Basic Hydrogen Research Articles

Versatile approach to α-alkoxy carbamate synthesis and stimulus-responsive alcohol release

A series of α-alkoxy carbamates that cleave under mild conditions to release alcohols has been synthesized through a multicomponent process. The relationship between structural features in these compounds and the rate of alcohol release in the presence of basic hydrogen peroxide has been studied. The preparation of carbamates that cleave under other conditions has been demonstrated.

Efficient pulsed chemical oxygen-iodine laser with instantaneous generation of atomic iodine by volumetric discharge

A pulsed chemical oxygen-iodine laser (COIL) using atomic iodine generated by volumetric discharge of CH3I is developed and tested. COIL with a gain length of 60 cm is energized by a square pipe-array jet singlet oxygen generator with basic hydrogen peroxide pumping circulations and operated at subsonic gas flow. Maximum output energy of 4.3 J, pulse duration of 50 μs, specific energy extraction from the active medium of 2.0 J/L, and the maximum chemical efficiency of 12.5% are achieved at a chlorine flow rate of 55 mmole/s.

Development Trends and Popularization Scenario for Fuel Cell Vehicle

The Toyota FCHV-adv that was released in 2008 has a cruising range in actual driving conditions of more than 500 km and can be started in temperatures as low as -30°, thereby overcoming two of the major obstacles to the practical adoption of FCVs. Toyota is continuing to resolve technical issues to popularize FCVs. For example, Toyota aims to reduce the cost to about 1/20 by further development work. In addition to improving commercial appeal, the widespread adoption of FCVs depends on the establishment of basic hydrogen infrastructure. Toward 2015, Car manufactures including Toyota are continuing to cooperate with governments and energy businesses to establish infrastructure and make the necessary modifications to laws and regulations. This article summarizes the technical progress for FCVs

Chemiluminescent reductive acridinium triggering (CRAT)—mechanism and applications

Acridinium esters traditionally are triggered using basic hydrogen peroxide. By serendipity, we have found that acridinium esters can also be triggered with emission of chemiluminescence by reductive triggering, e.g., by zinc metal or reduced forms of ferric and cupric salts. Furthermore, organic reducing compounds like dithiothreitol, tricarboxyethylphosphine or glutathione could be used in combination with organic oxidants like quinones or inorganic ferric or cupric salts. Mechanisms are proposed which involve the intermediacy of superoxide. Two forms of reactive oxygen species (i.e., hydrogen peroxide and superoxide) could be discriminated based on differences in kinetics. Some applications (improved detection of acridinium ester, use of acridinium ester as redox probes) are discussed.

Formation and Reactivity of a Biomimetic Hydroperoxocopper(II) Cryptate

AbstractCopper(II)‐hydroperoxo species are proposed as key intermediates in the catalytic cycles of copper‐monooxygenase enzymes that perform C–H bond hydroxylation. Herein we report on the oxidation chemistry of a copper(II) complex with a coordinating cryptand based on a peralkylated tetradentate tris(2‐aminoethyl)amine (tren) moiety. X‐ray crystallography of the copper(II) acetate complex of this cryptand revealed that the copper(II) ion is in a square‐pyramidal environment, with the cryptand acting only as a tridentate ligand. This geometry is conserved in solution and likely results from restraints imposed by the semi‐rigid cryptand. Reaction of this complex with basic hydrogen peroxide in methanol led to the decomposition of the complex with an oxygen‐atom transfer to the ligand, as evidenced by mass spectrometry analysis after reaction and demetallation. Low‐temperature stopped‐flow experiments (down to –90 °C) support the formation of a copper(II)‐hydroperoxo intermediate, CuOOH, before ligand oxygenation occurs. It is proposed that this intermediate performs the oxygen‐atom transfer to a weak benzylic C–H bond of the cryptand, thereby mimicking the behavior of dopamine‐β‐hydroxylase.

Current Understanding of the Transport Behavior of Hydrogen Species in MOS Stacks and Their Relation to Reliability Degradation

We review recent experiments that suggest a comprehensive model for the reversible hydrogen (H) transport between the poly-Si interface and the oxide/Si interface of MOS stacks. The H diffusion in intact model MOS structures is probed by H depth profiling via resonant 15N-H nuclear reaction analysis (NRA). It is demonstrated that MOS device degradation correlates with H accumulation in the oxide/Si interface region. A specific ultra-thin oxynitride is discovered in the poly-Si/oxynitride interface as well as in the near-surface region of N2-annealed nitride films and shown to function as a potential H-storage layer. The interfacial storage layer between the poly-Si gate and the oxynitride dielectric of MOS transistors is found to contain two kinds of H species, which are mobile and stable, respectively, versus irradiation-induced relocation. The mobile H, if stimulated by energetic carriers, migrates across the gate films and relocates to the SiO2/Si interface, causing device instabilities. Understanding this basic hydrogen transport behavior allows conceiving fabrication countermeasures to improve the device reliability.

Liquid-liquid reaction of hydrogen peroxide and sodium hypochlorite for the production of singlet oxygen in a centrifugal flow singlet oxygen generator

An attempt is made to produce gas-phase singlet oxygen O2(a1Δg) in a liquid-liquid reaction between acidic hydrogen peroxide (AHP) and sodium hypochlorite (NaOCl). The attempt arises from the fact that basic hydrogen peroxide (BHP) has long been the prime source for producing singlet delta oxygen through its reaction with chlorine. However, BHP suffers from the defect of being unstable during storage. Exploratory experiments were performed in a centrifugal flow singlet oxygen generator (CF-SOG) with two streams of solutions, AHP and NaOCl, mixed in a slit nozzle and then injected into the arc-shaped concavity in the CF-SOG to form a rotating liquid flow with a remarkable centrifugal force. With the help of this centrifugal force, the product of the O2(1Δ) reaction was quickly separated from the liquid phase. The gas-phase O2(1Δ) was detected via the spectrum of O2(1Δ) cooperative dimolecular emission with a CCD spectrograph. Experimental results show that it is feasible to produce gas-phase O2(1Δ) from the AHP + NaOCl reaction, and the stronger the acidity, the more efficient the O2(1Δ) production. However, since in the AHP + NaOCl reaction, Cl2 unavoidably appears as a byproduct, its catalytic action on the decomposition of H2O2 into ground-state O2 remains a major obstacle to utilising the AHP + NaOCl reaction in producing gas-phase O2(1Δ). Qualitative interpretation shows that the AHP + NaOCl reaction is virtually the reaction of interaction of molecular H2O2 with molecular HOCl, its mechanism being analogous to that of reaction of BHP with Cl2, where HOOCl is the key intermediate. It is difficult to form the intermediate HOOCl via the H2O2 + NaOCl reaction in a basic medium, thus gas-phase O2(1Δ) cannot be obtained in appreciable quantities.

Norharmane: Old yet highly selective dual channel ratiometric fluoride and hydrogen sulfate ion sensor

Norharmane provides a simple unexplored class of anion receptor, that allows for the ratiometric selective detection of F(-) and HSO(4)(-) ions. The presence of a strong base can easily form hydrogen bonds with the acidic hydrogen bond donor moiety and the relatively strong acid can easily protonate the basic hydrogen bond acceptor moiety, which can modulate the optical response and can detect the anions efficiently with high selectivity. In view of that, it is promising to conceive the use of these systems in various sensing applications as well as in other situations, such as anion transport and purification, where the availability of cheap and easy-to-make anion receptors, would be advantageous.

ChemInform Abstract: Mild Oxidative Conversion of Nitroalkanes into Carbonyl Compounds in Ionic Liquids.

AbstractOxidation of nitro‐derivatives in ionic liquids using basic hydrogen peroxide or sodium perborate provides a mild and efficient alternative to the traditional Nef reaction.

ChemInform Abstract: Facile One‐Pot Conversion of Aldehydes into Amides.

A facile one-pot synthesis of amides from aldehydes has been developed. This tandem process involves the formation of a nitrile intermediate obtained from the reaction of an aldehyde with hydroxylamine hydrochloride in dimethylsulfoxide at 100°C and the subsequent treatment of the nitrile with basic hydrogen peroxide. The resulting amide products were produced in good yields (67–95%) and purity (>95%).

Ruthenium Complexes Bearing N–H Acidic Pyrazole Ligands

AbstractChelate ligands containing at least one pyrazole group were treated with RuCl2(PPh3)3, RuHCl(CO)(PPh3)3 and RuH2(CO)(PPh3)3 to form ruthenium complexes bearing protic N–H groups in close proximity to the catalytically active ruthenium centre. In the case of the hydridoruthenium complex RuHCl(CO)(PPh3)3 the resulting complexes also contain abasic hydrido ligand. The combination of acidic and basic hydrogen species in one molecule and the arising two‐site reactivity was thoroughly investigated spectroscopically and by DFT calculations. Catalytic tests on the hydrogenation and transfer hydrogenation of acetophenone showed a general activity of these systems.

Dehydrogenation versus Decarbonylation of Oxygenates on Pd(110): Pure, Clean Pd Is a Poor Catalyst

Clean, pure Pd is a dehydrogenation catalyst and will crack many organic molecules interacting with it down to basic components, generally carbon, CO, and hydrogen. However, when the surface is passivated by adsorption in sufficient amount, the balance of reactivity changes, producing a more gentle catalytic material, which has much reduced dehydrogenation capabilities and more favors hydrogenation. In this paper, we describe molecular beam reactor measurements for the adsorption and reaction of C3 oxygenates with the Pd(110) surface, which clearly illustrate these properties.

Mild Oxidative Conversion of Nitroalkanes into Carbonyl Compounds in Ionic Liquids

Basic hydrogen peroxide and sodium perborate were found to be cheap and efficient alternatives for the conversion of primary and secondary nitro to carbonyl compounds (Nef reaction) in ionic liquids.

Facile One-Pot Conversion of Aldehydes into Amides

A facile one-pot synthesis of amides from aldehydes has been developed. This tandem process involves the formation of a nitrile intermediate obtained from the reaction of an aldehyde with hydroxylamine hydrochloride in dimethylsulfoxide at 100°C and the subsequent treatment of the nitrile with basic hydrogen peroxide. The resulting amide products were produced in good yields (67–95%) and purity (>95%).

Spray generator of singlet oxygen for a chemical oxygen-iodine laser

A spray type of singlet oxygen generator for driving the Chemical Oxygen-Iodine Laser was developed. Singlet oxygen, O2(1Δg), is generated by a fast reaction of chlorine with basic hydrogen peroxide solution in the form of a dense spray. A mathematical model of this reaction system showed that O2(1Δg) can be generated in this system with a high yield (0.70–0.80), high utilization of chlorine (0.75–0.95), and effective utilization of liquid (0.36–0.54) at very high generator pressures (35–75 kPa). Experimental studies of this reaction system without an efficient separation of liquid proved an efficient O2(1Δg) production characterized by a rather high product of chlorine utilization and O2(1Δg) yield (0.4–0.9) at very high generator pressures (30–80 kPa). This pressure is much higher than the operation pressure used in other generators, which should be beneficial for a pressure recovery system of the COIL. These results provided the basis for designing a centrifugal spray generator with an efficient separation of liquid from the gas flow, which is the subject of the following paper.

Effect of hydrogen on fatigue crack growth of metals

Abstract The present paper shows several important phenomena obtained by investigations of the effect of hydrogen on fatigue crack growth behaviour, including the measurement of the hydrogen content in various materials such as low-carbon, Cr–Mo and stainless steels. Particularly important phenomena are the localization of fatigue slip bands, strain-induced martensite in Types 304, 316 and even 316L, and also strong frequency effects on fatigue crack growth rates. For example, with a decrease in frequency of fatigue loading down to the level of 0.2 Hz, the fatigue crack growth rate of a Cr–Mo steel is accelerated by 10–30 times. The same phenomenon also occurs even in austenitic stainless steels at the frequency of the level of 0.001 Hz. Striation morphology is also influenced by hydrogen. It has been revealed by re-analysing the results of the authors’ separately published reports that this basic hydrogen embrittlement mechanism is essentially the same throughout all the materials, i.e. low-carbon, Cr–Mo and stainless steels. Thus, the coupled effects of hydrogen content, hydrogen diffusion coefficient (for BCC or FCC), load frequency, localization of fatigue slip bands and strain-induced martensite must be always considered in fatigue test and analysis of hydrogen embrittlement.

Research on Uniform-Droplet Singlet-Oxygen Generator

The formation of a uniform droplet is the key in a uniform-droplet singlet-oxygen generator (SOG). This paper is mainly on the condition of uniform droplet formation. Factors in uniform-droplet formation, such as basic hydrogen peroxide (BHP) liquid velocity, disturbance frequency, and the pressure distribution in the fluid infusion cavity, were analyzed and optimized in order to improve the performance of the uniform-droplet singlet-oxygen generator. The chlorine utilization, O2(1Δ) yield, H2O concentration, and laser power were measured. The output concentration of O2(1Δ) was as high as 2.94 ×1017/cm3. The maximum power density through the nozzle was 121.3 W/cm2.

Corrosion of equipment and its protection at producing and technical application of organofluorine products

Extension of the nomenclature of fluorine-containing products, and modernization of the methods for their synthesis (liquid-phase and gas-phase fluorination of the feedstock with hydrogen fluoride, electrochemical fluorination in anhydrous hydrogen fluoride, direct fluorination with gaseous fluorine and with the use of metals carrying fluorine, etc.) require extension of research on the corrosion safety of equipment at the implementation of new technologies. Therefore, the Laboratory of Corrosion is systematically involved in the work on improving the technology of producing basic fluorinating agents, elemental fluorine and hydrogen fluoride, that are highly aggressive towards structural materials.

Numerical Modelling of Cold Cracking Initiation and Propagation in S 1100 QL Steel Root Welds

Although the phenomenon of hydrogen assisted cold cracking (HACC) and respective avoidance procedures have extensively been investigated in the seventies and eighties, the reasons for recent failures are still a lack of knowledge about the basic hydrogen effects on steel microstructures and, in particular, a lack of welding procedure specifications and standards accounting directly and consistently for cold cracking avoidance in modern high strength structural steels with yield strengths of up to 1 100 MPa. In previous several contributions the consequences of various heat treatment procedures targeted at HACC avoidance have been shown, as for instance their effects on stress-strain build up and on hydrogen diffusion in high strength steel welds. But, a principal interaction of three local influences on hydrogen assisted cold cracking, i.e. local microstructure; local mechanical load and local hydrogen content have not yet been studied in detail for these materials. For this, a numerical model for HACC has been developed, accounting particularly for crack-initiation and crack-propagation criteria, like the hydrogen redistribution during the process of cracking. The numerical model has been used to investigate HACC in such materials, i.e. in the weld microstructures of an S 1100 QL steel, under severe restraint and various hydrogen levels. The results were achieved by in depth thermal and structural finite element simulations combined with numerical hydrogen diffusion modelling. By such procedure, HACC in single-layer welded plates with thickness of 20.0 mm at realistic restraints has been studied. As a particular result, it turned out that the crack-initiation location is typically in the centre of the weld metal (WM), where only a single crack is initiated at hydrogen contents of up to 10.0 Nml/100 g Fe. But, it was evidently shown by such analyses that the crack-initiation location is shifted into the HAZ and that multiple cracking occurs at higher hydrogen contents of up to 15.0 Nml/100 g Fe.

Design of a silicon‐based microscale trickle‐bed system for singlet‐oxygen production

AbstractDesign methodology and flow characterization of a miniaturized trickle‐bed system for singlet‐oxygen production via exothermic reaction of chlorine gas and basic hydrogen peroxide aqueous solution are reported. Miniaturized singlet oxygen production is accomplished by integration of several components developed for microsystems (uniform phase distributors, integrated on‐chip cooling, and capillary‐based phase separation) within a single device. Macroscale design equations for pressure‐drop and heat‐transfer rates are verified experimentally in the miniature trickle‐bed reactor. Flow regime data from the present study are summarized with previous reports in microdevices and compared to conventional multiphase flow maps; these maps are found to be incapable of accurately predicting the flow regime trends within the miniaturized trickle‐bed system. Operation of the silicon‐based miniaturized trickle‐bed reactor achieved estimated singlet‐oxygen yields of 78%, comparing well with the reactor model predictions. © 2008 American Institute of Chemical Engineers AIChE J, 2008