salt Content of Drinking Water Sources in Cairo

The contineous increase of population in Cairo exceeding 10 millions inhabitants lead to the search for supplementary potable water resources in addition to the Nile River which is the principle drinking water source. Groundwater represents the main supplementary source. Evaluation of the groundwater feeding the so-called El-America Water Treatment Station which is one of the biggest potable water supplies at the northern of Cairo was carried out. Chemical and isotopic techniques were applied to estimate the suitability of this groundwater for drinking purposes. The chemical analysis includes the determination of sodium, potasium, calcium and magnesium concentrations in addition to those of chlorides, sulphates, bicarbonates and silicates, while the isotopic analysis includes oxygen-18 and deuterium. The overall chemical- and isotopic investigations determined the conditions at which the examined groundwater is suitable for drinking purposes.     

New Methods for Fully Automated Isotope Ratio Determination from Hydrogen at the Natural Abundance Level

Abstract

A variety of methods for measurement of ²H/¹H from H₂ are evaluated for their ability to be fully automated and for applicability to automated isotopic analysis of water and organic compounds. Equilibration of water with H₂ gas with the aid of a platinum catalyst has been commercialized into a fully automated sample preparation device. A second and newer technique, involving injecting water, methane, or other volatile organic compounds onto hot chromium in a reactor attached to the dual inlet system of a gas isotope ratio mass spectrometer, can be integrated with a conventional GC-autosampler to allow automated analysis of a variety of substrates. Both techniques result in precisions around 1‰ (δ notation) on the VSMOW scale, and are fast and accurate, and with appropriate mass spectrometers require only negligible scaling for the SLAP/VSMOW difference. Several experimental methods which show considerable promise employ “isotope ratio monitoring” (irm) inlet systems, in which a carrier gas is used for transport of H₂ to the mass spectrometer. Any such method has to address the problem of He ions corrupting the measurement of the H₂ ions. One such approach uses a heated palladium membrane for selective introduction of H₂ into the mass spectrometer, and a second involves modifications to the ion optics to control the stray helium ions. Both approaches have significant limitations that must be overcome before irm techniques can be used in routine applications, in particular for measuring hydrogen isotopes from GC effluents (irm-GCMS).     

Fractionation of Oxygen and Hydrogen Isotopes at the Hydrate Gas forming in the Sea Sediments

The paper gives data on isotope composition of interstitial and near-bottom waters sampled in a region of gas-hydrate formation in the Sea of Okhotsk. The studies shows that heavy isotope of oxygen and hydrogen is used in gas-hydrate formation, with the result that isotope composition of its constitution water constitutes δ¹⁸O = +1.99‰, δD = +23‰ relatively to SMOW. Formation of autogenic carbonates leads to isotope exchange with interstitial water wich, in turn, changes its primary isotope composition in the direction of increasing of O-18 content. The near-bottom waters are isotope-light relatively to the SMOW standard and to the mean isotope composition of interstitial water in the studied region of gas-hydrate spreading.     

Preconcentration and Determination of Manganese and Nickel from Various Water Samples by Nano Zirconium Oxide/Boron Oxide

ABSTRACT

This work assesses the potential of the adsorptive material nano zirconium oxide/boron oxide (ZrO₂/B₂O₃) for removal of trace Mn(II) and Ni(II) from environmental samples. This method is based on the sorption of Mn(II) and Ni(II) ions directly onto nanosorbent, followed by the elution and determination by flame atomic absorption spectrometry (FAAS). Experimental parameters, including pH of sample solution, volume and concentration of eluent, sample volume, and flow rate of sample solution, that affect the recovery of the Mn(II) and Ni(II) ions from model solutions have been optimized. Under the optimum conditions, adsorption isotherms and adsorption capacities have been examined. The recoveries of Mn(II) and Ni(II) were 96% ± 2% and 95% ± 3% at 95% confidence level, respectively. The analytical detection limits for Mn(II) and Ni(II) were 1.9 and 4.9 µ g L^?1, respectively. Adsorption capacities of the nano ZrO₂/B₂O₃ were found as 92.8 mg g^?1 for Mn and 168.4 mg g^?1 for Ni. The accuracy of the method was checked by analyzing certified reference material (SPS-WW1 wastewater) and spiked real samples. The method was applied for the determination of analytes in water samples.