Electrochemical behavior of Alloy 22 and friction type rock bolt

NASA Astrophysics Data System (ADS)

Rahman, Md Sazzadur

Alloy 22 (Ni-22Cr-13Mo-3Fe-3W) is a candidate alloy for the outer shell of spent nuclear materials storage containers in the Yucca Mountain High Level Nuclear Waste Repository because of its excellent corrosion resistance. The nuclear waste container is cylindrical in shape and the end caps are welded. Typically, Alloy 22 retains the high temperature single phase cubic structure near room temperature, but topologically close packed (TCP) phases such as mu, P, sigma etc. and Cr rich carbides can form during thermal aging and welding. Rock bolts that are used for reinforcing subsurface tunnels are generally made of carbon or low alloy steels; these are being used in the nuclear repository tunnel. The corrosion behavior of these rock bolts have not been systematically evaluated under the environmental conditions of the repository. The ground waters at the Yucca Mountain (YM) repository permeate through the pores of the rock mass, and have propensity to corrode the rock bolts and waste package container. The environmental (aerated and deaerated) conditions influence the rate of corrosion in these material; these have not been systematically evaluated yet under the repository environment. In this study, the corrosion behavior of Alloy 22 and a friction type rock bolts was investigated as a function of temperature and concentration in complex multi-ionic electrolytes. Simulated electrolyte of YM ground water found in the repository environment was made in different concentrations (1X, 10X, and 100X). The interaction of simulated electrolytes in aerated and deaerated condition with Alloy 22 and low alloy steel of friction type rock bolt (split tapered cylinder type commercial design) has been investigated. Polarization resistance method was used to measure the corrosion rates. We found that the corrosion rate of Alloy 22 was higher in the deaerated electrolyte as compared to the aerated. The presence of oxygen in the electrolyte during aeration is conducive to formation of passive films that inhibits the corrosion process. The temperature dependency of the corrosion rate was affected by aeration and deaeration of the electrolytes. Another study related to corrosion behavior of weld Alloy 22 was undertaken to understand electrochemical behavior of welded structures. Corrosion studies were carried out in more aggressive electrolyte (0.1M HCl at 66°C) after solution annealing at 1121°C for 1 hr. In the as-welded structure a dendritic microstructure was observed in the weld region. However, after solution annealing these dendrites are not observed; suggesting homogenization of the grains. Three different specimens were made out from a welded Alloy 22 plates with large welded surface; weld interface, half weld and base metal away from the weld and heat affected zone, and corrosion rates of all these samples were measured. The results showed that the corrosion resistance of the solution annealed was higher in all three specimens than those of as-welded specimens. Corrosion rates of friction type set rock bolts (split set) were measured at 25°C, 45°C, 65°C and 90°C using 1X, 10X and 100X concentration of electrolyte both in aerated and deaerated conditions. The corrosion rates of rock bolts in 1X and 10X electrolyte showed ranged from ˜30 to 200mum/yr for deaerated and 150 to 1600 mum/yr for aerated. In summary, we have investigated the electrochemical behavior of the Alloy 22 and steels that have significance to the YM nuclear repository. The effects of temperature, type of electrolyte, condition of the alloys on the corrosion rates are reported.

System for Continuous Deaeration of Hydraulic Oil

NASA Technical Reports Server (NTRS)

Anderson, Christopher W.

2006-01-01

A system for continuous, rapid deaeration of hydraulic oil has been built to replace a prior system that effected deaeration more slowly in a cyclic pressure/ vacuum process. Such systems are needed because (1) hydraulic oil has an affinity for air, typically containing between 10 and 15 volume percent of air and (2) in the original application for which these systems were built, there is a requirement to keep the proportion of dissolved air below 1 volume percent because a greater proportion can lead to pump cavitation and excessive softness in hydraulic-actuator force-versus-displacement characteristics. In addition to overcoming several deficiencies of the prior deaeration system, the present system removes water from the oil. The system (see figure) includes a pump that continuously circulates oil at a rate of 10 gal/min (38 L/min) between an 80-gal (303-L) airless reservoir and a tank containing a vacuum. When the circulation pump is started, oil is pumped, at a pressure of 120 psi (827 kPa), through a venturi tube below the tank with a connection to a stand-pipe in the tank. This action draws oil out of the tank via the standpipe. At the same time, oil is sprayed into the tank in a fine mist, thereby exposing a large amount of oil to the vacuum. When the oil level in the tank falls below the lower of two level switches, a vacuum pump is started, drawing a hard vacuum on the tank through a trap that collects any oil and water entrained in the airflow. When the oil level rises above higher of the two level switches or when the system is shut down, a solenoid valve between the tank and the vacuum pump is closed to prevent suction of oil into the vacuum pump. Critical requirements that the system is designed to satisfy include the following: 1) The circulation pump must have sufficient volume and pressure to operate the venturi tube and spray nozzles. 2) The venturi tube must be sized to empty the tank (except for the oil retained by the standpipe) and maintain a vacuum against the vacuum pump. 3) The tank must be strong enough to withstand atmospheric pressure against the vacuum inside and must have sufficient volume to enable exposure of a sufficiently large amount of sprayed oil to the vacuum. 4) The spray nozzles must be sized to atomize the oil and to ensure that the rate of flow of sprayed oil does not exceed the rate at which the venturi action can empty the tank. 5) The vacuum pump must produce a hard vacuum against the venturi tube and continue to work when it ingests some oil and water. 6) Fittings must be made vacuum tight (by use of O-rings) to prevent leakage of air into the system. The system is fully automatic, and can be allowed to remain in operation with very little monitoring. It is capable of reducing the air content of the oil from 11 to less than 1 volume percent in about 4 hours and to keep the water content below 100 parts per million.

All-regime combined-cycle plant: Engineering solutions

NASA Astrophysics Data System (ADS)

Berezinets, P. A.; Tumanovskii, G. G.; Tereshina, G. E.; Krylova, I. N.; Markina, V. N.; Migun, E. N.

2016-12-01

The development of distributed power generation systems as a supplement to the centralized unified power grid increases the operational stability and efficiency of the entire power generation industry and improves the power supply to consumers. An all-regime cogeneration combined-cycle plant with a power of 20-25 mW (PGU-20/25T) and an electrical efficiency above 50% has been developed at the All-Russia Thermal Engineering Institute (ATEI) as a distributed power generation object. The PGU-20/25T two-circuit cogeneration plant provides a wide electrical and thermal power adjustment range and the absence of the mutual effect of electrical and thermal power output regimes at controlled frequency and power in a unified or isolated grid. The PGU-20/25T combined-cycle plant incorporates a gas-turbine unit (GTU) with a power of 16 MW, a heat recovery boiler (HRB) with two burners (before the boiler and the last heating stage), and a cogeneration steam turbine with a power of 6/9 MW. The PGU-20/25T plant has a maximum electrical power of 22 MW and an efficiency of 50.8% in the heat recovery regime and a maximum thermal power output of 16.3 MW (14 Gcal/h) in the cogeneration regime. The use of burners can increase the electrical power to 25 MW in the steam condensation regime at an efficiency of 49% and the maximum thermal power output to 29.5 MW (25.4 Gcal/h). When the steam turbine is shut down, the thermal power output can grow to 32.6 MW (28 Gcal/h). The innovative equipment, which was specially developed for PGU-20/25T, improves the reliability of this plant and simplifies its operation. Among this equipment are microflame burners in the heat recovery boiler, a vacuum system based on liquid-ring pumps, and a vacuum deaerator. To enable the application of PGU-20/25T in water-stressed regions, an air condenser preventing the heat-transfer tubes from the risk of covering with ice during operation in frost air has been developed. The vacuum system eliminates the need for an extraneous source of steam for the startup of the PGU-20/25T plant. The vacuum deaerator provides prestartup deaeration and the filling of the entire condensate feed pipeline with deaerated water and also enables the maintenance of the water temperature before the boiler at a level of no lower than 60°C and the oxygen content at a level of no higher than 10 μg/L during operation under load. The microflame burners in the heat recovery boiler enable the independent adjustment of the electrical power and the thermal power output from the PGU-20/25T plant. All the innovative equipment has been tested on experimental prototypes.

Methodological implications in pH standardization of exhaled breath condensate.

PubMed

Hoffmeyer, F; Berresheim, H; Beine, A; Sucker, K; Brüning, T; Bünger, J

2015-05-14

The variable amount of dissolved carbon dioxide is one of the main confounding factors of exhaled breath condensate (EBC) pH measurements. There have been many attempts at identifying the optimal approach to displace CO2 as a way to gain reproducible and valid pH values in EBC samples. The aim of the present study was to assess the correlation of pH and pCO2 in untreated, neat EBC samples and, after deaeration, to reevaluate the standardization of CO2 as a means to obtain valid pH values. A further aim was to evaluate the impact of deaeration on the acid-base balance in EBC samples. EBC was collected from seven female and 31 male subjects. The pH and pCO2 values immediately determined in untreated, neat EBC samples were strongly correlated (rp = -0.723, p <  0.0001). This correlation was not observed after deaeration with argon (rs = 0.264, p = 0.109). Based on a regression function for the pH/pCO2 relationship, the calculated pH at a pCO2 of 5.33 kPa was 6.07 (IQR 5.99, 6.20). No significant difference was observed between the pH measured in neat EBC samples and those calculated after deaeration with regression function and measured neat pCO2. Our data suggest that pCO2 is the most important confounder of pH measurement in EBC samples and, when adjusting for pCO2, the acid-base balance of EBC samples is not significantly influenced by the process of deaeration. Furthermore, measurement with a blood-gas analyzer and standardization of pH for pCO2 allows sensitive assaying of EBC samples. Therefore, this method provides a basis for detection of even small changes in airway pH due to inhalative exposure or respiratory disease.

The effect of long-term nitrate treatment on SRB activity, corrosion rate and bacterial community composition in offshore water injection systems.

PubMed

Bødtker, Gunhild; Thorstenson, Tore; Lillebø, Bente-Lise P; Thorbjørnsen, Bente E; Ulvøen, Rikke Helen; Sunde, Egil; Torsvik, Terje

2008-12-01

Biogenic production of hydrogen sulphide (H(2)S) is a problem for the oil industry as it leads to corrosion and reservoir souring. Continuous injection of a low nitrate concentration (0.25-0.33 mM) replaced glutaraldehyde as corrosion and souring control at the Veslefrikk and Gullfaks oil field (North Sea) in 1999. The response to nitrate treatment was a rapid reduction in number and activity of sulphate-reducing bacteria (SRB) in the water injection system biofilm at both fields. The present long-term study shows that SRB activity has remained low at < or =0.3 and < or =0.9 microg H(2)S/cm(2)/day at Veslefrikk and Gullfaks respectively, during the 7-8 years with continuous nitrate injection. At Veslefrikk, 16S rRNA gene based community analysis by PCR-DGGE showed that bacteria affiliated to nitrate-reducing sulphide-oxidizing Sulfurimonas (NR-SOB) formed major populations at the injection well head throughout the treatment period. Downstream of deaerator the presence of Sulfurimonas like bacteria was less pronounced, and were no longer observed 40 months into the treatment period. The biofilm community during nitrate treatment was highly diverse and relative stable for long periods of time. At the Gullfaks field, a reduction in corrosion of up to 40% was observed after switch to nitrate treatment. The present study show that nitrate injection may provide a stable long-term inhibition of SRB in sea water injection systems, and that corrosion may be significantly reduced when compared to traditional biocide treatment.

Catalytic two-electron reduction of dioxygen by ferrocene derivatives with manganese(V) corroles.

PubMed

Jung, Jieun; Liu, Shuo; Ohkubo, Kei; Abu-Omar, Mahdi M; Fukuzumi, Shunichi

2015-05-04

Electron transfer from octamethylferrocene (Me8Fc) to the manganese(V) imidocorrole complex (tpfc)Mn(V)(NAr) [tpfc = 5,10,15-tris(pentafluorophenyl)corrole; Ar = 2,6-Cl2C6H3] proceeds efficiently to give an octamethylferrocenium ion (Me8Fc(+)) and [(tpfc)Mn(IV)(NAr)](-) in acetonitrile (MeCN) at 298 K. Upon the addition of trifluoroacetic acid (TFA), further reduction of [(tpfc)Mn(IV)(NAr)](-) by Me8Fc gives (tpfc)Mn(III) and ArNH2 in deaerated MeCN. TFA also results in hydrolysis of (tpfc)Mn(V)(NAr) with residual water to produce a protonated manganese(V) oxocorrole complex ([(tpfc)Mn(V)(OH)](+)) in deaerated MeCN. [(tpfc)Mn(V)(OH)](+) is rapidly reduced by 2 equiv of Me8Fc in the presence of TFA to give (tpfc)Mn(III) in deaerated MeCN. In the presence of dioxygen (O2), (tpfc)Mn(III) catalyzes the two-electron reduction of O2 by Me8Fc with TFA in MeCN to produce H2O2 and Me8Fc(+). The rate of formation of Me8Fc(+) in the catalytic reduction of O2 follows zeroth-order kinetics with respect to the concentrations of Me8Fc and TFA, whereas the rate increases linearly with increasing concentrations of (tpfc)Mn(V)(NAr) and O2. These kinetic dependencies are consistent with the rate-determining step being electron transfer from (tpfc)Mn(III) to O2, followed by further proton-coupled electron transfer from Me8Fc to produce H2O2 and [(tpfc)Mn(IV)](+). Rapid electron transfer from Me8Fc to [(tpfc)Mn(IV)](+) regenerates (tpfc)Mn(III), completing the catalytic cycle. Thus, catalytic two-electron reduction of O2 by Me8Fc with (tpfc)Mn(V)(NAr) as a catalyst precursor proceeds via a Mn(III)/Mn(IV) redox cycle.

Galvanic corrosion of nitinol under deaerated and aerated conditions.

PubMed

Pound, Bruce G

2016-10-01

Various studies have examined the corrosion rate of nitinol generally under deaerated conditions. Likewise, galvanic corrosion studies have typically involved deaerated solutions. This work addressed the effect of galvanic coupling on the corrosion current of electropolished nitinol in phosphate buffered saline and 0.9% sodium chloride under dearated and aerated conditions for times up to 24 h. Tests were performed on nitinol alone and coupled with MP35N in both the mechanically polished and passivated conditions. Aeration and galvanic coupling were found to have relatively little effect, indicating that the corrosion current is controlled by the anodic reaction. The current can be attributed entirely to Ni(2+) dissolution, which appears to be governed by solid-state mass transport of Ni(2+) through the passive oxide film. Because corrosion of EP nitinol is controlled by the anodic reaction, contact between EP nitinol and MP35N or other biomedical Co-Cr alloys is unlikely to result in significant galvanic effects in vivo. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1322-1327, 2016. © 2015 Wiley Periodicals, Inc.

Development of Technologies on Innovative-Simplified Nuclear Power Plant using High-Efficiency Steam Injectors

NASA Astrophysics Data System (ADS)

Ohmori, Shuichi; Narabayashi, Tadashi; Mori, Michitsugu; Iwaki, Chikako; Asanuma, Yutaka; Goto, Shoji

A Steam Injector (SI) is a simple, compact and passive pump and also acts as a high-performance direct-contact heater. This provides SI with capability to serve also as a direct-contact feed-water heater that heats up feed-water by using extracted steam from turbine. Our technology development aims to significantly simplify equipment and reduce physical quantities by applying "High-Efficiency SI", which are applicable to a wide range of operation regimes beyond the performance and applicable range of existing SIs and enables unprecedented multistage and parallel operation, to the low-pressure feed-water heaters and Emergency Core Cooling System of nuclear power plants, as well as achieve high inherent safety to prevent severe accidents by keeping the core covered with water (a Severe Accident-Free Concept). This paper describes the results of the endurance and performance tests of low-pressure SIs for feed-water heaters with Jet-deaerator and core injection system.

Bactericidal Effect of Zero-Valent Iron Nanoparticles on Escherichia coli

PubMed Central

Lee, Changha; Kim, Jee Yeon; Lee, Won Il; Nelson, Kara L.; Yoon, Jeyong; Sedlak, David L.

2008-01-01

Zero-valent iron nanoparticles (nano-Fe0) in aqueous solution rapidly inactivated Escherichia coli (E. coli). A strong bactericidal effect of nano-Fe0 was found under deaerated conditions, with a linear correlation between log inactivation and nano-Fe0 dose (0.82 log inactivation / mg/L nano-Fe0 · hr). The inactivation of E. coli under air saturation required much higher nano-Fe0 doses due to the corrosion and surface oxidation of nano-Fe0 by dissolved oxygen. Significant physical disruption of the cell membranes was observed in E. coli exposed to nano-Fe0, which may have caused the inactivation, or enhanced the biocidal effects of dissolved iron. The reaction of Fe(II) with intracellular oxygen or hydrogen peroxide also may have induced oxidative stress by producing reactive oxygen species. The bactericidal effect of nano-Fe0 was a unique property of nano-Fe0, which was not observed in other types of iron-based compounds. PMID:18678028

The effects of temperature and aeration on the corrosion of A508III low alloy steel in boric acid solutions at 25-95 °C

NASA Astrophysics Data System (ADS)

Xiao, Qian; Lu, Zhanpeng; Chen, Junjie; Yao, Meiyi; Chen, Zhen; Ejaz, Ahsan

2016-11-01

The effects of temperature, solution composition and dissolved oxygen on the corrosion rate and electrochemical behavior of an A508III low alloy steel in boric acid solution with lithium hydroxide at 25-95 °C are investigated. In aerated solutions, increasing the boric acid concentration increases the corrosion rate and the anodic current density. The corrosion rate in deaerated solutions increases with increasing temperature. A corrosion rate peak value is found at approximately 75 °C in aerated solutions. Increasing temperature increases the oxygen diffusion coefficient, decreases the dissolved oxygen concentration, accelerates the hydrogen evolution reaction, and accelerates both the active dissolution and the film forming reactions. Increasing dissolved oxygen concentration does not significantly affect the corrosion rate at 50 and 60 °C, increases the corrosion rate at 70 and 80 °C, and decreases the corrosion rate at 87.5 and 95 °C in a high concentration boric acid solution with lithium hydroxide.

Effect of dissolved oxygen on the corrosion behavior of 304 SS in 0.1 N nitric acid containing chloride

NASA Astrophysics Data System (ADS)

Khobragade, Nilay N.; Bansod, Ankur V.; Patil, Awanikumar P.

2018-04-01

A study was undertaken in several selected mixed nitric acid/chloride ({{{{NO}}}3}-/{{{Cl}}}- ratio) electrolytes with the nitric acid concentration of 0.1 N and chloride concentration of 0, 10, 100, 1000 and 10 000 ppm. Electrochemical tests like potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS) and Mott-Schottky analysis (M-S) were carried out when the electrolytes were in deaerated condition and were in open to air (OTA) condition, and the effect of dissolved oxygen was evaluated on the corrosion behavior of 304 SS. It was found that at a critical {{{{NO}}}3}-/{{{Cl}}}- ratio, a passive state is attained at the earliest in OTA condition. Also, the passive film resistance showed higher values in OTA condition than in deaerated condition exhibiting the effect of dissolved oxygen. The results of EIS results confirmed the results obtained by potentiodynamic polarization wherein the low passive current densities were obtained in OTA condition. Mott-Schottky analysis revealed the lowest defect densities in 100 ppm Cl‑ solution in OTA condition and in 10 ppm Cl‑ solution in deaerated condition indicating less defective films formed in these solutions. XPS analysis showed that the film was bilayer in nature in confirmation with M-S analysis. The results were discussed with point defect model (PDM) and by competitive surface adsorption.

Process for making a noble metal on tin oxide catalyst

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Davis, Patricia (Inventor); Miller, Irvin M. (Inventor)

1989-01-01

A quantity of reagent grade tin metal or compound, chloride-free, and high-surface-area silica spheres are placed in deionized water, followed by deaerating the mixture by boiling and adding an oxidizing agent, such as nitric acid. The nitric acid oxidizes the tin to metastannic acid which coats the spheres because the acid is absorbed on the substrate. The metastannic acid becomes tin oxide upon drying and calcining. The tin-oxide coated silica spheres are then placed in water and boiled. A chloride-free precious metal compound in aqueous solution is then added to the mixture containing the spheres, and the precious metal compound is reduced to a precious metal by use of a suitable reducing agent such as formic acid. Very beneficial results were obtained using the precious metal compound tetraammine platinum(II) hydroxide.

Open-cycle systems performance analysis programming guide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olson, D.A.

1981-12-01

The Open-Cycle OTEC Systems Performance Analysis Program is an algorithm programmed on SERI's CDC Cyber 170/720 computer to predict the performance of a Claude-cycle, open-cycle OTEC plant. The algorithm models the Claude-cycle system as consisting of an evaporator, a turbine, a condenser, deaerators, a condenser gas exhaust, a cold water pipe and cold and warm seawater pumps. Each component is a separate subroutine in the main program. A description is given of how to write Fortran subroutines to fit into the main program for the components of the OTEC plant. An explanation is provided of how to use the algorithm.more » The main program and existing component subroutines are described. Appropriate common blocks and input and output variables are listed. Preprogrammed thermodynamic property functions for steam, fresh water, and seawater are described.« less

Production of gaseous fuel by pyrolysis of municipal solid waste

NASA Technical Reports Server (NTRS)

Crane, T. H.; Ringer, H. N.; Bridges, D. W.

1975-01-01

Pilot plant tests were conducted on a simulated solid waste which was a mixture of shredded newspaper, wood waste, polyethylene plastics, crushed glass, steel turnings, and water. Tests were conducted at 1400 F in a lead-bath pyrolyser. Cold feed was deaerated by compression and was dropped onto a moving hearth of molten lead before being transported to a sealed storage container. About 80 percent of the feed's organic content was converted to gaseous products which contain over 90 percent of the potential waste energy; 12 percent was converted to water; and 8 percent remained as partially pyrolyzed char and tars. Nearly half of the carbon in the feed is converted to benzene, toluene and medium-quality fuel gas, a potential credit of over $25 per ton of solid waste. The system was shown to require minimal preprocessing and less sorting then other methods.

Corrosion behavior of ceramic-coated ZIRLO™ exposed to supercritical water

NASA Astrophysics Data System (ADS)

Mandapaka, Kiran K.; Cahyadi, Rico S.; Yalisove, Steven; Kuang, Wenjun; Sickafus, K.; Patel, Maulik K.; Was, Gary S.

2018-01-01

The corrosion behavior of ceramic coated ZIRLO™ tubing was evaluated in a supercritical water (SCW) environment to determine its behavior in high temperature water. Two coating architectures were analyzed; a 4 bi-layer TiAlN/TiN coating with Ti bond coat, and a TiN monolithic coating with Ti bond layer on ZIRLO™ tubes using cathodic arc physical vapor deposition (CA-PVD) technique. Femtosecond laser ablation was used to introduce reproducible defects in some of the coated tubes. On exposure to deaerated supercritical water at 542 °C for 48 h, coated tubes exhibited significantly higher weight gain compared to uncoated ZIRLO™. Examination revealed formation of a uniform ZrO2 layer beneath the coating of a thickness similar to that on the uncoated tube inner surface. The defects generated during the coating process acted as preferential paths for diffusion of oxygen resulting in the oxidation of substrate ZIRLO™. However, there was no delamination of the coating. There were insignificant differences in the oxidation weight gain between laser ablated and non-ablated tubes and the laser induced defects did not spread beyond their original size.

11. Building Layout, 185189 D, U.S. Atomic Energy Commission, Richland ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

11. Building Layout, 185-189 D, U.S. Atomic Energy Commission, Richland Operations Office, Dwg. No. H-1-14844, 1957. - D-Reactor Complex, Deaeration Plant-Refrigeration Buildings, Area 100-D, Richland, Benton County, WA

Formation of combustible hydrocarbons and H2 during photocatalytic decomposition of various organic compounds under aerated and deaerated conditions.

PubMed

Mozia, Sylwia; Kułagowska, Aleksandra; Morawski, Antoni W

2014-11-26

A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air) was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence of air, the gaseous phase contained CO2, CH4 and H2, regardless of the substrate used. Moreover, formation of C2H6 and C3H8 in the case of acetic acid and C2H6 in the case of ethanol was observed. In case of acetic acid and methanol an increase in H2 evolution under aerated conditions was observed. It was concluded that the photocatalytic decomposition of organic compounds with simultaneous generation of combustible hydrocarbons and hydrogen could be a promising method of "green energy" production.

12. General Arrangement Plan, Building 189D, U.S. Atomic Energy Commission, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

12. General Arrangement Plan, Building 189-D, U.S. Atomic Energy Commission, General Electric Company, Dwg. No. H-1-11068, 1958. - D-Reactor Complex, Deaeration Plant-Refrigeration Buildings, Area 100-D, Richland, Benton County, WA

13. Architectural First Floor Plan Buildings 185189 D, U.S. Atomic ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

13. Architectural First Floor Plan Buildings 185-189 D, U.S. Atomic Energy Commission, General Electric Company, Dwg. NO. H-1-11825, 1959. - D-Reactor Complex, Deaeration Plant-Refrigeration Buildings, Area 100-D, Richland, Benton County, WA

10. Floor Layout of Thermal Hydraulics Laboratory, from The Thermal ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

10. Floor Layout of Thermal Hydraulics Laboratory, from The Thermal Hydraulics Laboratory at Hanford. General Electric Company, Hanford Atomic Products Operation, Richland, Washington, 1961. - D-Reactor Complex, Deaeration Plant-Refrigeration Buildings, Area 100-D, Richland, Benton County, WA

1. 185/189D in center, north end west facades (190D front ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. 185/189-D in center, north end west facades (190-D front left and west facade; 195-D rear right). Looking south. - D-Reactor Complex, Deaeration Plant-Refrigeration Buildings, Area 100-D, Richland, Benton County, WA

Degradation kinetic modelling of ascorbic acid and colour intensity in pasteurised blood orange juice during storage.

PubMed

Remini, Hocine; Mertz, Christian; Belbahi, Amine; Achir, Nawel; Dornier, Manuel; Madani, Khodir

2015-04-15

The stability of ascorbic acid and colour intensity in pasteurised blood orange juice (Citrus sinensis [L.] Osbeck) during one month of storage was investigated at 4-37 °C. The effects of ascorbic acid fortification (at 100, 200 mg L(-1)) and deaeration, temperature/time storage on the kinetic behaviour were determined. Ascorbic acid was monitored by HPLC-DAD and colour intensity by spectrophotometric measurements. Degradation kinetics were best fitted by first-order reaction models for both ascorbic acid and colour intensity. Three models (Arrhenius, Eyring and Ball) were used to assess the temperature-dependent degradation. Following the Arrhenius model, activation energies were ranged from 51 to 135 kJ mol(-1) for ascorbic acid and from 49 to 99 kJ mol(-1) for colour intensity. The effect of storage temperature and deaeration are the most influent factors on kinetics degradation, while the fortification revealed no significant effect on ascorbic acid content and colour intensity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Modified Silicone-Rubber Tooling For Molding Composite Parts

NASA Technical Reports Server (NTRS)

Baucom, Robert M.; Snoha, John J.; Weiser, Erik S.

1995-01-01

Reduced-thermal-expansion, reduced-bulk-modulus silicone rubber for use in mold tooling made by incorporating silica powder into silicone rubber. Pressure exerted by thermal expansion reduced even further by allowing air bubbles to remain in silicone rubber instead of deaerating it. Bubbles reduce bulk modulus of material.

Interaction of Black Phosphorus with Oxygen and Water

DOE PAGES

Huang, Yuan; Qiao, Jingsi; He, Kai; ...

2016-10-24

Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. Chemical reactions with different ambient species, notably oxygen and water, are important as they govern key properties such as stability in air, electronic structure and charge transport, wetting by aqueous solutions, etc. Here, we report experiments combined with ab-initio calculations that address the effects of oxygen and water in contact with BP. Our results show that the reaction with oxygen is primarily responsible for changing properties of BP. Oxidation involving the dissociative chemisorption of O 2 causes the decomposition of BPmore » and continuously lowers the conductance of BP field-effect transistors (FETs). In contrast, BP is stable in contact with deaerated (i.e., O 2 depleted) water and the carrier mobility in BP FETs gated by H 2O increases significantly due to efficient dielectric screening of scattering centers by the high-k dielectric. Isotope labeling experiments, contact angle measurements and calculations show that the pristine BP surface is hydrophobic, but is turned progressively hydrophilic by oxidation. Lastly, our results open new avenues for exploring applications that require contact of BP with aqueous solutions including solution gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP.« less

Antioxidant activities of nano-bubble hydrogen-dissolved water assessed by ESR and 2,2'-bipyridyl methods.

PubMed

Kato, Shinya; Matsuoka, Daigo; Miwa, Nobuhiko

2015-08-01

We prepared nano-bubble hydrogen-dissolved water (nano-H water) which contained hydrogen nano-bubbles of <717-nm diameter for 54% of total bubbles. In the DMPO-spin trap electron spin resonance (ESR) method, the DMPO-OH:MnO ratio, being attributed to amounts of hydroxyl radicals (OH), was 2.78 for pure water (dissolved hydrogen [DH]≤0.01 ppm, oxidation-reduction potential [ORP]=+324 mV), 2.73 for tap water (0.01 ppm, +286 mV), 2.93 for commercially available hydrogen water (0.075 ppm, +49 mV), and 2.66 for manufactured hydrogen water (0.788 ppm, -614 mV), whereas the nano-H water (0.678 ppm, -644 mV) exhibited 2.05, showing the superiority of nano-H water to other types of hydrogen water in terms of OH-scavenging activity. Then, the reduction activity of nano-H water was assessed spectrophotometrically by the 2,2'-bipyridyl method. Differential absorbance at 530 nm was in the order: 0.018 for pure water, 0.055 for tap water, 0.079 for nano-H water, 0.085 for commercially available hydrogen water, and 0.090 for manufactured hydrogen water, indicating a prominent reduction activity of hydrogen water and nano-H water against oxidation in ascorbate-coupled ferric ion-bipyridyl reaction. Thus, nano-H water has an improved antioxidant activity as compared to hydrogen water of similar DH-level, indicating the more marked importance of nano-bubbles rather than the concentration of hydrogen in terms of OH-scavenging. Copyright © 2015 Elsevier B.V. All rights reserved.

Open-cycle OTEC system performance analysis. [Claude cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewandowski, A.A.; Olson, D.A.; Johnson, D.H.

1980-10-01

An algorithm developed to calculate the performance of Claude-Cycle ocean thermal energy conversion (OTEC) systems is described. The algorithm treats each component of the system separately and then interfaces them to form a complete system, allowing a component to be changed without changing the rest of the algorithm. Two components that are subject to change are the evaporator and condenser. For this study we developed mathematical models of a channel-flow evaporator and both a horizontal jet and spray director contact condenser. The algorithm was then programmed to run on SERI's CDC 7600 computer and used to calculate the effect onmore » performance of deaerating the warm and cold water streams before entering the evaporator and condenser, respectively. This study indicates that there is no advantage to removing air from these streams compared with removing the air from the condenser.« less

A new trinuclear complex of platinum and iron efficiently promotes cleavage of plasmid DNA.

PubMed Central

Lempers, E L; Bashkin, J S; Kostić, N M

1993-01-01

The compound [[Pt(trpy)]2Arg-EDTA]+ is synthesized in five steps, purified, and characterized by 1H, 13C, and 195Pt NMR spectroscopy, mass spectrometry, UV-vis spectrophotometry, and elemental analysis. The binuclear [[(Pt(trpy)]2Arg]3+ moiety binds to double-stranded DNA, and the chelating EDTA moiety holds metal cations. In the presence of ferrous ions and the reductant dithiothreitol, the new compound cleaves DNA. It cleaves a single strand in the pBR322 plasmid nearly as efficiently as methidiumrpropyl-EDTA (MPE), and it cleaves a restriction fragment of the XP10 plasmid nonselectively and more efficiently than [Fe(EDTA)]2-. The mechanism of cleavage was studied in control experiments involving different transition-metal ions, superoxide dismutase, catalase, glucose oxidase with glucose, metal-sequestering agents, and deaeration. These experiments indicate that adventitious iron and copper ions, superoxide anion, and hydrogen peroxide are not involved and that dioxygen is required. The cleavage apparently is done by hydroxyl radicals generated in the vicinity of the DNA molecule. The reagent [[Pt(trypy)]2Arg-EDTA]+ differs from methidiumpropyl-EDTA in not containing an intercalator. This difference in binding modes between the binuclear platinum(II) complex and the planar heterocycle may cause useful differences between the two reagents in cleavage of nucleic acids. Images PMID:8493109

Water reactive hydrogen fuel cell power system

DOEpatents

Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

2014-01-21

A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into a fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

Water reactive hydrogen fuel cell power system

DOEpatents

Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

2014-11-25

A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into the fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

Hydrogen Treatment Protects against Cell Death and Senescence Induced by Oxidative Damage.

PubMed

Han, A Lum; Park, Seong-Hoon; Park, Mi Sung

2017-02-28

Hydrogen has potential for preventive and therapeutic applications as an antioxidant. However, micro- and macroparticles of hydrogen in water disappear easily over time. In order to eliminate reactive oxygen species (ROS) related with the aging process, we used functional water containing nanoparticle hydrogen. Nanoparticle hydrogen does not disappear easily and collapse under water after long periods of time. We used murine embryonic fibroblasts that were isolated from 12.5-day embryos of C57BL/6 mice. We investigated the ability of nanoparticle hydrogen in water to suppress hydroxyurea-induced ROS production, cytotoxicity, and the accumulation of β-galactosidase (an indicator of aging), and promote cell proliferation. The accumulation of β-galactosidase in the cytoplasm and the appearance of abnormal nuclei were inhibited by daily treatment of cells with hydrogen water. When the aging process was accelerated by hydroxyurea-induced oxidative stress, the effect of hydrogen water was even more remarkable. Thus, this study showed the antioxidant and anti-senescence effects of hydrogen water. Nanoparticle hydrogen water is potentially a potent anti-aging agent.

The influence of the Tbeta level upon fluorescence and laser properties of aromatic compounds.

PubMed

Nijegorodov, N; Winkoun, D P; Nkoma, J S

2004-07-01

The fluorescence and laser properties of seven specially chosen aromatic compounds are studied at 293 degrees C. The quantum yield of fluorescence, gamma, decay times, tauf, of the deaerated and non-deaerated solutions are measured. The oscillator strength, fe, fluorescence rate constants, kf, natural lifetimes, tauT0, and intersystem crossing rate constants, kST, are calculated. Some laser parameters are calculated or measured experimentally. It is found that the position of the Tbeta level plays an important role in the fluorescence and laser properties of aromatic compounds. If the Tbeta level is situated below the Sp level, it decreases the quantum yield of fluorescence and the decay time and increases the threshold of laser action. If, due to some structural changes of a molecule, the Tbeta level is situated higher than the Sp level, then the quantum yield of fluorescence and the decay times are increasing and the threshold of laser action is decreasing. Such influence of the position of the Tbeta level upon fluorescence and laser properties of aromatic compound is explained by the fact that the Sp level mixes with the Tbeta level more readily than with other taupipi* levels.

Process for exchanging hydrogen isotopes between gaseous hydrogen and water

DOEpatents

Hindin, Saul G.; Roberts, George W.

1980-08-12

A process for exchanging isotopes of hydrogen, particularly tritium, between gaseous hydrogen and water is provided whereby gaseous hydrogen depeleted in tritium and liquid or gaseous water containing tritium are reacted in the presence of a metallic catalyst.

Corrosion evaluation of heat recovery steam generator superheater tube in two methods of testing: Tafel polarization and electrochemical impedance spectroscopy (EIS)

NASA Astrophysics Data System (ADS)

Santoso, Rio Pudjidarma; Riastuti, Rini

2018-05-01

The purpose of this research is to evaluate the corrosion process which occurs on the water side of Heat Recovery Steam Generator (HRSG) superheater tube. The tube was 13CrMo44 and divided into 3 types of specimen: new tube, used tube (with oxide layer on surface), cleaned-used tube (without oxide layer on surface). The evaluation of corrosion parameters wasperformed using deaerated ultra-high purity water (boiler feed water) in two methods of testing: Tafel polarization and Electrochemical Impedance Spectroscopy (EIS). Tafel polarization was excellent as its capability to show the value of corrosion current and the corrosion rate explicitly, on the other hand, EIS was excellent as its capability to explain for corrosion mechanism on metal interface in detail. Both methods showed that the increase of electrolyte temperature from 25°C to 55°C would increase the corrosion rate with the mechanism of decreasing polarization resistance due to thinning out the passive film thickness and enlarge the area of reduction reaction of cathode. Magnetite oxide scale which is laid on the surface of used tube specimen shows protective nature to reduce the corrosion rate, and clear up this oxide would increase the corrosion rate back as new tube.

Molecular dynamics simulation study of hydrogen bonding in aqueous poly(ethylene oxide) solutions.

PubMed

Smith, G D; Bedrov, D; Borodin, O

2000-12-25

A molecular dynamics simulation study of hydrogen bonding in poly(ethylene oxide) (PEO)/water solutions was performed. PEO-water and water-water hydrogen bonding manifested complex dependence on both composition and temperature. Strong water clustering in concentrated solutions was seen. Saturation of hydrogen bonding at w(p) approximately equal to 0.5 and a dramatic decrease in PEO-water hydrogen bonding with increasing temperature, consistent with experimentally observed closed-loop phase behavior, were observed. Little tendency toward intermolecular bridging of PEO chains by water molecules was seen.

D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

USGS Publications Warehouse

Schimmelmann, A.; Lewan, M.D.; Wintsch, R.P.

1999-01-01

Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310-381??C), time (12-144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil-hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330??C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ~ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381 ??C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350??C for 72 h, or 330??C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115??C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected by exchange with water hydrogen at typical reservoir conditions over geologic time. It will be difficult to utilize D/H ratios of thermally mature bulk or fractions of organic matter to quantitatively reconstruct isotopic aspects of paleoclimate and paleoenvironment. Hope resides in compound-specific D/H ratios of thermally stable, extractable biomarkers ('molecular fossils') that are less susceptible to hydrogen exchange with water-derived hydrogen.

Production of hydrogen, liquid fuels, and chemicals from catalytic processing of bio-oils

DOEpatents

Huber, George W; Vispute, Tushar P; Routray, Kamalakanta

2014-06-03

Disclosed herein is a method of generating hydrogen from a bio-oil, comprising hydrogenating a water-soluble fraction of the bio-oil with hydrogen in the presence of a hydrogenation catalyst, and reforming the water-soluble fraction by aqueous-phase reforming in the presence of a reforming catalyst, wherein hydrogen is generated by the reforming, and the amount of hydrogen generated is greater than that consumed by the hydrogenating. The method can further comprise hydrocracking or hydrotreating a lignin fraction of the bio-oil with hydrogen in the presence of a hydrocracking catalyst wherein the lignin fraction of bio-oil is obtained as a water-insoluble fraction from aqueous extraction of bio-oil. The hydrogen used in the hydrogenating and in the hydrocracking or hydrotreating can be generated by reforming the water-soluble fraction of bio-oil.

Environmentally induced crack propagation in Inconel alloys 600 and 690 under hydrogen supersaturated steam

NASA Astrophysics Data System (ADS)

Ali, Mehboob Muzzammil

Intergranular stress corrosion cracking (IGSCC) of Inconel alloys 600 and 690 was investigated by exposing them to 300--400°C in deaerated hydrogen supersaturated steam. Crack growth rates were measured in-situ for the above alloys using modified wedge-opening-loaded (M-WOL) linear elastic fracture specimens under constant displacement conditions. The applied stress intensity factors (K) used varied from 29--90 MPam1/2. An activation energy of 120 kJ/mol was found for crack growth rates as a function of temperature. This activation energy is close to the one corresponding to grain boundary self diffusion of nickel. In addition, it was found that the apparent crack growth rates (da/dt) exhibited a linear dependence with KI, given by (da/dt) = A.KIn, where n = 1 in our case. Microstructurally, crack propagation in both the alloys was predominantly along the grain boundaries. It is suggested that high fugacity hydrogen was generated at the tip of the crack, as a result of the reaction of H2O with Cr2O3 on the fracture surface leading to IGSCC. It was found that the rates of crack propagation in both alloys 600 and 690 are very similar. Moreover, under the applied KIs, both alloys 600 and 690 show a similar tendency to crack intergranularly in a direction perpendicular to the applied stress. Crack branching was also exhibited by both the alloys 600 as well as 690. The difference in the crack growth rates of alloys 600 and 690 was found to be only about 2%, which indicates that the crack growth rates in these alloys is independent of the alloy chromium content and that, possibly very similar crack growth mechanisms are active in both the alloys 600 and 690 under similar conditions of KI and temperature. HREM images at the crack tip of alloy 690 exhibit two distinct regions---a crystalline region, and an adjacent amorphous region, which is likely to be either a hydroxide or an amorphous oxide layer. This layer is expected to result from passivation reactions as the crack surface is exposed to the corrosive environment.

Separation of gaseous hydrogen from a water-hydrogen mixture in a fuel cell power system operating in a weightless environment

NASA Technical Reports Server (NTRS)

Romanowski, William E. (Inventor); Suljak, George T. (Inventor)

1989-01-01

A fuel cell power system for use in a weightless environment, such as in space, includes a device for removing water from a water-hydrogen mixture condensed from the exhaust from the fuel cell power section of the system. Water is removed from the mixture in a centrifugal separator, and is fed into a holding, pressure operated water discharge valve via a Pitot tube. Entrained nondissolved hydrogen is removed from the Pitot tube by a bleed orifice in the Pitot tube before the water reaches the water discharge valve. Water discharged from the valve thus has a substantially reduced hydrogen content.

Water and hydrogen are immiscible in Earth's mantle.

PubMed

Bali, Enikő; Audétat, Andreas; Keppler, Hans

2013-03-14

In the deep, chemically reducing parts of Earth's mantle, hydrous fluids contain significant amounts of molecular hydrogen (H2). Thermodynamic models of fluids in Earth's mantle so far have always assumed that molecular hydrogen and water are completely miscible. Here we show experimental evidence that water and hydrogen can coexist as two separate, immiscible phases. Immiscibility between water and hydrogen may be the cause of the formation of enigmatic, ultra-reducing domains in the mantle that contain moissanite (SiC) and other phases indicative of extremely reducing conditions. Moreover, the immiscibility between water and hydrogen may provide a mechanism for the rapid oxidation of Earth's upper mantle immediately following core formation.

Inhalation of water electrolysis-derived hydrogen ameliorates cerebral ischemia-reperfusion injury in rats - A possible new hydrogen resource for clinical use.

PubMed

Cui, Jin; Chen, Xiao; Zhai, Xiao; Shi, Dongchen; Zhang, Rongjia; Zhi, Xin; Li, Xiaoqun; Gu, Zhengrong; Cao, Liehu; Weng, Weizong; Zhang, Jun; Wang, Liping; Sun, Xuejun; Ji, Fang; Hou, Jiong; Su, Jiacan

2016-10-29

Hydrogen is a kind of noble gas with the character to selectively neutralize reactive oxygen species. Former researches proved that low-concentration of hydrogen can be used to ameliorating cerebral ischemia/reperfusion injury. Hydrogen electrolyzed from water has a hydrogen concentration of 66.7%, which is much higher than that used in previous studies. And water electrolysis is a potential new hydrogen resource for regular clinical use. This study was designed and carried out for the determination of safety and neuroprotective effects of water electrolysis-derived hydrogen. Sprague-Dawley rats were used as experimental animals, and middle cerebral artery occlusion was used to make cerebral ischemia/reperfusion model. Pathologically, tissues from rats in hydrogen inhalation group showed no significant difference compared with the control group in HE staining pictures. The blood biochemical findings matched the HE staining result. TTC, Nissl, and TUNEL staining showed the significant improvement of infarction volume, neuron morphology, and neuron apoptosis in rat with hydrogen treatment. Biochemically, hydrogen inhalation decreased brain caspase-3, 3-nitrotyrosine and 8-hydroxy-2-deoxyguanosine-positive cells and inflammation factors concentration. Water electrolysis-derived hydrogen inhalation had neuroprotective effects on cerebral ischemia/reperfusion injury in rats with the effect of suppressing oxidative stress and inflammation, and it is a possible new hydrogen resource to electrolyze water at the bedside clinically. Copyright © 2016. Published by Elsevier Ltd.

Selective electrochemical generation of hydrogen peroxide from water oxidation

DOE PAGES

Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

2015-10-08

Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H 2O 2 and the 4e– oxidation to O 2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO 2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H 2O 2 evolution selectively.« less

Dose-dependent inhibition of gastric injury by hydrogen in alkaline electrolyzed drinking water

PubMed Central

2014-01-01

Background Hydrogen has been reported to relieve damage in many disease models, and is a potential additive in drinking water to provide protective effects for patients as several clinical studies revealed. However, the absence of a dose–response relationship in the application of hydrogen is puzzling. We attempted to identify the dose–response relationship of hydrogen in alkaline electrolyzed drinking water through the aspirin induced gastric injury model. Methods In this study, hydrogen-rich alkaline water was obtained by adding H2 to electrolyzed water at one atmosphere pressure. After 2 weeks of drinking, we detected the gastric mucosal damage together with MPO, MDA and 8-OHdG in rat aspirin induced gastric injury model. Results Hydrogen-dose dependent inhibition was observed in stomach mucosal. Under pH 8.5, 0.07, 0.22 and 0.84 ppm hydrogen exhibited a high correlation with inhibitory effects showed by erosion area, MPO activity and MDA content in the stomach. Gastric histology also demonstrated the inhibition of damage by hydrogen-rich alkaline water. However, 8-OHdG level in serum did not have significant hydrogen-dose dependent effect. pH 9.5 showed higher but not significant inhibitory response compared with pH 8.5. Conclusions Hydrogen is effective in relieving the gastric injury induced by aspirin-HCl, and the inhibitory effect is dose-dependent. The reason behind this may be that hydrogen-rich water directly interacted with the target tissue, while the hydrogen concentration in blood was buffered by liver glycogen, evoking a suppressed dose–response effect. Drinking hydrogen-rich water may protect healthy individuals from gastric damage caused by oxidative stress. PMID:24589018

Dose-dependent inhibition of gastric injury by hydrogen in alkaline electrolyzed drinking water.

PubMed

Xue, Jinling; Shang, Guodong; Tanaka, Yoshinori; Saihara, Yasuhiro; Hou, Lingyan; Velasquez, Natalia; Liu, Wenjun; Lu, Yun

2014-03-03

Hydrogen has been reported to relieve damage in many disease models, and is a potential additive in drinking water to provide protective effects for patients as several clinical studies revealed. However, the absence of a dose-response relationship in the application of hydrogen is puzzling. We attempted to identify the dose-response relationship of hydrogen in alkaline electrolyzed drinking water through the aspirin induced gastric injury model. In this study, hydrogen-rich alkaline water was obtained by adding H2 to electrolyzed water at one atmosphere pressure. After 2 weeks of drinking, we detected the gastric mucosal damage together with MPO, MDA and 8-OHdG in rat aspirin induced gastric injury model. Hydrogen-dose dependent inhibition was observed in stomach mucosal. Under pH 8.5, 0.07, 0.22 and 0.84 ppm hydrogen exhibited a high correlation with inhibitory effects showed by erosion area, MPO activity and MDA content in the stomach. Gastric histology also demonstrated the inhibition of damage by hydrogen-rich alkaline water. However, 8-OHdG level in serum did not have significant hydrogen-dose dependent effect. pH 9.5 showed higher but not significant inhibitory response compared with pH 8.5. Hydrogen is effective in relieving the gastric injury induced by aspirin-HCl, and the inhibitory effect is dose-dependent. The reason behind this may be that hydrogen-rich water directly interacted with the target tissue, while the hydrogen concentration in blood was buffered by liver glycogen, evoking a suppressed dose-response effect. Drinking hydrogen-rich water may protect healthy individuals from gastric damage caused by oxidative stress.

Electrochemically reduced water exerts superior reactive oxygen species scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water

PubMed Central

Hamasaki, Takeki; Harada, Gakuro; Nakamichi, Noboru; Kabayama, Shigeru; Teruya, Kiichiro; Fugetsu, Bunshi; Gong, Wei; Sakata, Ichiro; Shirahata, Sanetaka

2017-01-01

Electrochemically reduced water (ERW) is produced near a cathode during electrolysis and exhibits an alkaline pH, contains richly dissolved hydrogen, and contains a small amount of platinum nanoparticles. ERW has reactive oxygen species (ROS)-scavenging activity and recent studies demonstrated that hydrogen-dissolved water exhibits ROS-scavenging activity. Thus, the antioxidative capacity of ERW is postulated to be dependent on the presence of hydrogen levels; however, there is no report verifying the role of dissolved hydrogen in ERW. In this report, we clarify whether the responsive factor for antioxidative activity in ERW is dissolved hydrogen. The intracellular ROS scavenging activity of ERW and hydrogen-dissolved water was tested by both fluorescent stain method and immuno spin trapping assay. We confirm that ERW possessed electrolysis intensity-dependent intracellular ROS-scavenging activity, and ERW exerts significantly superior ROS-scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water. ERW retained its ROS-scavenging activity after removal of dissolved hydrogen, but lost its activity when autoclaved. An oxygen radical absorbance capacity assay, the 2,2-diphenyl-1-picrylhydrazyl assay and chemiluminescence assay could not detect radical-scavenging activity in both ERW and hydrogen-dissolved water. These results indicate that ERW contains electrolysis-dependent hydrogen and an additional antioxidative factor predicted to be platinum nanoparticles. PMID:28182635

Electrochemically reduced water exerts superior reactive oxygen species scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water.

PubMed

Hamasaki, Takeki; Harada, Gakuro; Nakamichi, Noboru; Kabayama, Shigeru; Teruya, Kiichiro; Fugetsu, Bunshi; Gong, Wei; Sakata, Ichiro; Shirahata, Sanetaka

2017-01-01

Electrochemically reduced water (ERW) is produced near a cathode during electrolysis and exhibits an alkaline pH, contains richly dissolved hydrogen, and contains a small amount of platinum nanoparticles. ERW has reactive oxygen species (ROS)-scavenging activity and recent studies demonstrated that hydrogen-dissolved water exhibits ROS-scavenging activity. Thus, the antioxidative capacity of ERW is postulated to be dependent on the presence of hydrogen levels; however, there is no report verifying the role of dissolved hydrogen in ERW. In this report, we clarify whether the responsive factor for antioxidative activity in ERW is dissolved hydrogen. The intracellular ROS scavenging activity of ERW and hydrogen-dissolved water was tested by both fluorescent stain method and immuno spin trapping assay. We confirm that ERW possessed electrolysis intensity-dependent intracellular ROS-scavenging activity, and ERW exerts significantly superior ROS-scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water. ERW retained its ROS-scavenging activity after removal of dissolved hydrogen, but lost its activity when autoclaved. An oxygen radical absorbance capacity assay, the 2,2-diphenyl-1-picrylhydrazyl assay and chemiluminescence assay could not detect radical-scavenging activity in both ERW and hydrogen-dissolved water. These results indicate that ERW contains electrolysis-dependent hydrogen and an additional antioxidative factor predicted to be platinum nanoparticles.

Photodegradation of naproxen and its photoproducts in aqueous solution at 254 nm: a kinetic investigation.

PubMed

Marotta, Raffaele; Spasiano, Danilo; Di Somma, Ilaria; Andreozzi, Roberto

2013-01-01

The kinetics of photodegradation of the non steroidal anti-inflammatory drug naproxen (+)-S-2-(6-methoxynaphthalen-2-yl)propanoic acid, an emerging organic pollutant, was studied in aqueous solutions under deaerated and aerated conditions. The photolysis experiments were carried out under monochromatic irradiation (λ = 254 nm) at pH = 7.0 and T = 25 °C. Simplified reaction schemes of photodegradation of naproxen are proposed in absence and in presence of oxygen respectively. The schemes take into account the photolysis of naproxen and its photoproducts and the reactions of the measured species with oxygen dissolved in the liquid bulk. According to these schemes, two kinetic models were developed which correlate the experimental data, for runs performed in absence and in presence of oxygen, with a fair accuracy and allowed to estimate the best values for the unknown kinetic parameters. The calculated quantum yield of direct photolysis of naproxen under deaerated media is in good agreement with the one previously reported. Under aerated conditions, the generation of singlet oxygen has also been taken into account. The obtained results, under the adopted conditions, indicated a marked influence of dissolved oxygen on the photodegradation rates of naproxen and the relative distribution of the major reaction intermediates. Copyright © 2012 Elsevier Ltd. All rights reserved.

Use of Electrochemical Noise (EN) Technique to Study the Effect of sulfate and Chloride Ions on Passivation and Pitting Corrosion Behavior of 316 Stainless Steel

NASA Astrophysics Data System (ADS)

Pujar, M. G.; Anita, T.; Shaikh, H.; Dayal, R. K.; Khatak, H. S.

2007-08-01

In the present paper, studies were conducted on AISI Type 316 stainless steel (SS) in deaerated solutions of sodium sulfate as well as sodium chloride to establish the effect of sulfate and chloride ions on the electrochemical corrosion behavior of the material. The experiments were conducted in deaerated solutions of 0.5 M sodium sulfate as well as 0.5 M sodium chloride using electrochemical noise (EN) technique at open circuit potential (OCP) to collect the correlated current and potential signals. Visual records of the current and potential, analysis of data to arrive at the statistical parameters, spectral density estimation using the maximum entropy method (MEM) showed that sulfate ions were incorporated in the passive film to strengthen the same. However, the adsorption of chloride ions resulted in pitting corrosion thereby adversely affecting noise resistance ( R N). Distinct current and potential signals were observed for metastable pitting, stable pitting and passive film build-up. Distinct changes in the values of the statistical parameters like R N and the spectral noise resistance at zero frequency ( R°SN) revealed adsorption and incorporation of sulfate and chloride ions on the passive film/solution interface.

Photoelectrochemical water splitting in separate oxygen and hydrogen cells

NASA Astrophysics Data System (ADS)

Landman, Avigail; Dotan, Hen; Shter, Gennady E.; Wullenkord, Michael; Houaijia, Anis; Maljusch, Artjom; Grader, Gideon S.; Rothschild, Avner

2017-06-01

Solar water splitting provides a promising path for sustainable hydrogen production and solar energy storage. One of the greatest challenges towards large-scale utilization of this technology is reducing the hydrogen production cost. The conventional electrolyser architecture, where hydrogen and oxygen are co-produced in the same cell, gives rise to critical challenges in photoelectrochemical water splitting cells that directly convert solar energy and water to hydrogen. Here we overcome these challenges by separating the hydrogen and oxygen cells. The ion exchange in our cells is mediated by auxiliary electrodes, and the cells are connected to each other only by metal wires, enabling centralized hydrogen production. We demonstrate hydrogen generation in separate cells with solar-to-hydrogen conversion efficiency of 7.5%, which can readily surpass 10% using standard commercial components. A basic cost comparison shows that our approach is competitive with conventional photoelectrochemical systems, enabling safe and potentially affordable solar hydrogen production.

Drinking hydrogen water ameliorated cognitive impairment in senescence-accelerated mice.

PubMed

Gu, Yeunhwa; Huang, Chien-Sheng; Inoue, Tota; Yamashita, Takenori; Ishida, Torao; Kang, Ki-Mun; Nakao, Atsunori

2010-05-01

Hydrogen has been reported to have neuron protective effects due to its antioxidant properties, but the effects of hydrogen on cognitive impairment due to senescence-related brain alterations and the underlying mechanisms have not been characterized. In this study, we investigated the efficacies of drinking hydrogen water for prevention of spatial memory decline and age-related brain alterations using senescence-accelerated prone mouse 8 (SAMP8), which exhibits early aging syndromes including declining learning ability and memory. However, treatment with hydrogen water for 30 days prevented age-related declines in cognitive ability seen in SAMP8 as assessed by a water maze test and was associated with increased brain serotonin levels and elevated serum antioxidant activity. In addition, drinking hydrogen water for 18 weeks inhibited neurodegeneration in hippocampus, while marked loss of neurons was noted in control, aged brains of mice receiving regular water. On the basis of our results, hydrogen water merits further investigation for possible therapeutic/preventative use for age-related cognitive disorders.

Hydrogen-rich water attenuates experimental periodontitis in a rat model.

PubMed

Kasuyama, Kenta; Tomofuji, Takaaki; Ekuni, Daisuke; Tamaki, Naofumi; Azuma, Tetsuji; Irie, Koichiro; Endo, Yasumasa; Morita, Manabu

2011-12-01

Reactive oxygen species (ROS) contribute to the development of periodontitis. As molecular hydrogen can act as a scavenger of ROS, we examined the effects of treatment with hydrogen-rich water on a rat model of periodontitis. A ligature was placed around the maxillary molars for 4 weeks to induce periodontitis, and the animals were given drinking water with or without hydrogen-rich water. The rats with periodontitis which were treated with pure water showed a time-dependent increase in serum ROS level. Compared with the rats without periodontitis, the periodontitis-induced rats which were given pure water also showed polymorphonuclear leucocyte infiltration and alveolar bone loss at 4 weeks. Hydrogen-rich water intake inhibited an increase in serum ROS level and lowered expression of 8-hydroxydeoxyguanosine and nitrotyrosine in the periodontal tissue at 4 weeks. Such conditions prevented polymorphonuclear leucocyte infiltration and osteoclast differentiation following periodontitis progression. Furthermore, inflammatory signalling pathways, such as mitogen-activated protein kinases, were less activated in periodontal lesions from hydrogen-rich water-treated rats as compared with pure water-treated rats. Consuming hydrogen-rich water might be beneficial in suppressing periodontitis progression by decreasing gingival oxidative stress. © 2011 John Wiley & Sons A/S.

Antitumor effects of nano-bubble hydrogen-dissolved water are enhanced by coexistent platinum colloid and the combined hyperthermia with apoptosis-like cell death.

PubMed

Asada, Ryoko; Kageyama, Katsuhiro; Tanaka, Hiroshi; Matsui, Hisakazu; Kimura, Masatsugu; Saitoh, Yasukazu; Miwa, Nobuhiko

2010-12-01

In order to erase reactive oxygen species (ROS) related with the proliferation of tumor cells by reducing activity of hydrogen, we developed functional water containing nano-bubbles (diameters: <900 nm for 71%/population) hydrogen of 1.1-1.5 ppm (the theoretical maximum: 1.6 ppm) with a reducing ability (an oxidation-reduction potential -650 mV, normal water: +100-200 mV) using a microporous-filter hydrogen-jetting device. We showed that hydrogen water erased ROS indispensable for tumor cell growth by ESR/spin trap, the redox indicator CDCFH-DA assay, and was cytotoxic to Ehrlich ascites tumor cells as assessed by WST-8 assay, crystal violet dye stain and scanning electron microscopy, after 24-h or 48-h incubation sequent to warming at 37°C or 42°C. Hydrogen water supplemented with platinum colloid (0.3 ppm Pt in 4% polyvinylpyrrolidone) had more antitumor activity than hydrogen water alone, mineral water alone (15.6%), hydrogen water plus mineral water, or platinum colloid alone as observed by decreased cell numbers, cell shrinkage and pycnosis (nuclear condensation)/karyorrhexis (nuclear fragmentation) indicative of apoptosis, together with cell deformation and disappearance of microvilli on the membrane surface. These antitumor effects were promoted by combination with hyperthermia at 42°C. Thus, the nano-bubble hydrogen water with platinum colloid is potent as an anti-tumor agent.

Polymer formulation for removing hydrogen and liquid water from an enclosed space

DOEpatents

Shepodd, Timothy J [Livermore, CA

2006-02-21

This invention describes a solution to the particular problem of liquid water formation in hydrogen getters exposed to quantities of oxygen. Water formation is usually desired because the recombination reaction removes hydrogen without affecting gettering capacity and the oxygen removal reduces the chances for a hydrogen explosion once free oxygen is essentially removed. The present invention describes a getter incorporating a polyacrylate compound that can absorb up to 500% of its own weight in liquid water without significantly affecting its hydrogen gettering/recombination properties, but that also is insensitive to water vapor.

Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

NASA Technical Reports Server (NTRS)

Ota, K.; Conger, W. L.

1977-01-01

The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

Spectroscopic and thermodynamic properties of molecular hydrogen dissolved in water at pressures up to 200 MPa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borysow, Jacek, E-mail: jborysow@mtu.edu; Rosso, Leonardo del; Celli, Milva

2014-04-28

We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines weremore » narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.« less

Spectroscopic and thermodynamic properties of molecular hydrogen dissolved in water at pressures up to 200 MPa.

PubMed

Borysow, Jacek; del Rosso, Leonardo; Celli, Milva; Moraldi, Massimo; Ulivi, Lorenzo

2014-04-28

We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines were narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.

Spectroscopic and thermodynamic properties of molecular hydrogen dissolved in water at pressures up to 200 MPa

NASA Astrophysics Data System (ADS)

Borysow, Jacek; del Rosso, Leonardo; Celli, Milva; Moraldi, Massimo; Ulivi, Lorenzo

2014-04-01

We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines were narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.

Enhanced Inactivation of Escherichia coli and MS2 Coliphage by Cupric Ion in the Presence of Hydroxylamine: Dual Microbicidal Effects.

PubMed

Kim, Hyung-Eun; Nguyen, Thuy T M; Lee, Hongshin; Lee, Changha

2015-12-15

The inactivation of Escherichia coli and MS2 coliphage by Cu(II) is found to be significantly enhanced in the presence of hydroxylamine (HA). The addition of a small amount of HA (i.e., 5-20 μM) increased the inactivation efficacies of E. coli and MS2 coliphage by 5- to 100-fold, depending on the conditions. Dual effects were anticipated to enhance the biocidal activity of Cu(II) by the addition of HA, viz. (i) the accelerated reduction of Cu(II) into Cu(I) (a stronger biocide) and (ii) the production of reactive oxidants from the reaction of Cu(I) with dissolved oxygen (evidenced by the oxidative transformation of methanol into formaldehyde). Deaeration enhanced the inactivation of E. coli but slightly decreased the inactivation efficacy of MS2 coliphage. The addition of 10 μM hydrogen peroxide (H2O2) greatly enhanced the MS2 inactivation, whereas the same concentration of H2O2 did not significantly affect the inactivation efficacy of E. coli Observations collectively indicate that different biocidal actions lead to the inactivation of E. coli and MS2 coliphage. The toxicity of Cu(I) is dominantly responsible for the E. coli inactivation. However, for the MS2 coliphage inactivation, the oxidative damage induced by reactive oxidants is as important as the effect of Cu(I).

Process for hydrogen isotope concentration between liquid water and hydrogen gas

DOEpatents

Stevens, William H.

1976-09-21

A process for hydrogen isotope exchange and concentration between liquid water and hydrogen gas, wherein liquid water and hydrogen gas are contacted, in an exchange section, with one another and with at least one catalyst body comprising at least one metal selected from Group VIII of the Periodic Table and preferably a support therefor, the catalyst body has a liquid-water-repellent, gas permeable polymer or organic resin coating, preferably a fluorinated olefin polymer or silicone coating, so that the isotope concentration takes place by two simultaneously occurring steps, namely, ##EQU1## WHILE THE HYDROGEN GAS FED TO THE EXCHANGE SECTION IS DERIVED IN A REACTOR VESSEL FROM LIQUID WATER THAT HAS PASSED THROUGH THE EXCHANGE SECTION.

Photoelectrochemical hydrogen production from biomass derivatives and water.

PubMed

Lu, Xihong; Xie, Shilei; Yang, Hao; Tong, Yexiang; Ji, Hongbing

2014-11-21

Hydrogen, a clean energy carrier with high energy capacity, is a very promising candidate as a primary energy source for the future. Photoelectrochemical (PEC) hydrogen production from renewable biomass derivatives and water is one of the most promising approaches to producing green chemical fuel. Compared to water splitting, hydrogen production from renewable biomass derivatives and water through a PEC process is more efficient from the viewpoint of thermodynamics. Additionally, the carbon dioxide formed can be re-transformed into carbohydrates via photosynthesis in plants. In this review, we focus on the development of photoanodes and systems for PEC hydrogen production from water and renewable biomass derivatives, such as methanol, ethanol, glycerol and sugars. We also discuss the future challenges and opportunities for the design of the state-of-the-art photoanodes and PEC systems for hydrogen production from biomass derivatives and water.

Solar hydrogen generator

NASA Technical Reports Server (NTRS)

Sebacher, D. I.; Sabol, A. P. (Inventor)

1977-01-01

An apparatus, using solar energy to manufacture hydrogen by dissociating water molecules into hydrogen and oxygen molecules is described. Solar energy is concentrated on a globe containing water thereby heating the water to its dissociation temperature. The globe is pervious to hydrogen molecules permitting them to pass through the globe while being essentially impervious to oxygen molecules. The hydrogen molecules are collected after passing through the globe and the oxygen molecules are removed from the globe.

Effect of water on hydrogen permeability

NASA Technical Reports Server (NTRS)

Hulligan, David; Tomazic, William A.

1987-01-01

Doping of hydrogen with CO and CO2 was developed to reduce hydrogen permeation in Stirling engines by forming a low permeability oxide coating on the inner surface of the heater head tubes. Although doping worked well, under certain circumstances the protective oxide could be chemically reduced by the hydrogen in the engine. Some oxygen is required in the hydrogen to prevent reduction. Eventually, all the oxygen in the hydrogen gas - whatever its source - shows up as water. This is the result of hydrogen reducing the CO, CO2, or the protective inner surface oxides. This water can condense in the engine system under the right conditions. If the concentration of water vapor is reduced to a low enough level, the hydrogen can chemically reduce the oxide coating, resulting in an increase in permeability. This work was done to define the minimum water content required to avoid this reduction in the oxide coating. The results of this testing show that a minimum of approximately 750 ppm water is required to prevent an increase in permeability of CG-27, a high temperature metal alloy selected for Stirling engine heater tubes.

Effects of hydrogen-rich water on aging periodontal tissues in rats

PubMed Central

Tomofuji, Takaaki; Kawabata, Yuya; Kasuyama, Kenta; Endo, Yasumasa; Yoneda, Toshiki; Yamane, Mayu; Azuma, Tetsuji; Ekuni, Daisuke; Morita, Manabu

2014-01-01

Oxidative damage is involved in age-related inflammatory reactions. The anti-oxidative effects of hydrogen-rich water suppress oxidative damage, which may aid in inhibiting age-related inflammatory reactions. We investigated the effects of drinking hydrogen-rich water on aging periodontal tissues in healthy rats. Four-month-old male Fischer 344 rats (n = 12) were divided into two groups: the experimental group (hydrogen-rich water treatment) and the control group (distilled water treatment). The rats consumed hydrogen-rich water or distilled water until 16 months of age. The experimental group exhibited lower periodontal oxidative damage at 16 months of age than the control group. Although protein expression of interleukin-1β did not differ, gene expression of Nod-like receptor protein 3 inflammasomes was activated in periodontal tissues from the experimental group as compared with the control group. Drinking hydrogen-rich water is proposed to have anti-aging effects on periodontal oxidative damage, but not on inflammatory reactions in healthy rats. PMID:24985521

Process for the production of hydrogen from water

DOEpatents

Miller, William E [Naperville, IL; Maroni, Victor A [Naperville, IL; Willit, James L [Batavia, IL

2010-05-25

A method and device for the production of hydrogen from water and electricity using an active metal alloy. The active metal alloy reacts with water producing hydrogen and a metal hydroxide. The metal hydroxide is consumed, restoring the active metal alloy, by applying a voltage between the active metal alloy and the metal hydroxide. As the process is sustainable, only water and electricity is required to sustain the reaction generating hydrogen.

Hydration dynamics of a lipid membrane: Hydrogen bond networks and lipid-lipid associations

NASA Astrophysics Data System (ADS)

Srivastava, Abhinav; Debnath, Ananya

2018-03-01

Dynamics of hydration layers of a dimyristoylphosphatidylcholine (DMPC) bilayer are investigated using an all atom molecular dynamics simulation. Based upon the geometric criteria, continuously residing interface water molecules which form hydrogen bonds solely among themselves and then concertedly hydrogen bonded to carbonyl, phosphate, and glycerol head groups of DMPC are identified. The interface water hydrogen bonded to lipids shows slower relaxation rates for translational and rotational dynamics compared to that of the bulk water and is found to follow sub-diffusive and non-diffusive behaviors, respectively. The mean square displacements and the reorientational auto-correlation functions are slowest for the interfacial waters hydrogen bonded to the carbonyl oxygen since these are buried deep in the hydrophobic core among all interfacial water studied. The intermittent hydrogen bond auto-correlation functions are calculated, which allows breaking and reformations of the hydrogen bonds. The auto-correlation functions for interfacial hydrogen bonded networks develop humps during a transition from cage-like motion to eventual power law behavior of t-3/2. The asymptotic t-3/2 behavior indicates translational diffusion dictated dynamics during hydrogen bond breaking and formation irrespective of the nature of the chemical confinement. Employing reactive flux correlation analysis, the forward rate constant of hydrogen bond breaking and formation is calculated which is used to obtain Gibbs energy of activation of the hydrogen bond breaking. The relaxation rates of the networks buried in the hydrophobic core are slower than the networks near the lipid-water interface which is again slower than bulk due to the higher Gibbs energy of activation. Since hydrogen bond breakage follows a translational diffusion dictated mechanism, chemically confined hydrogen bond networks need an activation energy to diffuse through water depleted hydrophobic environments. Our calculations reveal that the slow relaxation rates of interfacial waters in the vicinity of lipids are originated from the chemical confinement of concerted hydrogen bond networks. The analysis suggests that the networks in the hydration layer of membranes dynamically facilitate the water mediated lipid-lipid associations which can provide insights on the thermodynamic stability of soft interfaces relevant to biological systems in the future.

First-principles quantum mechanical investigations: Catalytic reactions of furfural on Pd(111) and at the water/Pd(111) interface

NASA Astrophysics Data System (ADS)

Xue, Wenhua

Bio-oils have drawn more and more attention from scientists as a promising new clean, cheap energy source. One of the most interesting relevant issues is the effect of catalysts on the catalytic reactions that are used for producing bio-oils. Furfural, as a very important intermediate during these reactions, has attracted significant studies. However, the effect of catalysts, including particularly the liquid/solid interface formed by a metal catalyst and liquid water, in the catalytic reactions involving furfural still remains elusive. In this research, we performed ab initio molecular dynamics simulations and first-principles density-functional theory calculations to investigate the atomic-scale mechanisms of catalytic hydrogenation of furfural on the palladium surface and at the liquid/state interface formed by the palladium surface and liquid water. We studied all the possible mechanisms that lead to formation of furfuryl alcohol (FOL), formation of tetrahydrofurfural (THFAL), and formation of tetrahydrofurfurfuryl alcohol (THFOL). We found that liquid water plays a significant role in the hydrogenation reactions. During the reaction in the presence of water and the palladium catalyst, in particular, water directly participates in the hydrogenation of the aldehyde group of furfural and facilitates the formation of FOL by reducing the activation energy. Our calculations show that water provides hydrogen for the hydrogenation of the aldehyde group, and at the same time, a pre-existing hydrogen atom, which is resulted from dissociation of molecular hydrogen (experimentally, molecular hydrogen is always supplied for hydrogenation) on the palladium surface, is bonded to water, making the water molecule intact in structure. In the absence of water, on the other hand, formation of FOL and THFAL on the palladium surface involves almost the same energy barriers, suggesting a comparable selectivity. Overall, as water reduces the activation energy for the formation of FOL while increases the energy barrier slightly for hydrogenation of the furan ring, water changes the reaction selectivity and promotes the formation of furfuryl alcohol.

On the nature of hydrogen bonding between the phosphatidylcholine head group and water and dimethylsulfoxide

NASA Astrophysics Data System (ADS)

Dabkowska, Aleksandra P.; Lawrence, M. Jayne; McLain, Sylvia E.; Lorenz, Christian D.

2013-01-01

Molecular dynamics simulations are used to provide a detailed investigation of the hydrogen bond networks around the phosphatidylcholine (PC) head group in 1,2-dipropionyl-sn-glycero-3-phosphocholine in pure water, 10 mol.% and 30 mol.% dimethylsulfoxide (DMSO)-water solutions. Specifically, it is observed that DMSO replaces those water molecules that are within the first solvation shell of the choline, phosphate and ester groups of the PC head group, but are not hydrogen-bonded to the group. The effect of the presence of DMSO on the hydrogen bond network around the PC head groups of the lipid changes with the concentration of DMSO. In comparison to the hydrogen bond network observed in the pure water system, the number of hydrogen-bonded chains of solvent molecules increases slightly for the 10 mol.% DMSO system, while, in the 30 mol.% DMSO system, the number of hydrogen-bonded chains of solvent molecules decreases.

A ketone/alcohol polymer for cycle of electrolytic hydrogen-fixing with water and releasing under mild conditions

PubMed Central

Kato, Ryo; Yoshimasa, Keisuke; Egashira, Tatsuya; Oya, Takahiro; Oyaizu, Kenichi; Nishide, Hiroyuki

2016-01-01

Finding a safe and efficient carrier of hydrogen is a major challenge. Recently, hydrogenated organic compounds have been studied as hydrogen storage materials because of their ability to stably and reversibly store hydrogen by forming chemical bonds; however, these compounds often suffer from safety issues and are usually hydrogenated with hydrogen at high pressure and/or temperature. Here we present a ketone (fluorenone) polymer that can be moulded as a plastic sheet and fixes hydrogen via a simple electrolytic hydrogenation at −1.5 V (versus Ag/AgCl) in water at room temperature. The hydrogenated alcohol derivative (the fluorenol polymer) reversibly releases hydrogen by heating (80 °C) in the presence of an aqueous iridium catalyst. Both the use of a ketone polymer and the efficient hydrogen fixing with water as a proton source are completely different from other (de)hydrogenated compounds and hydrogenation processes. The easy handling and mouldable polymers could suggest a pocketable hydrogen carrier. PMID:27687772

Method for simultaneous recovery of hydrogen from water and from hydrocarbons

DOEpatents

Willms, R. Scott

1996-01-01

Method for simultaneous recovery of hydrogen and hydrogen isotopes from water and from hydrocarbons. A palladium membrane, when utilized in cooperation with a nickel catalyst in a reactor, has been found to drive reactions such as water gas shift, steam reforming and methane cracking to substantial completion by removing the product hydrogen from the reacting mixture. In addition, ultrapure hydrogen is produced, thereby eliminating the need for an additional processing step.

Influence of drinking water and diet on the stable-hydrogen isotope ratios of animal tissues

PubMed Central

Hobson, Keith A.; Atwell, Lisa; Wassenaar, Leonard I.

1999-01-01

Despite considerable interest in using stable-hydrogen isotope ratio (δD) measurements in ecological research, it was previously unknown whether hydrogen derived from drinking water, in addition to that derived from diet, contributed to the nonexchangeable hydrogen in animal tissues. We raised four experimental groups of quail (Coturnix coturnix japonica) from hatch on two isotopically distinct diets (mean nonexchangeable δD: −146 and −60‰, Vienna Standard Mean Ocean Water Standard) and drinking waters (mean δD: −130 and +196‰, Vienna Standard Mean Ocean Water Standard). Here we show that both dietary and drinking water hydrogen are incorporated into nonexchangeable hydrogen in both metabolically active (i.e., muscle, liver, blood, fat) and inactive (i.e., feather, nail) tissues. Approximately 20% of hydrogen in metabolically active quail tissues and 26–32% of feathers and nail was derived from drinking water. Our findings suggest environmental interpretations of δD values from modern and fossil animal tissues may need to account for potentially large isotopic differences between drinking water and food and require a good understanding of the physiological ecology of study organisms. PMID:10393937

Thermochemical water decomposition. [hydrogen separation for energy applications

NASA Technical Reports Server (NTRS)

Funk, J. E.

1977-01-01

At present, nearly all of the hydrogen consumed in the world is produced by reacting hydrocarbons with water. As the supply of hydrocarbons diminishes, the problem of producing hydrogen from water alone will become increasingly important. Furthermore, producing hydrogen from water is a means of energy conversion by which thermal energy from a primary source, such as solar or nuclear fusion of fission, can be changed into an easily transportable and ecologically acceptable fuel. The attraction of thermochemical processes is that they offer the potential for converting thermal energy to hydrogen more efficiently than by water electrolysis. A thermochemical hydrogen-production process is one which requires only water as material input and mainly thermal energy, or heat, as an energy input. Attention is given to a definition of process thermal efficiency, the thermodynamics of the overall process, the single-stage process, the two-stage process, multistage processes, the work of separation and a process evaluation.

Using permeable membranes to produce hydrogen and oxygen from water

NASA Technical Reports Server (NTRS)

Sanders, A. P.; Williams, R. J.; Downs, W. R.; Mcbryar, H.

1975-01-01

Concept may make it profitable to obtain hydrogen fuel from water. Laboratory tests have demonstrated that method enables decomposition of water several orders of magnitude beyond equilibrium state where only small amounts of free hydrogen are present.

Hydrogen-Rich Water Intake Accelerates Oral Palatal Wound Healing via Activation of the Nrf2/Antioxidant Defense Pathways in a Rat Model

PubMed Central

Orihuela-Campos, Rita Cristina; Fukui, Makoto; Ito, Hiro-O

2016-01-01

The wound healing process attempts to restore the integrity and function of the injured tissue. Additionally, proinflammatory cytokines, growth factors, and oxidative stress play important roles in wound healing. The aim of this study was to determine whether hydrogen-rich water intake induces the activation of the Nrf2/antioxidant defense pathway in rat palatal tissue, thereby reducing systemic oxidative stress and proinflammatory cytokine levels and promoting healing-associated genes. A circular excisional wound was created in the oral palatal region, and the wound healing process was observed. The rats were divided into two experimental groups in which either hydrogen-rich water or distilled water was consumed. In the drinking hydrogen-rich water, the palatal wound healing process was accelerated compared to that in the control group. As molecular hydrogen upregulated the Nrf2 pathway, systemic oxidative stresses were decreased by the activation of antioxidant activity. Furthermore, hydrogen-rich water intake reduced proinflammatory cytokine levels and promoted the expression of healing-associated factors in rat palatal tissue. In conclusion, hydrogen-rich water intake exhibited multiple beneficial effects through activation of the Nrf2/antioxidant defense pathway. The results of this study support the hypothesis that oral administration of hydrogen-rich water benefits the wound healing process by decreasing oxidative stress and inflammatory responses. PMID:26798423

Hydrogen-Rich Water Intake Accelerates Oral Palatal Wound Healing via Activation of the Nrf2/Antioxidant Defense Pathways in a Rat Model.

PubMed

Tamaki, Naofumi; Orihuela-Campos, Rita Cristina; Fukui, Makoto; Ito, Hiro-O

2016-01-01

The wound healing process attempts to restore the integrity and function of the injured tissue. Additionally, proinflammatory cytokines, growth factors, and oxidative stress play important roles in wound healing. The aim of this study was to determine whether hydrogen-rich water intake induces the activation of the Nrf2/antioxidant defense pathway in rat palatal tissue, thereby reducing systemic oxidative stress and proinflammatory cytokine levels and promoting healing-associated genes. A circular excisional wound was created in the oral palatal region, and the wound healing process was observed. The rats were divided into two experimental groups in which either hydrogen-rich water or distilled water was consumed. In the drinking hydrogen-rich water, the palatal wound healing process was accelerated compared to that in the control group. As molecular hydrogen upregulated the Nrf2 pathway, systemic oxidative stresses were decreased by the activation of antioxidant activity. Furthermore, hydrogen-rich water intake reduced proinflammatory cytokine levels and promoted the expression of healing-associated factors in rat palatal tissue. In conclusion, hydrogen-rich water intake exhibited multiple beneficial effects through activation of the Nrf2/antioxidant defense pathway. The results of this study support the hypothesis that oral administration of hydrogen-rich water benefits the wound healing process by decreasing oxidative stress and inflammatory responses.

Dye-sensitized photocatalyst for effective water splitting catalyst

NASA Astrophysics Data System (ADS)

Watanabe, Motonori

2017-12-01

Renewable hydrogen production is a sustainable method for the development of next-generation energy technologies. Utilising solar energy and photocatalysts to split water is an ideal method to produce hydrogen. In this review, the fundamental principles and recent progress of hydrogen production by artificial photosynthesis are reviewed, focusing on hydrogen production from photocatalytic water splitting using organic-inorganic composite-based photocatalysts.

Behavior of tritium permeation induced by water corrosion of alpha iron around room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Otsuka, T.; Hashizume, K.

2015-03-15

Tritium (T) permeation leakage to surroundings is a great safety concern in fission and fusion reactor systems. T permeation potentially occurs from T contaminated water through cooling tubes or storage tank made of metals which dissolve some T evolved by water corrosion. In order to understand behaviors of hydrogen uptake and permeation in pure α-iron (αFe) during water corrosion around room temperature, hydrogen permeation experiments for an αFe membrane have been conducted by means of tritium tracer techniques. The present study suggests that hydrogen produced by water corrosion of αFe is trapped in product oxide layers to delay hydrogen uptakemore » in αFe for a moment. However, the oxide layers do not work as a sufficient barrier for hydrogen uptake. Some of hydrogen dissolved in αFe normally diffuses and permeates through the bulk in the early stage of permeation. In a later stage, hydrogen permeation could be apparently stopped by the disappearance of concentration difference of tritium. Hydrogen partial pressure at the water/αFe interface could be ranged from 0.7 to 9.5 kPa around room temperature.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H 2O 2 and the 4e– oxidation to O 2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO 2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H 2O 2 evolution selectively.« less

Research on Liquid Management Technology in Water Tank and Reactor for Propulsion System with Hydrogen Production System Utilizing Aluminum and Water Reaction

NASA Astrophysics Data System (ADS)

Imai, Ryoji; Imamura, Takuya; Sugioka, Masatoshi; Higashino, Kazuyuki

2017-12-01

High pressure hydrogen produced by aluminum and water reaction is considered to be applied to space propulsion system. Water tank and hydrogen production reactor in this propulsion system require gas and liquid separation function under microgravity condition. We consider to install vane type liquid acquisition device (LAD) utilizing surface tension in the water tank, and install gas-liquid separation mechanism by centrifugal force which swirling flow creates in the hydrogen reactor. In water tank, hydrophilic coating was covered on both tank wall and vane surface to improve wettability. Function of LAD in water tank and gas-liquid separation in reaction vessel were evaluated by short duration microgravity experiments using drop tower facility. In the water tank, it was confirmed that liquid was driven and acquired on the outlet due to capillary force created by vanes. In addition of this, it was found that gas-liquid separation worked well by swirling flow in hydrogen production reactor. However, collection of hydrogen gas bubble was sometimes suppressed by aluminum alloy particles, which is open problem to be solved.

Estimation of the degree of hydrogen bonding between quinoline and water by ultraviolet-visible absorbance spectroscopy in sub- and supercritical water

NASA Astrophysics Data System (ADS)

Osada, Mitsumasa; Toyoshima, Katsunori; Mizutani, Takakazu; Minami, Kimitaka; Watanabe, Masaru; Adschiri, Tadafumi; Arai, Kunio

2003-03-01

UV-visible spectra of quinoline was measured in sub- and supercritical water (25 °C

Relative Importance of Various Sources of Defect-Producing Hydrogen Introduced into Steel During Application of Vitreous Coatings

NASA Technical Reports Server (NTRS)

Moore, Dwight G; Mason, Mary A; Harrison, William N

1953-01-01

When porcelain enamels or vitreous-type ceramic coatings are applied to ferrous metals, there is believed to be an evolution of hydrogen gas both during and after the firing operation. At elevated temperatures rapid evolution may result in blistering while if hydrogen becomes trapped in the steel during the rapid cooling following the firing operation gas pressures may be generated at the coating-metal interface and flakes of the coating literally blown off the metal. To determine experimentally the relative importance of the principal sources of the hydrogen causing the defects, a procedure was devised in which heavy hydrogen (deuterium) was substituted in turn for regular hydrogen in each of five possible hydrogen-producing operations in the coating process. The findings of the study were as follows: (1) the principal source of the defect-producing hydrogen was the dissolved water present in the enamel frit that was incorporated into the coating. (2) the acid pickling, the milling water, the chemically combined water in the clay, and the quenching water were all minor sources of defect-producing hydrogen under the test conditions used. Confirming experiments showed that fishscaling could be eliminated by using a water-free coating.

Status of research and development on photoelectrochemical hydrogen production in Korea

NASA Astrophysics Data System (ADS)

Kim, Jong Won; Lee, Jae S.; Baeg, Jin-Ook

2010-08-01

Conversion of solar energy into hydrogen is one of the most promising renewable energy technologies. Photocatalytic production of hydrogen from water, H2S and organic wastes using semiconductors is one of the potential strategies for converting the sunlight energy into chemical energy. Korea government paid great attention to the hydrogen economy and launched the HERC (Hydrogen Energy R&D Center) for supporting the R&D topics on hydrogen related technologies. The key issue for realizing the commercial application of solar water splitting hydrogen production technique is to find an efficient, stable and low-cost photocatalyst. Our research groups have continuously investigated to find oxide and composite photocatalysts for photoelectrochemical cell with high efficiency using computational design and synthesis method. But, fundamental research on semiconductor doping for band gap shifting and surface chemistry modification is still required. Various reaction media containing sacrificial agents should be developed to match with high activity photocatalysts to further improve the system efficiency. Water containing organic/inorganic waste and sea water are particularly suggested in the consideration that all these water sources are the most available water on the earth to the final commercial application of photocatalytic water splitting technique.

Process for forming hydrogen and other fuels utilizing magma

DOEpatents

Galt, John K.; Gerlach, Terrence M.; Modreski, Peter J.; Northrup, Jr., Clyde J. M.

1978-01-01

The disclosure relates to a method for extracting hydrogen from magma and water by injecting water from above the earth's surface into a pocket of magma and extracting hydrogen produced by the water-magma reaction from the vicinity of the magma.

A statistical mechanical theory for a two-dimensional model of water

NASA Astrophysics Data System (ADS)

Urbic, Tomaz; Dill, Ken A.

2010-06-01

We develop a statistical mechanical model for the thermal and volumetric properties of waterlike fluids. Each water molecule is a two-dimensional disk with three hydrogen-bonding arms. Each water interacts with neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of the Truskett and Dill (TD) treatment of the "Mercedes-Benz" (MB) model. The present model gives better predictions than TD for hydrogen-bond populations in liquid water by distinguishing strong cooperative hydrogen bonds from weaker ones. We explore properties versus temperature T and pressure p. We find that the volumetric and thermal properties follow the same trends with T as real water and are in good general agreement with Monte Carlo simulations of MB water, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds for increasing temperature. The model reproduces that pressure squeezes out water's heat capacity and leads to a negative thermal expansion coefficient at low temperatures. In terms of water structuring, the variance in hydrogen-bonding angles increases with both T and p, while the variance in water density increases with T but decreases with p. Hydrogen bonding is an energy storage mechanism that leads to water's large heat capacity (for its size) and to the fragility in its cagelike structures, which are easily melted by temperature and pressure to a more van der Waals-like liquid state.

A statistical mechanical theory for a two-dimensional model of water.

PubMed

Urbic, Tomaz; Dill, Ken A

2010-06-14

We develop a statistical mechanical model for the thermal and volumetric properties of waterlike fluids. Each water molecule is a two-dimensional disk with three hydrogen-bonding arms. Each water interacts with neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of the Truskett and Dill (TD) treatment of the "Mercedes-Benz" (MB) model. The present model gives better predictions than TD for hydrogen-bond populations in liquid water by distinguishing strong cooperative hydrogen bonds from weaker ones. We explore properties versus temperature T and pressure p. We find that the volumetric and thermal properties follow the same trends with T as real water and are in good general agreement with Monte Carlo simulations of MB water, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds for increasing temperature. The model reproduces that pressure squeezes out water's heat capacity and leads to a negative thermal expansion coefficient at low temperatures. In terms of water structuring, the variance in hydrogen-bonding angles increases with both T and p, while the variance in water density increases with T but decreases with p. Hydrogen bonding is an energy storage mechanism that leads to water's large heat capacity (for its size) and to the fragility in its cagelike structures, which are easily melted by temperature and pressure to a more van der Waals-like liquid state.

Hydrophobic fluorine mediated switching of the hydrogen bonding site as well as orientation of water molecules in the aqueous mixture of monofluoroethanol: IR, molecular dynamics and quantum chemical studies.

PubMed

Mondal, Saptarsi; Biswas, Biswajit; Nandy, Tonima; Singh, Prashant Chandra

2017-09-20

The local structures between water-water, alcohol-water and alcohol-alcohol have been investigated for aqueous mixtures of ethanol (ETH) and monofluoroethanol (MFE) by the deconvolution of IR bands in the OH stretching region, molecular dynamics simulation and quantum chemical calculations. It has been found that the addition of a small amount of ETH into the aqueous medium increases the strength of the hydrogen bonds between water molecules. In an aqueous mixture of MFE, the substitution of a single fluorine induces a change in the orientation as well as the hydrogen bonding site of water molecules from the oxygen to the fluorine terminal of MFE. The switching of the hydrogen bonding site of water in the aqueous mixture of MFE results in comparatively strong hydrogen bonds between MFE and water molecules as well as less clustering of water molecules, unlike the case of the aqueous mixture of ETH. These findings about the modification of a hydrogen bond network by the hydrophobic fluorine group probably make fluorinated molecules useful for pharmaceutical as well as biological applications.

Structure and dynamics of water in mixed solutions including laponite and PEO

NASA Astrophysics Data System (ADS)

Morikubo, Satoshi; Sekine, Yurina; Ikeda-Fukazawa, Tomoko

2011-01-01

To investigate the structure and dynamics of water in mixed solutions including laponite clay particles and poly(ethylene oxide) (PEO), we measured the Raman spectra of the mixed solutions in the temperature range 283-313 K. The results show that the vibrational energies of the O-H stretching modes in the mixed solutions depend on the water content and temperature. The energy shifts of the O-H stretching modes are attributed to changes in the water structure. By applying a structural model of bulk water to the spectra in the O-H stretching region, the local structures of water in the solutions were analyzed. The result shows that the formation probability of hydrogen bonds in the solutions decreases as the water content decreases. Laponite and PEO have effects to disrupt the network structure of hydrogen bonds between water molecules. Further, it was found that laponite and PEO cause increase in the strength of hydrogen bonds of surrounding water,although the strength of the hydrogen bonds increases with the order water-laponite < water-water < water-PEO. It is concluded that water in laponite-PEO mixed solutions has a less-networked structure with strong hydrogen bonds compared with bulk water.

Molecular mechanism of gelation upon the addition of water to a solution of poly(acrylonitrile) in dimethylsulfoxide

NASA Astrophysics Data System (ADS)

Vettegren, V. I.; Kulik, V. B.; Savitskii, A. V.; Fetisov, O. I.; Usov, V. V.

2010-05-01

The solidification of a solution of poly(acrylonitrile) (PAN) in dimethylsulfoxide (DMSO) upon introduction of water into the solution is studied by Raman spectroscopy. In the absence of water, DMSO molecules are found to produce dipole-dipole bonds with PAN molecules. Upon the introduction of water, DMSO molecules produce hydrogen bonds with it and bands at 1005 and 1015 cm-1 appear in the Raman spectrum, which are assigned to the valence vibrations of S=O bonds involved in the hydrogen bonds. Simultaneously, water molecules produce hydrogen bonds with PAN molecules: R-C≡N...H-O-H...N≡C-R, where R is the carbon skeleton of a PAN molecule. Accordingly, a band at 2250 cm-1 arises in the Raman spectrum, which is assigned to the valence vibrations of C≡N bonds producing hydrogen bonds with a water molecule. When the water content is low and the DMSO concentration is high, the length of the hydrogen bonds varies in wide limits and the band at 2250 cm-1 is wide. As the water content rises, DMSO molecules come out of PAN, the variation of the hydrogen bond length in it decreases (the band at 2250 cm-1 narrows), and a high-viscosity system (gel) arises that consists of PAN molecules bonded to water molecules via “equally strong” hydrogen bonds.

New porous water ice metastable at atmospheric pressure obtained by emptying a hydrogen-filled ice

PubMed Central

del Rosso, Leonardo; Celli, Milva; Ulivi, Lorenzo

2016-01-01

The properties of some forms of water ice reserve still intriguing surprises. Besides the several stable or metastable phases of pure ice, solid mixtures of water with gases are precursors of other ices, as in some cases they may be emptied, leaving a metastable hydrogen-bound water structure. We present here the first characterization of a new form of ice, obtained from the crystalline solid compound of water and molecular hydrogen called C0-structure filled ice. By means of Raman spectroscopy, we measure the hydrogen release at different temperatures and succeed in rapidly removing all the hydrogen molecules, obtaining a new form of ice (ice XVII). Its structure is determined by means of neutron diffraction measurements. Of paramount interest is that the emptied crystal can adsorb again hydrogen and release it repeatedly, showing a temperature-dependent hysteresis. PMID:27819265

Hydrogen considerations in light-water power reactons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keilholtz, G.W.

1976-02-01

A critical review of the literature now available on hydrogen considerations in light-water power reactors (LWRs) and a bibliography of that literature are presented. The subject matter includes mechanisms for the generation of hydrogen-oxygen mixtures, a description of the fundamental properties of such mixtures, and their spontaneous ignition in both static and dynamic systems. The limits for hydrogen flammability and flame propagation are examined in terms of the effects of pressure, temperature, and additives; the emphasis is on the effects of steam and water vapor. The containment systems for pressurized-water reactors (PWRs) and boiling-water reactors (BWRs) are compared, and methodsmore » to control hydrogen and oxygen under the conditions of both normal operation and postulated accidents are reviewed. It is concluded that hydrogen can be controlled so that serious complications from the production of hydrogen will not occur. The bibliography contains abstracts from the computerized files of the Nuclear Safety Information Center. Key-word, author, and permuted-title indexes are provided. The bibliography includes responses to questions asked by the U. S. Nuclear Regulatory Commission (NRC) which relate to hydrogen, as well as information on normal operations and postulated accidents including generation of hydrogen from core sprays. Other topics included in the ten sections of the bibliography are metal-water reactions, containment atmosphere, radiolytic gas, and recombiners.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ionita, G.; Stefanescu, I.

The nature and performance of our patented catalysts, with platinum on carbon and polytetrafluorethylene [Pt/C/PTFE] and platinum on styrenedivynilbenzene and polystyrene [Pt/STB/PS], used in a water-hydrogen isotope exchange process are presented. The behaviour of the two catalysts in tritiated water was tested by determining their physical and structural characteristics as well as the catalytic activity before and after immersion in tritiated water. The test results emphasized that the two catalysts are highly active in the hydrogen - water vapor (H{sub 2(g)}-H{sub 2}O{sub (v)}) isotopic exchange and highly stable to tritium radiation. It was discovered that Pt/SDB/PS catalyst proved to bemore » quite unstable in the hydrogen- water vapor - water (H{sub 2(g)}-H{sub 2}O{sub (v)}-H{sub 2}O{sub (1)}) isotopic exchange, while the Pt/C/PTFE catalyst was highly stable. Thus, the Pt/C/PTFE catalyst was chosen for hydrogen isotope separation by liquid hydrogen cryogenic distillation combined with water - hydrogen isotopic exchange in a demonstration scale plant. 5 refs., 8 figs., 2 tabs.« less

Some perspective decisions for the regeneration system equipment of the thermal and nuclear power plants decreasing the probability of water ingress into the turbine and rotor acceleration by return steam flow

NASA Astrophysics Data System (ADS)

Trifonov, N. N.; Svyatkin, F. A.; Sintsova, T. G.; Ukhanova, M. G.; Yesin, S. B.; Nikolayenkova, E. K.; Yurchenko, A. Yu.; Grigorieva, E. B.

2016-03-01

The regeneration system heaters are one of the sources of possible ingress of the water into the turbine. The water penetrates into the turbine either at the heaters overflow or with the return flow of steam generated when the water being in the heater boils up in the dynamic operation modes or at deenergization of the power-generating unit. The return flow of steam and water is dangerous to the turbine blades and can result in the rotor acceleration. The known protective devices used to prevent the overflow of the low-pressure and high-pressure heaters (LPH and HPH), of the horizontal and vertical heaters of heating-system water (HWH and VWH), as well as of the deaerators and low-pressure mixing heaters (LPMH) were considered. The main protective methods of the steam and water return flows supplied by the heaters in dynamic operation modes or at deenergization of the power-generating unit are described. Previous operating experience shows that the available protections do not fully prevent water ingress into the turbine and the rotor acceleration and, therefore, the development of measures to decrease the possibility of ingress of the water into the turbine is an actual problem. The measures allowing eliminating or reducing the water mass in the heaters are expounded; some of them were designed by the specialists of OAO Polzunov Scientific and Development Association on Research and Design of Power Equipment (NPO CKTI) and are efficiently introduced at heat power plants and nuclear power plants. The suggested technical solutions allow reducing the possibility of the water ingress into the turbine and rotor acceleration by return steam flow in the dynamic operation modes or in the case of power generating unit deenergization. Some of these solutions have been tested in experimental-industrial exploitation and can be used in industry.

Mechanical properties of several nickel alloys in hydrogen at elevated temperatures

NASA Technical Reports Server (NTRS)

Warren, J. R.; Harris, J. A., Jr.; Vanwanderham, M. C.

1977-01-01

Tests were performed to determine low cycle fatigue and crack growth rate properties of one iron-base and two forms of one cast nickel-base alloy. The alloys were tested in various forms and/or heat-treat conditions that are proposed for use in a high-pressure hydrogen or a hydrogen-water vapor environment. Some general conclusions can be made comparing the results of tests in a hydrogen environment with those in a hydrogen-water vapor environment. The hydrogen-water vapor environment caused a 50 percent average reduction in fatigue life, indicating extreme degradation when compared with tests conducted in air, for Incoloy 903 at 1033 K (1400 F). Crack growth rates increased significantly for all materials with increasing test temperature. A very significant increase (three orders of magnitude) in crack growth rate occurred for Incoloy 903 tested in the hydrogen-water vapor environment when compared with testing done in hydrogen along at 922 K (1200 F).

Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

PubMed Central

Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

2016-01-01

Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH→Ni(OH)2) and an anodic OH− oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion. PMID:27199009

The influence of hydrogen bonding on partition coefficients

NASA Astrophysics Data System (ADS)

Borges, Nádia Melo; Kenny, Peter W.; Montanari, Carlos A.; Prokopczyk, Igor M.; Ribeiro, Jean F. R.; Rocha, Josmar R.; Sartori, Geraldo Rodrigues

2017-02-01

This Perspective explores how consideration of hydrogen bonding can be used to both predict and better understand partition coefficients. It is shown how polarity of both compounds and substructures can be estimated from measured alkane/water partition coefficients. When polarity is defined in this manner, hydrogen bond donors are typically less polar than hydrogen bond acceptors. Analysis of alkane/water partition coefficients in conjunction with molecular electrostatic potential calculations suggests that aromatic chloro substituents may be less lipophilic than is generally believed and that some of the effect of chloro-substitution stems from making the aromatic π-cloud less available to hydrogen bond donors. Relationships between polarity and calculated hydrogen bond basicity are derived for aromatic nitrogen and carbonyl oxygen. Aligned hydrogen bond acceptors appear to present special challenges for prediction of alkane/water partition coefficients and this may reflect `frustration' of solvation resulting from overlapping hydration spheres. It is also shown how calculated hydrogen bond basicity can be used to model the effect of aromatic aza-substitution on octanol/water partition coefficients.

Water oxidation catalysts and methods of use thereof

DOEpatents

Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

2017-12-05

Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

Polyoxometalate water oxidation catalysts and methods of use thereof

DOEpatents

Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

2014-09-02

Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

Aqueous heterogeneity at the air/water interface revealed by 2D-HD-SFG spectroscopy.

PubMed

Hsieh, Cho-Shuen; Okuno, Masanari; Hunger, Johannes; Backus, Ellen H G; Nagata, Yuki; Bonn, Mischa

2014-07-28

Water molecules interact strongly with each other through hydrogen bonds. This efficient intermolecular coupling causes strong delocalization of molecular vibrations in bulk water. We study intermolecular coupling at the air/water interface and find intermolecular coupling 1) to be significantly reduced and 2) to vary strongly for different water molecules at the interface--whereas in bulk water the coupling is homogeneous. For strongly hydrogen-bonded OH groups, coupling is roughly half of that of bulk water, due to the lower density in the near-surface region. For weakly hydrogen-bonded OH groups that absorb around 3500 cm(-1), which are assigned to the outermost, yet hydrogen-bonded OH groups pointing towards the liquid, coupling is further reduced by an additional factor of 2. Remarkably, despite the reduced structural constraints imposed by the interfacial hydrogen-bond environment, the structural relaxation is slow and the intermolecular coupling of these water molecules is weak. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composition and method for hydrogen storage

NASA Technical Reports Server (NTRS)

Mao, Wendy L. (Inventor); Mao, Ho-Kwang (Inventor)

2004-01-01

A method for hydrogen storage includes providing water and hydrogen gas to a containment volume, reducing the temperature of the water and hydrogen gas to form a hydrogen clathrate at a first cryogenic temperature and a first pressure and maintaining the hydrogen clathrate at second cryogenic temperature within a temperature range of up to 250 K to effect hydrogen storage. The low-pressure hydrogen hydrate includes H.sub.2 O molecules, H.sub.2 molecules and a unit cell including polyhedron cages of hydrogen-bonded frameworks of the H.sub.2 O molecules built around the H.sub.2 molecules.

The dynamics of solvation dictates the conformation of polyethylene oxide in aqueous, isobutyric acid and binary solutions.

PubMed

Dahal, Udaya R; Dormidontova, Elena E

2017-04-12

Polymers hydrogen-bonding with solvent represent an important broad class of polymers, properties of which depend on solvation. Using atomistic molecular dynamics simulations with the OPLS/AA force field we investigate the effect of hydrogen bonding on PEO conformation and chain mobility by comparing its behavior in isobutyric acid and aqueous solutions. In agreement with experimental data, we found that in isobutyric acid PEO forms a rather rigid extended helical structure, while in water it assumes a highly flexible coil conformation. We show that the difference in PEO conformation and flexibility is the result of the hydrogen bond stability and overall solvent dynamics near PEO. Isobutyric acid forms up to one hydrogen bond per repeat unit of PEO and interacts with PEO for a prolonged period of time, thereby stabilizing the helical structure of the polymer and reducing its segmental mobility. In contrast, water forms on average 1.2 hydrogen bonds per repeat unit of PEO (with 60% of water forming a single hydrogen bond and 40% of water forming two hydrogen bonds) and resides near PEO for a noticeably shorter time than isobutyric acid, leading to the well-documented high segmental mobility of PEO in water. We also analyze PEO conformation, hydrogen bonding and segmental mobility in binary water/isobutyric acid solutions and find that in the phase separated region PEO resides in the isobutyric-rich phase forming about 25% of its hydrogen bonds with isobutyric acid and 75% with water. We show that the dynamics of solvation affects the equilibrium properties of macromolecules, such as conformation, and by mixing of hydrogen bond-donating solvents one can significantly alter both polymer conformation and its local dynamics.

Variations of the Hydrogen Bonding and of the Hydrogen Bonded Network in Ethanol-Water Mixtures on Cooling.

PubMed

Pothoczki, Szilvia; Pusztai, Laszlo; Bako, Imre

2018-06-12

Molecular dynamics computer simulations have been conducted for ethanol-water liquid mixtures in the water-rich side of the composition range, with 10, 20 and 30 mol % of the alcohol, at temperatures between room temperature and the experimental freezing point of the given mixture. All-atom type (OPLS) interatomic potentials have been assumed for ethanol, in combination with two kinds of rigid water models (SPC/E and TIP4P/2005). Both combinations have provided excellent reproductions of the experimental X-ray total structure factors at each temperature; this yielded a strong basis for further structural analyses. Beyond partial radial distribution functions, various descriptors of hydrogen bonded assemblies, as well as of the hydrogen bonded network have been determined. A clear tendency was observed towards that an increasing proportion of water molecules participate in hydrogen bonding with exactly 2 donor- and 2 acceptor sites as temperature decreases. Concerning larger assemblies held together by hydrogen bonding, the main focus was put on the properties of cyclic entities: it was found that, similarly to methanol-water mixtures, the number of hydrogen bonded rings has increased with lowering temperature. However, for ethanol-water mixtures the dominance of not the six-, but of the five-fold rings could be observed.

Hydrogen production from salt water by Marine blue green algae and solar radiation

NASA Technical Reports Server (NTRS)

Mitsui, A.; Rosner, D.; Kumazawa, S.; Barciela, S.; Phlips, E.

1985-01-01

Two marine bluegreen algae, Oscillatoria sp. Miami BG 7 and Synechococcus sp Miami 041511 have been selected as the result of over 10 years continuous and intensive effort of isolation, growth examination, and the screening of hydrogen photoproduction capability in this laboratory. Both strains photoproduced hydrogen for several days at high rates and a quantity of hydrogen was accumulated in a closed vessel. Overall hydrogen donor substance of the hydrogen photoproduction was found to be salt water. Using strain Miami BG 7, a two step method of hydrogen photoproduction from salt water was successfully developed and this was recycled several times over a one month period using both free cells and immobilized cells in both indoor and outdoor under natural sunlight. According to these experiments, a prototype floating hydrogen production system was designed for further development of the biosolar hydrogen production system.

Structure and Dynamics of Water Confined in Imogolite Nanotubes.

PubMed

Scalfi, Laura; Fraux, Guillaume; Boutin, Anne; Coudert, François-Xavier

2018-06-12

We have studied the properties of water adsorbed inside nanotubes of hydrophilic imogolite, an aluminum silicate clay mineral, by means of molecular simulations. We used a classical force field to describe the water and the flexible imogolite nanotube and validated it against the data obtained from first-principles molecular dynamics. With it, we observe a strong structuration of the water confined in the nanotube, with specific adsorption sites and a distribution of hydrogen bond patterns. The combination of number of adsorption sites, their geometry, and the preferential tetrahedral hydrogen bonding pattern of water leads to frustration and disorder. We further characterize the dynamics of the water, as well as the hydrogen bonds formed between water molecules and the nanotube, which is found to be more than 1 order of magnitude longer than water-water hydrogen bonds.

Reactor Experiments at the University of Minnesota.

DTIC Science & Technology

1987-07-15

metallurgy; zinc, zinc oxide; solar thermal,’ solar Pi% thermoelectrochemical’ water splitting, separation devices; reactors e, ? 20. AeSiRACT (Continue oe...reported. Water splitting, recovery of hydrogen 4. and sulfur from hydrogen sulfide, electrolysis of zinc oxide in vapor and liquid phases, oil...CH4-CO2 reforming process. 2. Hydrogen production from water and the production of hydrogen and sulfur (or ammonia and sulfuric acid) from H2S. 3

Statics and dynamics of free and hydrogen-bonded OH groups at the air/water interface.

PubMed

Vila Verde, Ana; Bolhuis, Peter G; Campen, R Kramer

2012-08-09

We use classical atomistic molecular dynamics simulations of two water models (SPC/E and TIP4P/2005) to investigate the orientation and reorientation dynamics of two subpopulations of OH groups belonging to water molecules at the air/water interface at 300 K: those OH groups that donate a hydrogen bond (called "bonded") and those that do not (called "free"). Free interfacial OH groups reorient in two distinct regimes: a fast regime from 0 to 1 ps and a slow regime thereafter. Qualitatively similar behavior was reported by others for free OH groups near extended hydrophobic surfaces. In contrast, the net reorientation of bonded OH groups occurs at a rate similar to that of bulk water. This similarity in reorientation rate results from compensation of two effects: decreasing frequency of hydrogen-bond breaking/formation (i.e., hydrogen-bond exchange) and faster rotation of intact hydrogen bonds. Both changes result from the decrease in density at the air/water interface relative to the bulk. Interestingly, because of the presence of capillary waves, the slowdown of hydrogen-bond exchange is significantly smaller than that reported for water near extended hydrophobic surfaces, but it is almost identical to that reported for water near small hydrophobic solutes. In this sense water at the air/water interface has characteristics of water of hydration of both small and extended hydrophobic solutes.

Hydrogen generation by reaction of Si nanopowder with neutral water

NASA Astrophysics Data System (ADS)

Kobayashi, Yuki; Matsuda, Shinsuke; Imamura, Kentaro; Kobayashi, Hikaru

2017-05-01

Si and its oxide are nonpoisonous materials, and thus, it can be taken for medical effects. We have developed a method of generation of hydrogen by use of reactions of Si nanopowder with water in the neutral pH region. Si nanopowder is fabricated by the simple bead milling method. Si nanopowder reacts with water to generate hydrogen even in cases where pH is set at the neutral region between 7.0 and 8.6. The hydrogen generation rate strongly depends on pH and in the case of pH 8.0, ˜55 ml/g hydrogen which corresponds to that contained in approximately 3 L saturated hydrogen-rich water is generated in 1 h. The reaction rate for hydrogen generation greatly increases with pH, indicating that the reacting species is hydroxide ions. The change of pH after the hydrogen generation reaction is negligibly low compared with that estimated assuming that hydroxide ions are consumed by the reaction. From these results, we conclude the following reaction mechanism: Si nanopowder reacts with hydroxide ions in the rate-determining reaction to form hydrogen molecules, SiO2, and electrons in the conduction band. Then, generated electrons are accepted by water molecules, resulting in production of hydrogen molecules and hydroxide ions. The hydrogen generation rate strongly depends on the crystallite size of Si nanopowder, but not on the size of aggregates of Si nanopowder. The present study shows a possibility to use Si nanopowder for hydrogen generation in the body in order to eliminate hydroxyl radicals which cause various diseases.

Nano-ferrites for Water Splitting: Unprecedented High Photocatalytic Hydrogen Production under Visible Light

EPA Science Inventory

In the present investigation, hydrogen production via water splitting by nano ferrites has been studied using ethanol as the sacrificial donor. The nano ferrite has shown great potential in hydrogen generation with hydrogen yield of 8275 9moles/h/ g of photocatalyst under visible...

Hydrogen and water reactor safety: proceedings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1982-01-01

Separate abstracts were prepared for papers presented in the following areas of interest: 1) hydrogen research programs; 2) hydrogen behavior during light water reactor accidents; 3) combustible gas generation; 4) hydrogen transport and mixing; 5) combustion modeling and experiments; 6) accelerated flames and detonations; 7) combustion mitigation and control; and 8) equipment survivability.

A statistical mechanical theory for a two-dimensional model of water

PubMed Central

Urbic, Tomaz; Dill, Ken A.

2010-01-01

We develop a statistical mechanical model for the thermal and volumetric properties of waterlike fluids. Each water molecule is a two-dimensional disk with three hydrogen-bonding arms. Each water interacts with neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of the Truskett and Dill (TD) treatment of the “Mercedes-Benz” (MB) model. The present model gives better predictions than TD for hydrogen-bond populations in liquid water by distinguishing strong cooperative hydrogen bonds from weaker ones. We explore properties versus temperature T and pressure p. We find that the volumetric and thermal properties follow the same trends with T as real water and are in good general agreement with Monte Carlo simulations of MB water, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds for increasing temperature. The model reproduces that pressure squeezes out water’s heat capacity and leads to a negative thermal expansion coefficient at low temperatures. In terms of water structuring, the variance in hydrogen-bonding angles increases with both T and p, while the variance in water density increases with T but decreases with p. Hydrogen bonding is an energy storage mechanism that leads to water’s large heat capacity (for its size) and to the fragility in its cagelike structures, which are easily melted by temperature and pressure to a more van der Waals-like liquid state. PMID:20550408

Characterization of the hydrogen-bond network of water around sucrose and trehalose: Microwave and terahertz spectroscopic study

NASA Astrophysics Data System (ADS)

Shiraga, Keiichiro; Adachi, Aya; Nakamura, Masahito; Tajima, Takuro; Ajito, Katsuhiro; Ogawa, Yuichi

2017-03-01

Modification of the water hydrogen bond network imposed by disaccharides is known to serve as a bioprotective agent in living organisms, though its comprehensive understanding is still yet to be reached. In this study, aiming to characterize the dynamical slowing down and destructuring effect of disaccharides, we performed broadband dielectric spectroscopy, ranging from 0.5 GHz to 12 THz, of sucrose and trehalose aqueous solutions. The destructuring effect was examined in two ways (the hydrogen bond fragmentation and disordering) and our result showed that both sucrose and trehalose exhibit an obvious destructuring effect with a similar strength, by fragmenting hydrogen bonds and distorting the tetrahedral-like structure of water. This observation strongly supports a chaotropic (structure-breaking) aspect of disaccharides on the water structure. At the same time, hydration water was found to exhibit slower dynamics and a greater reorientational cooperativity than bulk water because of the strengthened hydrogen bonds. These results lead to the conclusion that strong disaccharide-water hydrogen bonds structurally incompatible with native water-water bonds lead to the rigid but destructured hydrogen bond network around disaccharides. Another important finding in this study is that the greater dynamical slowing down of trehalose was found compared with that of sucrose, at variance with the destructuring effect where no solute dependent difference was observed. This discovery suggests that the exceptionally greater bioprotective impact especially of trehalose among disaccharides is mainly associated with the dynamical slowing down (rather than the destructuring effect).

Influence of the hydrogen bond quantum nature in liquid water and heavy water on stimulated Raman scattering

NASA Astrophysics Data System (ADS)

Li, Fabing; Li, Zhanlong; Li, Shuo; Fang, Wenhui; Sun, Chenglin; Men, Zhiwei

2018-06-01

Stimulated Raman scattering (SRS) of liquid water and heavy water have been investigated using Nd:YAG laser. The SRS spectra of liquid heavy water indicate that ice-VII and ice-VIII structures are formed by shock-induced compression (SIC) in forward and backward directions, respectively. Simultaneously, the SRS spectra reveal of liquid water that only ice-VII structure is formed in the backward direction. The difference in ice structures formed by SIC in liquid water and heavy water could be attributed to the effect of the hydrogen bond quantum nature with H+. SRS spectra of 2 M NaOH water solution with ice-VII and ice-VIII structures have been successfully obtained in forward and backward, respectively, as OH- greatly reduce the quantum nature of hydrogen bonds by neutralizing H+ in water. The hydrogen bond quantum nature is important for understanding isotope calibration test structure and isotopic effect.

Water in Earth's mantle: Hydrogen analysis of mantle olivine, pyroxenes and garnet using the SIMS

NASA Technical Reports Server (NTRS)

Kurosawa, Masanori; Yurimoto, Hisayoshi; Sueno, Shigeho

1993-01-01

Hydrogen (or water) in the Earth's interior plays a key role in the evolution and dynamics of the planet. However, the abundance and the existence form of the hydrogen have scarcely been clear in practice. Hydrogen in the mantle was incorporated in the interior during the formation of the Earth. The incorporated hydrogen was hardly possible to concentrate locally inside the Earth considering its high mobility and high reactivity. The hydrogen, preferably, could be distributed homogeneously over the mantle and the core by the subsequent physical and chemical processes. Therefore, hydrogen in the mantle could be present in the form of trace hydrogen in nominally anhydrous mantle minerals. The hydrogen and the other trace elements in mantle olivines, orthopyroxenes, clinopyroxenes, and garnets were determined using secondary ion mass spectrometry (SIMS) for elucidating (1) the exact hydrogen contents, (2) the correlation between the hydrogen and the other trace elements, (3) the dependence of the hydrogen contents on the depth, and (4) the dependence of the whole rock water contents on the depth.

Process for thermochemically producing hydrogen

DOEpatents

Bamberger, Carlos E.; Richardson, Donald M.

1976-01-01

Hydrogen is produced by the reaction of water with chromium sesquioxide and strontium oxide. The hydrogen producing reaction is combined with other reactions to produce a closed chemical cycle for the thermal decomposition of water.

Molecular interaction of (ethanol)2-water heterotrimers.

PubMed

Mejía, Sol M; Espinal, Juan F; Restrepo, Albeiro; Mondragón, Fanor

2007-08-23

The potential energy surface of the (ethanol)2-water heterotrimers for the trans and gauche conformers of ethanol was studied using density functional theory. The same approximation was used for characterizing representative clusters of (ethanol)3, (methanol)3, and (methanol)2-water. Trimerization energies and enthalpies as well as the analysis of geometric parameters suggest that the structures with a cyclic pattern in the three hydrogen bonds of the type O-H---O (primary hydrogen bonds), where all molecules are proton donor-acceptor at the same time, are more stable than those with just two primary hydrogen bonds. Additionally, we propose the formation of "secondary hydrogen bonds" between hydrogen atoms of the methyl group of ethanol and the oxygen atom of water or other ethanol molecule (C-H---O), which were found to be weaker than the primary hydrogen bonds.

Process for photosynthetically splitting water

DOEpatents

Greenbaum, Elias

1984-01-01

The invention is an improved process for producing gaseous hydrogen and oxygen from water. The process is conducted in a photolytic reactor which contains a water-suspension of a photoactive material containing a hydrogen-liberating catalyst. The reactor also includes a volume for receiving gaseous hydrogen and oxygen evolved from the liquid phase. To avoid oxygen-inactivation of the catalyst, the reactor is evacuated continuously by an external pump which circulates the evolved gases through means for selectively recovering hydrogen therefrom. The pump also cools the reactor by evaporating water from the liquid phase. Preferably, product recovery is effected by selectively diffusing the hydrogen through a heated semipermeable membrane, while maintaining across the membrane a magnetic field gradient which biases the oxygen away from the heated membrane. This promotes separation, minimizes the back-reaction of hydrogen and oxygen, and protects the membrane.

Analysis Sharpens Mars Hydrogen Map, Hinting Equatorial Water Ice

NASA Image and Video Library

2017-09-28

Re-analysis of 2002-2009 data from a hydrogen-finding instrument on NASA's Mars Odyssey orbiter increased the resolution of maps of hydrogen abundance. The reprocessed data (lower map) shows more "water-equivalent hydrogen" (darker blue) in some parts of this equatorial region of Mars. Puzzingly, this suggests the possible presence of water ice just beneath the surface near the equator, though it would not be thermodynamically stable there. The upper map uses raw data from Odyssey's neutron spectrometer instrument, which senses the energy state of neutrons coming from Mars, providing an indication of how much hydrogen is present in the top 3 feet (1 meter) of the surface. Hydrogen detected by Odyssey at high latitudes of Mars in 2002 was confirmed to be in the form of water ice by the follow-up NASA Phoenix Mars Lander mission in 2008. A 2017 reprocessing of the older data applied image-reconstruction techniques often used to reduce blurring from medical imaging data. The results are shown here for an area straddling the equator for about one-fourth the circumference of the planet, centered at 175 degrees west longitude. The white contours outline lobes of a formation called Medusae Fossae, coinciding with some areas of higher hydrogen abundance in the enhanced-resolution analysis. The black line indicates the limit of a relatively young lava plain, coinciding with areas of lower hydrogen abundance in the enhanced-resolution analysis. The color-coding key for hydrogen abundance in both maps is indicated by the horizontal bar, in units expressed as how much water would be present in the ground if the hydrogen is all in the form of water. Units of the equivalent water weight, as a percentage of the material in the ground, are correlated with counts recorded by the spectrometer, ranging from less than 1 weight-percent water equivalent (red) to more than 30 percent (dark blue). https://photojournal.jpl.nasa.gov/catalog/PIA21848

Hollow fiber membrane systems for advanced life support systems

NASA Technical Reports Server (NTRS)

Roebelen, G. J., Jr.; Lysaght, M. J.

1976-01-01

The practicability of utilizing hollow fiber membranes in vehicular and portable life support system applications is described. A preliminary screening of potential advanced life support applications resulted in the selection of five applications for feasibility study and testing. As a result of the feasibility study and testing, three applications, heat rejection, deaeration, and bacteria filtration, were chosen for breadboard development testing; breadboard hardware was manufactured and tested, and the physical properties of the hollow fiber membrane assemblies are characterized.

Lunar Water Resource Demonstration (LWRD) Test Results

NASA Technical Reports Server (NTRS)

Muscatello, Anthony C.; Captain, Janine E.; Quinn, Jacqueline W.; Gibson, Tracy L.; Perusich, Stephen A.; Weis, Kyle H.

2009-01-01

NASA has undertaken the In-Situ Resource Utilization (lSRU) project called RESOLVE (Regolith and Environment Science & Oxygen and Lunar Volatile Extraction). This project is an Earth-based lunar precursor demonstration of a system that could be sent to explore permanently shadowed polar lunar craters, where it would drill into regolith, quantify the volatiles that are present, and extract oxygen by hydrogen reduction of iron oxides. The RESOLVE chemical processing system was mounted within the CMU rover "Scarab" and successfully demonstrated on Hawaii's Mauna Kea volcano in November 2008. This technology could be used on Mars as well. As described at the 2008 Mars Society Convention, the Lunar Water Resource Demonstration (LWRD) supports the objectives of the RESOLVE project by capturing and quantifying water and hydrogen released by regolith upon heating. Field test results for the quantification of water using LWRD showed that the volcanic ash (tephra) samples contained 0.15-0.41% water, in agreement with GC water measurements. Reduction of the RH in the surge tank to near zero during recirculation show that the water is captured by the water beds as desired. The water can be recovered by heating the Water Beds to 230 C or higher. Test results for the capture and quantification of pure hydrogen have shown that over 90% of the hydrogen can be captured and 98% of the absorbed hydrogen can be recovered upon heating the hydride to 400 C and desorbing the hydrogen several times into the evacuated surge tank. Thus, the essential requirement of capturing hydrogen and recovering it has been demonstrated. ,

Simulation of the effect of hydrogen bonds on water activity of glucose and dextran using the Veytsman model.

PubMed

De Vito, Francesca; Veytsman, Boris; Painter, Paul; Kokini, Jozef L

2015-03-06

Carbohydrates exhibit either van der Waals and ionic interactions or strong hydrogen bonding interactions. The prominence and large number of hydrogen bonds results in major contributions to phase behavior. A thermodynamic framework that accounts for hydrogen bonding interactions is therefore necessary. We have developed an extension of the thermodynamic model based on the Veytsman association theory to predict the contribution of hydrogen bonds to the behavior of glucose-water and dextran-water systems and we have calculated the free energy of mixing and its derivative leading to chemical potential and water activity. We compared our calculations with experimental data of water activity for glucose and dextran and found excellent agreement far superior to the Flory-Huggins theory. The validation of our calculations using experimental data demonstrated the validity of the Veytsman model in properly accounting for the hydrogen bonding interactions and successfully predicting water activity of glucose and dextran. Our calculations of the concentration of hydrogen bonds using the Veytsman model were instrumental in our ability to explain the difference between glucose and dextran and the role that hydrogen bonds play in contributing to these differences. The miscibility predictions showed that the Veytsman model is also able to correctly describe the phase behavior of glucose and dextran. Copyright © 2014 Elsevier Ltd. All rights reserved.

Preparation of organic and water hydrogen for stable isotope analysis. Effects due to reaction vessels and zinc reagent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schimmelmann, A.; DeNiro, M.J.

1993-03-15

Combustion of organic matter in sealed Pyrex, Vycor, and quartz ampules at temperatures between 520 and 900[degrees]C yields less than stoichiometric amounts of water. The loss of hydrogen to hydration reactions between water vapor and glass/quartz interferes with the determination of C/H and N/H elemental ratios in organic matter. The effect increases from quartz to Vycor to Pyrex, but the incomplete yield does not significantly affect the precision and accuracy of the determination of stable hydrogen isotope ratios. Reactions between water and Pyrex do not affect the conversion of water to hydrogen with zinc in Pyrex ampules at 500[degrees]C, whichmore » is quantitative, but even preoutgassed zinc contains a deuterium-depleted hydrogen blank. D/H ratios in hydrogen from the Zn method require a nonlinear correction to achieve compatibility with [delta]D values from the uranium method. 19 refs., 4 tabs.« less

Water: two liquids divided by a common hydrogen bond.

PubMed

Soper, Alan K

2011-12-08

The structure of water is the subject of a long and ongoing controversy. Unlike simpler liquids, where atomic interactions are dominated by strong repulsive forces at short distances and weaker attractive (van der Waals) forces at longer distances, giving rise to local atomic coordination numbers of order 12, water has pronounced and directional hydrogen bonds which cause the dense liquid close-packed structure to open out into a disordered and dynamic network, with coordination number 4-5. Here I show that water structure can be accurately represented as a mixture of two identical, interpenetrating, molecular species separated by common hydrogen bonds. Molecules of one type can form hydrogen bonds with molecules of the other type but cannot form hydrogen bonds with molecules of the same type. These hydrogen bonds are strong along the bond but weak with respect to changes in the angle between neighboring bonds. The observed pressure and temperature dependence of water structure and thermodynamic properties follow naturally from this choice of water model, and it also gives a simple explanation of the enduring claims based on spectroscopic evidence that water is a mixture of two components. © 2011 American Chemical Society

Response surface methodology as a tool for modeling and optimization of Bacillus subtilis spores inactivation by UV/ nano-Fe0 process for safe water production.

PubMed

Yousefzadeh, Samira; Matin, Atiyeh Rajabi; Ahmadi, Ehsan; Sabeti, Zahra; Alimohammadi, Mahmood; Aslani, Hassan; Nabizadeh, Ramin

2018-04-01

One of the most important aspects of environmental issues is the demand for clean and safe water. Meanwhile, disinfection process is one of the most important steps in safe water production. The present study aims at estimating the performance of UV, nano Zero-Valent Iron particles (nZVI, nano-Fe 0 ), and UV treatment with the addition of nZVI (combined process) for Bacillus subtilis spores inactivation. Effects of different factors on inactivation including contact time, initial nZVI concentration, UV irradiance and various aerations conditions were investigated. Response surface methodology, based on a five-level, two variable central composite design, was used to optimize target microorganism reduction and the experimental parameters. The results indicated that the disinfection time had the greatest positive impact on disinfection ability among the different selected independent variables. According to the results, it can be concluded that microbial reduction by UV alone was more effective than nZVI while the combined UV/nZVI process demonstrated the maximum log reduction. The optimum reduction of about 4 logs was observed at 491 mg/L of nZVI and 60 min of contact time when spores were exposed to UV radiation under deaerated condition. Therefore, UV/nZVI process can be suggested as a reliable method for Bacillus subtilis spores inactivation. Copyright © 2018. Published by Elsevier Ltd.

Imaging nanobubble nucleation and hydrogen spillover during electrocatalytic water splitting.

PubMed

Hao, Rui; Fan, Yunshan; Howard, Marco D; Vaughan, Joshua C; Zhang, Bo

2018-06-05

Nucleation and growth of hydrogen nanobubbles are key initial steps in electrochemical water splitting. These processes remain largely unexplored due to a lack of proper tools to probe the nanobubble's interfacial structure with sufficient spatial and temporal resolution. We report the use of superresolution microscopy to image transient formation and growth of single hydrogen nanobubbles at the electrode/solution interface during electrocatalytic water splitting. We found hydrogen nanobubbles can be generated even at very early stages in water electrolysis, i.e., ∼500 mV before reaching its thermodynamic reduction potential. The ability to image single nanobubbles on an electrode enabled us to observe in real time the process of hydrogen spillover from ultrathin gold nanocatalysts supported on indium-tin oxide.

Quantum nature of protons in water probed by scanning tunneling microscopy and spectroscopy

NASA Astrophysics Data System (ADS)

Guo, Jing; Lü, Jing-Tao; Feng, Yexin; Chen, Ji; Peng, Jinbo; Lin, Zeren; Meng, Xiangzhi; Wang, Zhichang; Li, Xin-Zheng; Wang, En-Ge; Jiang, Ying; Jing-Tao Lü Team; Xin-Zheng Li Team

The complexity of hydrogen-bonding interaction largely arises from the quantum nature of light hydrogen nuclei, which has remained elusive for decades. Here we report the direct assessment of nuclear quantum effects on the strength of a single hydrogen bond formed at a water-salt interface, using tip-enhanced inelastic electron tunneling spectroscopy (IETS) based on a low-temperature scanning tunneling microscope (STM). The IETS signals are resonantly enhanced by gating the frontier orbitals of water via a chlorine-terminated STM tip, such that the hydrogen-bonding strength can be determined with unprecedentedly high accuracy from the redshift in the O-H stretching frequency of water. Isotopic substitution experiments combined with quantum simulations reveal that the anharmonic quantum fluctuations of hydrogen nuclei weaken the weak hydrogen bonds and strengthen the relatively strong ones. However, this trend can be completely reversed when the hydrogen bond is strongly coupled to the polar atomic sites of the surface.

A second order thermodynamic perturbation theory for hydrogen bond cooperativity in water

NASA Astrophysics Data System (ADS)

Marshall, Bennett D.

2017-05-01

It has been extensively demonstrated through first principles quantum mechanics calculations that water exhibits strong hydrogen bond cooperativity. Equations of state developed from statistical mechanics typically assume pairwise additivity, meaning they cannot account for these 3-body and higher cooperative effects. In this paper, we extend a second order thermodynamic perturbation theory to correct for hydrogen bond cooperativity in 4 site water. We demonstrate that the theory predicts hydrogen bonding structure consistent spectroscopy, neutron diffraction, and molecular simulation data. Finally, we implement the approach into a general equation of state for water.

Preventive Effects of Drinking Hydrogen-Rich Water on Gingival Oxidative Stress and Alveolar Bone Resorption in Rats Fed a High-Fat Diet

PubMed Central

Yoneda, Toshiki; Tomofuji, Takaaki; Kunitomo, Muneyoshi; Ekuni, Daisuke; Irie, Koichiro; Azuma, Tetsuji; Machida, Tatsuya; Miyai, Hisataka; Fujimori, Kouhei; Morita, Manabu

2017-01-01

Obesity induces gingival oxidative stress, which is involved in the progression of alveolar bone resorption. The antioxidant effect of hydrogen-rich water may attenuate gingival oxidative stress and prevent alveolar bone resorption in cases of obesity. We examined whether hydrogen-rich water could suppress gingival oxidative stress and alveolar bone resorption in obese rats fed a high-fat diet. Male Fischer 344 rats (n = 18) were divided into three groups of six rats each: a control group (fed a regular diet and drinking distilled water) and two experimental groups (fed a high-fat diet and drinking distilled water or hydrogen-rich water). The level of 8-hydroxydeoxyguanosine was determined to evaluate oxidative stress. The bone mineral density of the alveolar bone was analyzed by micro-computerized tomography. Obese rats, induced by a high-fat diet, showed a higher gingival level of 8-hydroxydeoxyguanosine and a lower level of alveolar bone density compared to the control group. Drinking hydrogen-rich water suppressed body weight gain, lowered gingival level of 8-hydroxydeoxyguanosine, and reduced alveolar bone resorption in rats on a high-fat diet. The results indicate that hydrogen-rich water could suppress gingival oxidative stress and alveolar bone resorption by limiting obesity. PMID:28098768

Preventive Effects of Drinking Hydrogen-Rich Water on Gingival Oxidative Stress and Alveolar Bone Resorption in Rats Fed a High-Fat Diet.

PubMed

Yoneda, Toshiki; Tomofuji, Takaaki; Kunitomo, Muneyoshi; Ekuni, Daisuke; Irie, Koichiro; Azuma, Tetsuji; Machida, Tatsuya; Miyai, Hisataka; Fujimori, Kouhei; Morita, Manabu

2017-01-13

Obesity induces gingival oxidative stress, which is involved in the progression of alveolar bone resorption. The antioxidant effect of hydrogen-rich water may attenuate gingival oxidative stress and prevent alveolar bone resorption in cases of obesity. We examined whether hydrogen-rich water could suppress gingival oxidative stress and alveolar bone resorption in obese rats fed a high-fat diet. Male Fischer 344 rats ( n = 18) were divided into three groups of six rats each: a control group (fed a regular diet and drinking distilled water) and two experimental groups (fed a high-fat diet and drinking distilled water or hydrogen-rich water). The level of 8-hydroxydeoxyguanosine was determined to evaluate oxidative stress. The bone mineral density of the alveolar bone was analyzed by micro-computerized tomography. Obese rats, induced by a high-fat diet, showed a higher gingival level of 8-hydroxydeoxyguanosine and a lower level of alveolar bone density compared to the control group. Drinking hydrogen-rich water suppressed body weight gain, lowered gingival level of 8-hydroxydeoxyguanosine, and reduced alveolar bone resorption in rats on a high-fat diet. The results indicate that hydrogen-rich water could suppress gingival oxidative stress and alveolar bone resorption by limiting obesity.

Water cavities of sH clathrate hydrate stabilized by molecular hydrogen.

PubMed

Strobel, Timothy A; Koh, Carolyn A; Sloan, E Dendy

2008-02-21

X-ray diffraction and Raman spectroscopic measurements confirm that molecular hydrogen can be contained within the small water cavities of a binary sH clathrate hydrate using large guest molecules that stabilize the large cavity. The potential increase in hydrogen storage could be more than 40% when compared with binary sII hydrates. This work demonstrates the stabilization of hydrogen in a hydrate structure previously unknown for encapsulating molecular hydrogen, indicating the potential for other inclusion compound materials with even greater hydrogen storage capabilities.

Studies of the use of heat from high temperature nuclear sources for hydrogen production processes

NASA Technical Reports Server (NTRS)

Farbman, G. H.

1976-01-01

Future uses of hydrogen and hydrogen production processes that can meet the demand for hydrogen in the coming decades were considered. To do this, a projection was made of the market for hydrogen through the year 2000. Four hydrogen production processes were selected, from among water electrolysis, fossil based and thermochemical water decomposition systems, and evaluated, using a consistent set of ground rules, in terms of relative performance, economics, resource requirements, and technology status.

In-Situ Formed Hydroxide Accelerating Water Dissociation Kinetics on Co3N for Hydrogen Production in Alkaline Solution.

PubMed

Xu, Zhe; Li, Wenchao; Yan, Yadong; Wang, HongXu; Zhu, Heng; Zhao, Meiming; Yan, Shicheng; Zou, Zhigang

2018-06-21

Sluggish water dissociation kinetics on nonprecious metal electrocatalysts limits the development of economical hydrogen production from water-alkali electrolyzers. Here, using Co 3 N electrocatalyst as a prototype, we find that during water splitting in alkaline electrolyte a cobalt-containing hydroxide formed on the surface of Co 3 N, which greatly decreased the activation energy of water dissociation (Volmer step, a main rate-determining step for water splitting in alkaline electrolytes). Combining the cobalt ion poisoning test and theoretical calculations, the efficient hydrogen production on Co 3 N electrocatalysts would benefit from favorable water dissociation on in-situ formed cobalt-containing hydroxide and low hydrogen production barrier on the nitrogen sites of Co 3 N. As a result, the Co 3 N catalyst exhibits a low water-splitting activation energy (26.57 kJ mol -1 ) that approaches the value of platinum electrodes (11.69 kJ mol -1 ). Our findings offer new insight into understanding the catalytic mechanism of nitride electrocatalysts, thus contributing to the development of economical hydrogen production in alkaline electrolytes.

Effectiveness of hydrogen rich water on antioxidant status of subjects with potential metabolic syndrome-an open label pilot study.

PubMed

Nakao, Atsunori; Toyoda, Yoshiya; Sharma, Prachi; Evans, Malkanthi; Guthrie, Najla

2010-03-01

Metabolic syndrome is characterized by cardiometabolic risk factors that include obesity, insulin resistance, hypertension and dyslipidemia. Oxidative stress is known to play a major role in the pathogenesis of metabolic syndrome. The objective of this study was to examine the effectiveness of hydrogen rich water (1.5-2 L/day) in an open label, 8-week study on 20 subjects with potential metabolic syndrome. Hydrogen rich water was produced, by placing a metallic magnesium stick into drinking water (hydrogen concentration; 0.55-0.65 mM), by the following chemical reaction; Mg + 2H(2)O --> Mg (OH)(2) + H(2). The consumption of hydrogen rich water for 8 weeks resulted in a 39% increase (p<0.05) in antioxidant enzyme superoxide dismutase (SOD) and a 43% decrease (p<0.05) in thiobarbituric acid reactive substances (TBARS) in urine. Further, subjects demonstrated an 8% increase in high density lipoprotein (HDL)-cholesterol and a 13% decrease in total cholesterol/HDL-cholesterol from baseline to week 4. There was no change in fasting glucose levels during the 8 week study. In conclusion, drinking hydrogen rich water represents a potentially novel therapeutic and preventive strategy for metabolic syndrome. The portable magnesium stick was a safe, easy and effective method of delivering hydrogen rich water for daily consumption by participants in the study.

Thermodynamics of hydrogen bond patterns in supramolecular assemblies of water molecules.

PubMed

Henry, Marc

2002-07-02

The PACHA (Partial Atomic Charges and Hardnesses Analysis) formalism is applied to various supramolecular assemblies of water molecules. After a detailed study of all available crystal structures for ice polymorphs, we shown that the hydrogen bond strength is roughly constant below 1 GPa and considerably weakened above that value. New hydrogen bond patterns are proposed for ice IV, V, and VI after (EB) (electrostatic balance) minimization. For other polymorphs, there is an almost perfect coincidence between experimental and predicted hydrogen bond patterns. The evolution of hydrogen bond energy as a function of molecular geometry in water clusters with up to 280 water molecules and in large supramolecular compounds is quantitatively described. Intermolecular hydrogen bonds are found to lie between -9 and -32 kJ mol-1, the stronger interaction occurs within the spherical fully disordered water droplet buried at the heart of Müller's superfullerene keplerate. The weakest one occurs in a chiral molecular snub cube built from six calix[4]resorcinarene and eight water molecules. Intramolecular hydrogen bonds are found in the range -10-100 kJ mol-1 and can thus be considerably stronger than intermolecular bonds. Finally, through the investigation of a clathrate type I compound, it was possible to obtain a deep insight of the host-guest interactions and self-assembly rules of water cages in these materials.

Characterization of the hydrogen-bond network of water around sucrose and trehalose: H-O-H bending analysis

NASA Astrophysics Data System (ADS)

Shiraga, Keiichiro; Adachi, Aya; Ogawa, Yuichi

2017-06-01

The bioprotective properties of disaccharides have been linked to destructuring effect on the hydrogen-bond structure of the interfacial water around the disaccharide solute, but its detailed mechanisms are yet to be provided. In this study, we characterized the destructuring effect based on the complex dielectric constants of interfacial water around sucrose and trehalose in the H-O-H bending region. Our analysis showed that the destructuring effect around disaccharides involves substantial disordering of the hydrogen-bond structure and formation of strong disaccharide-water hydrogen-bond. Such a destructuring effect caused by disaccharides is totally distinct from what happens with temperature increases of neat water.

Hydrogen-water ameliorates radiation-induced gastrointestinal toxicity via MyD88’s effects on the gut microbiota

PubMed Central

Xiao, Hui-wen; Li, Yuan; Luo, Dan; Dong, Jia-li; Zhou, Li-xin; Zhao, Shu-yi; Zheng, Qi-sheng; Wang, Hai-chao; Cui, Ming; Fan, Sai-jun

2018-01-01

Although radiation therapy is a cornerstone of modern management of malignancies, various side effects are inevitably linked to abdominal and pelvic cancer after radiotherapy. Radiation-mediated gastrointestinal (GI) toxicity impairs the life quality of cancer survivors and even shortens their lifespan. Hydrogen has been shown to protect against tissue injuries caused by oxidative stress and excessive inflammation, but its effect on radiation-induced intestinal injury was previously unknown. In the present study, we found that oral gavage with hydrogen-water increased the survival rate and body weight of mice exposed to total abdominal irradiation (TAI); oral gavage with hydrogen-water was also associated with an improvement in GI tract function and the epithelial integrity of the small intestine. Mechanistically, microarray analysis revealed that hydrogen-water administration upregulated miR-1968-5p levels, thus resulting in parallel downregulation of MyD88 expression in the small intestine after TAI exposure. Additionally, high-throughput sequencing showed that hydrogen-water oral gavage resulted in retention of the TAI-shifted intestinal bacterial composition in mice. Collectively, our findings suggested that hydrogen-water might be used as a potential therapeutic to alleviate intestinal injury induced by radiotherapy for abdominal and pelvic cancer in preclinical settings. PMID:29371696

Occurrence and distribution of color and hydrogen sulfide in water of the principal artesian aquifers in the Valdosta area, Georgia

USGS Publications Warehouse

Krause, Richard E.

1976-01-01

Hydrogen sulfide and color occur in objectionable amounts in ground water from the principal artesian aquifer in the Valdosta , Ga., area. Generally, water from wells south of Valdosta is high in hydrogen sulfide; water from wells north of the city is high in color. Water with high sulfate is likely to be a problem in wells deeper than about 540 ft. Heavy pumpage concentrated in a small area may cause high-sulfate water to migrate vertically upward into shallower wells. (Woodard-USGS)

Molecular cobalt pentapyridine catalysts for generating hydrogen from water

DOEpatents

Long, Jeffrey R; Chang, Christopher J; Sun, Yujie

2013-11-05

A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition including the moiety of the general formula. [(PY5Me.sub.2)CoL].sup.2+, where L can be H.sub.2O, OH.sup.-, a halide, alcohol, ether, amine, and the like. In embodiments of the invention, water, such as tap water or sea water can be subject to low electric potentials, with the result being, among other things, the generation of hydrogen.

Decades After Developing Technology, NREL Sets New Solar-to-Hydrogen Record

Science.gov Websites

recently achieved 16.2% solar-to-hydrogen conversion efficiency. Photo by Dennis Schroeder Innovation is to split water into hydrogen and oxygen. Photo by Dennis Schroeder Photo shows a photoelectrochemical device to split water into hydrogen and oxygen. Photo by Dennis Schroeder Second Look Leads to Record

Polymer system for gettering hydrogen

DOEpatents

Shepodd, Timothy Jon; Whinnery, LeRoy L.

2000-01-01

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, Timothy Jon; Whinnery, LeRoy L.

1998-11-17

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Water-splitting using photocatalytic porphyrin-nanotube composite devices

DOEpatents

Shelnutt, John A [Tijeras, NM; Miller, James E [Albuquerque, NM; Wang, Zhongchun [Albuquerque, NM; Medforth, Craig J [Winters, CA

2008-03-04

A method for generating hydrogen by photocatalytic decomposition of water using porphyrin nanotube composites. In some embodiments, both hydrogen and oxygen are generated by photocatalytic decomposition of water.

Fracture toughness of Alloy 690 and EN52 weld in air and water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, C.M.; Mills, W.J.

1999-06-01

The effect of low and high temperature water with high hydrogen on the fracture toughness of Alloy 690 and its weld, EN52, was characterized using elastic-plastic J{sub IC} methodology. While both materials display excellent fracture resistance in air and elevated temperature (>93 C) water, a dramatic degradation in toughness is observed in 54 C water. The loss of toughness is associated with a hydrogen-induced intergranular cracking mechanism where hydrogen is picked up from the water. Comparison of the cracking behavior in low temperature water with that for hydrogen-precharged specimens tested in air indicates that the critical local hydrogen content requiredmore » to cause low temperature embrittlement is on the order of 120 to 160 ppm. Loading rate studies show that the cracking resistance is significantly improved at rates above ca. 1000 MPa{radical}m/h because there is insufficient time to produce grain boundary embrittlement. Electron fractographic examinations were performed to correlate cracking behavior with microstructural features and operative fracture mechanics.« less

Fracture toughness of alloy 690 and EN52 welds in air and water

NASA Astrophysics Data System (ADS)

Brown, C. M.; Mills, W. J.

2002-06-01

The effect of low- and high-temperature water with high hydrogen on the fracture toughness of alloy 690 and its weld, EN52, was characterized using elastic-plastic J IC methodology. While both materials display excellent fracture resistance in air and elevated-temperature (>93 °C) water, a dramatic degradation in toughness is observed in 54 °C water. The loss of toughness is associated with a hydrogen-induced intergranular cracking mechanism, where hydrogen is picked up from the water. Comparison of the cracking behavior in low-temperature water with that for hydrogen-precharged specimens tested in air indicates that the critical local hydrogen content required to cause low-temperature embrittlement is on the order of 120 to 160 ppm. Loading-rate studies show that cracking resistance is improved at rates above ˜ 1000 MPa √m/h, because there is insufficient time to produce grain-boundary embrittlement. Electron fractographic examinations were performed to correlate cracking behavior with microstructural features and operative fracture mechanisms.

Effect of water on hydrogen permeability. [Stirling engines

NASA Technical Reports Server (NTRS)

Hulligan, D. D.; Tomazic, W. A.

1984-01-01

Doping of hydrogen with CO or CO2 was developed to reduce hydrogen permeation in Stirling engines by forming low permeability oxide coatings in the heater tubes. An end product of this process is water - which can condense in the cold parts of the engine system. If the water vapor is reduced to a low enough level, the hydrogen can reduce the oxide coating resulting in increased permeability. The equilibrium level of water (oxygen bearing gas) required to avoid reduction of the oxide coating was investigated. Results at 720 C and 13.8 MPa have shown that: (1) pure hydrogen will reduce the coating; (2) 500 ppm CO (500 ppm water equivalent) does not prevent the reduction; and (3) 500 ppm CO2 (1000 ppm water) appears to be close to the equilibrium level. Further tests are planned to define the equilibrium level more precisely and to extend the data to 820 C and 3.4, 6.9, and 13.8 MPa.

Selective reduction of condensed N-heterocycles using water as a solvent and a hydrogen source.

PubMed

Cho, Hyejin; Török, Fanni; Török, Béla

2013-02-21

The reduction of unprotected indoles and quinolines is described using water as a hydrogen source. The method is based on the application of a RANEY® type Ni-Al alloy in an aqueous medium. During the reaction the Al content of the alloy, used as reductants, reacts with water in situ providing hydrogen and a RANEY® Ni catalyst, thus the alloy serves as a hydrogen generator as well as a hydrogenation catalyst. The simplicity and efficacy of the method are illustrated by the selective reduction of a variety of substituted indoles and quinolines to indolines and tetrahydroquinolines, respectively.

A XPS Study of the Passivity of Stainless Steels Influenced by Sulfate-Reducing Bacteria.

NASA Astrophysics Data System (ADS)

Chen, Guocun

The influence of sulfate-reducing bacteria (SRB) on the passivity of type 304 and 317L stainless steels (SS) was investigated by x-ray photoelectron spectroscopy (XPS), microbiological and electrochemical techniques. Samples were exposed to SRB, and then the resultant surfaces were analyzed by XPS, and the corrosion resistance by potentiodynamic polarization in deaerated 0.1 M HCl. To further understand their passivity, the SRB-exposed samples were analyzed by XPS after potentiostatic polarization at a passive potential in the hydrochloric solution. The characterization was performed under two surface conditions: unrinsed and rinsed by deaerated alcohol and deionized water. Comparisons were made with control samples immersed in uninoculated medium. SRB caused a severe loss of the passivity of 304 SS through sulfide formation and possible additional activation to form hexavalent chromium. The sulfides included FeS, FeS_2, Cr_2S _3, NiS and possibly Fe_ {rm 1-x}S. The interaction took place nonuniformly, resulting in undercutting of the passive film and preferential hydration of inner surface layers. The bacterial activation of the Cr^{6+ }^ecies was magnified by subsequent potentiostatic polarization. In contrast, 317L SS exhibited a limited passivity. The sulfides were formed mainly in the outer layers. Although Cr^{6+}^ecies were observed after the exposure, they were dissolved upon polarization. Since 317L SS has a higher Mo content, its higher passivity was ascribed to Mo existing as molybdate on the surface and Mo^{5+} species in the biofilm. Consequently, the interaction of SRB with Mo was studied. It was observed that molybdate could be retained on the surfaces of Mo coupons by corrosion products. In the presence of SRB, however, a considerable portion of the molybdate interacted with intermediate sulfur -containing proteins, forming Mo(V)-S complexes and reducing bacterial growth and sulfate reduction. The limited insolubility of the Mo(V)-S complexes in 0.1 M HCl provided a certain protection so that the pitting potential of the SRB-exposed Mo coupons was not considerably decreased. The interaction of the sulfur-containing proteins with Mo also provided mechanistic information about the adhesion of biofilm to Mo-bearing steels. Additionally, the interactions of SRB with other alloying elements, Cr and Ni, were investigated.

Hydrogen-rich Water Exerting a Protective Effect on Ovarian Reserve Function in a Mouse Model of Immune Premature Ovarian Failure Induced by Zona Pellucida 3

PubMed Central

He, Xin; Wang, Shu-Yu; Yin, Cheng-Hong; Wang, Tong; Jia, Chan-Wei; Ma, Yan-Min

2016-01-01

Background: Premature ovarian failure (POF) is a disease that affects female fertility but has few effective treatments. Ovarian reserve function plays an important role in female fertility. Recent studies have reported that hydrogen can protect male fertility. Therefore, we explored the potential protective effect of hydrogen-rich water on ovarian reserve function through a mouse immune POF model. Methods: To set up immune POF model, fifty female BALB/c mice were randomly divided into four groups: Control (mice consumed normal water, n = 10), hydrogen (mice consumed hydrogen-rich water, n = 10), model (mice were immunized with zona pellucida glycoprotein 3 [ZP3] and consumed normal water, n = 15), and model-hydrogen (mice were immunized with ZP3 and consumed hydrogen-rich water, n = 15) groups. After 5 weeks, mice were sacrificed. Serum anti-Müllerian hormone (AMH) levels, granulosa cell (GC) apoptotic index (AI), B-cell leukemia/lymphoma 2 (Bcl-2), and BCL2-associated X protein (Bax) expression were examined. Analyses were performed using SPSS 17.0 (SPSS Inc., Chicago, IL, USA) software. Results: Immune POF model, model group exhibited markedly reduced serum AMH levels compared with those of the control group (5.41 ± 0.91 ng/ml vs. 16.23 ± 1.97 ng/ml, P = 0.033) and the hydrogen group (19.65 ± 7.82 ng/ml, P = 0.006). The model-hydrogen group displayed significantly higher AMH concentrations compared with that of the model group (15.03 ± 2.75 ng/ml vs. 5.41 ± 0.91 ng/ml, P = 0.021). The GC AI was significantly higher in the model group (21.30 ± 1.74%) than those in the control (7.06 ± 0.27%), hydrogen (5.17 ± 0.41%), and model-hydrogen groups (11.24 ± 0.58%) (all P < 0.001). The GC AI was significantly higher in the model-hydrogen group compared with that of the hydrogen group (11.24 ± 0.58% vs. 5.17 ± 0.41%, P = 0.021). Compared with those of the model group, ovarian tissue Bcl-2 levels increased (2.18 ± 0.30 vs. 3.01 ± 0.33, P = 0.045) and the Bax/Bcl-2 ratio decreased in the model-hydrogen group. Conclusions: Hydrogen-rich water may improve serum AMH levels and reduce ovarian GC apoptosis in a mouse immune POF model induced by ZP3. PMID:27647193

Insight into hydrogen bonds and characterization of interlayer spacing of hydrated graphene oxide.

PubMed

Liu, Liyan; Zhang, Ruifeng; Liu, Ying; Tan, Wei; Zhu, Guorui

2018-05-28

The number of hydrogen bonds and detailed information on the interlayer spacing of graphene oxide (GO) confined water molecules were calculated through experiments and molecular dynamics simulations. Experiments play a crucial role in the modeling strategy and verification of the simulation results. The binding of GO and water molecules is essentially controlled by hydrogen bond networks involving functional groups and water molecules confined in the GO layers. With the increase in the water content, the clusters of water molecules are more evident. The water molecules bounding to GO layers are transformed to a free state, making the removal of water molecules from the system difficult at low water contents. The diffuse behaviors of the water molecules are more evident at high water contents. With an increase in the water content, the functional groups are surrounded by fewer water molecules, and the distance between the functional groups and water molecules increases. As a result, the water molecules adsorbed into the GO interlamination will enlarge the interlayer spacing. The interlayer spacing is also affected by the number of GO layers. These results were confirmed by the calculations of number of hydrogen bonds, water state, mean square displacement, radial distribution function, and interlayer spacing of hydrated GO. Graphical Abstract This work research the interaction between GO functional groups and confined water molecules. The state of water molecules and interlayer spacing of graphene oxide were proved to be related to the number of hydrogen bonds.

Ab initio simulation of particle momentum distributions in high-pressure water

NASA Astrophysics Data System (ADS)

Ceriotti, M.

2014-12-01

Applying pressure to water reduces the average oxygen-oxygen distance, and facilitates the delocalisation of protons along the hydrogen bond. This pressure-induced delocalisation is further enhanced by the quantum nature of hydrogen nuclei, which is very significant even well above room temperature. Here we will evaluate the quantum kinetic energy and the particle momentum distribution of hydrogen and oxygen nuclei in water at extreme pressure, using ab initio path integral molecular dynamics. We will show that (transient) dissociation of water molecules induce measurable changes in the kinetic energy hydrogen atoms, although current deep inelastic scattering experiments are probably unable to capture the heterogeneity of the sample.

Microwave Spectrum of the Isopropanol-Water Dimer

NASA Astrophysics Data System (ADS)

Mead, Griffin; Finneran, Ian A.; Carroll, Brandon; Blake, Geoffrey

2016-06-01

Microwave spectroscopy provides a unique opportunity to study model non-covalent interactions. Of particular interest is the hydrogen bonding of water, whose various molecular properties are influenced by both strong and weak intermolecular forces. More specifically, measuring the hydrogen bonded structures of water-alcohol dimers investigates both strong (OH ··· OH) and weak (CH ··· OH) hydrogen bond interactions. Recently, we have measured the pure rotational spectrum of the isopropanol-water dimer using chirped-pulse Fourier transform microwave spectroscopy (CP-FTMW) between 8-18 GHz. Here, we present the spectrum of this dimer and elaborate on the structure's strong and weak hydrogen bonding.

Microsolvation of Fluoromethane.

PubMed

Rosenberg, Robert E

2016-09-29

Fluorinated organic compounds are ubiquitous in the pharmaceutical and agricultural industries. To better discern the mode of action of these compounds, it is critical to understand the potential for and strength of hydrogen bonds involving fluorine. It is known that CH3F forms a hydrogen bond with H2O in the gas phase but does not dissolve in bulk water. This paper examines CH3F surrounded by one to six water molecules. For systems of similar topologies, CH3F formed hydrogen bonds of nearly the same strength as water. Although CH3F can bind to a second water cluster with only a modest loss in binding energy, it must bind to these clusters as a double hydrogen bond acceptor. This means that CH3F cannot form a low-energy cyclic 2D hydrogen bonding network with water molecules, which limits its solubility in bulk water. However, CH3F should be able to bind to the periphery of small hydrogen bonding networks. These conclusions were not appreciably altered by SMD calculations. A more complete consideration of solvation, especially entropic effects, was not undertaken. Data for geometries, population changes, and vibrational frequency shifts were also analyzed and compared to binding energies.

Molecular mechanism of H+ conduction in the single-file water chain of the gramicidin channel.

PubMed

Pomès, Régis; Roux, Benoît

2002-05-01

The conduction of protons in the hydrogen-bonded chain of water molecules (or "proton wire") embedded in the lumen of gramicidin A is studied with molecular dynamics free energy simulations. The process may be described as a "hop-and-turn" or Grotthuss mechanism involving the chemical exchange (hop) of hydrogen nuclei between hydrogen-bonded water molecules arranged in single file in the lumen of the pore, and the subsequent reorganization (turn) of the hydrogen-bonded network. Accordingly, the conduction cycle is modeled by two complementary steps corresponding respectively to the translocation 1) of an ionic defect (H+) and 2) of a bonding defect along the hydrogen-bonded chain of water molecules in the pore interior. The molecular mechanism and the potential of mean force are analyzed for each of these two translocation steps. It is found that the mobility of protons in gramicidin A is essentially determined by the fine structure and the dynamic fluctuations of the hydrogen-bonded network. The translocation of H+ is mediated by spontaneous (thermal) fluctuations in the relative positions of oxygen atoms in the wire. In this diffusive mechanism, a shallow free-energy well slightly favors the presence of the excess proton near the middle of the channel. In the absence of H+, the water chain adopts either one of two polarized configurations, each of which corresponds to an oriented donor-acceptor hydrogen-bond pattern along the channel axis. Interconversion between these two conformations is an activated process that occurs through the sequential and directional reorientation of water molecules of the wire. The effect of hydrogen-bonding interactions between channel and water on proton translocation is analyzed from a comparison to the results obtained previously in a study of model nonpolar channels, in which such interactions were missing. Hydrogen-bond donation from water to the backbone carbonyl oxygen atoms lining the pore interior has a dual effect: it provides a coordination of water molecules well suited both to proton hydration and to high proton mobility, and it facilitates the slower reorientation or turn step of the Grotthuss mechanism by stabilizing intermediate configurations of the hydrogen-bonded network in which water molecules are in the process of flipping between their two preferred, polarized states. This mechanism offers a detailed molecular model for the rapid transport of protons in channels, in energy-transducing membrane proteins, and in enzymes.

How ions affect the structure of water.

PubMed

Hribar, Barbara; Southall, Noel T; Vlachy, Vojko; Dill, Ken A

2002-10-16

We model ion solvation in water. We use the MB model of water, a simple two-dimensional statistical mechanical model in which waters are represented as Lennard-Jones disks having Gaussian hydrogen-bonding arms. We introduce a charge dipole into MB waters. We perform (NPT) Monte Carlo simulations to explore how water molecules are organized around ions and around nonpolar solutes in salt solutions. The model gives good qualitative agreement with experiments, including Jones-Dole viscosity B coefficients, Samoilov and Hirata ion hydration activation energies, ion solvation thermodynamics, and Setschenow coefficients for Hofmeister series ions, which describe the salt concentration dependence of the solubilities of hydrophobic solutes. The two main ideas captured here are (1) that charge densities govern the interactions of ions with water, and (2) that a balance of forces determines water structure: electrostatics (water's dipole interacting with ions) and hydrogen bonding (water interacting with neighboring waters). Small ions (kosmotropes) have high charge densities so they cause strong electrostatic ordering of nearby waters, breaking hydrogen bonds. In contrast, large ions (chaotropes) have low charge densities, and surrounding water molecules are largely hydrogen bonded.

Hydrogen bond dynamics in bulk alcohols.

PubMed

Shinokita, Keisuke; Cunha, Ana V; Jansen, Thomas L C; Pshenichnikov, Maxim S

2015-06-07

Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics-quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid--alcohols--has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups.

Combined energy production and waste management in manned spacecraft utilizing on-demand hydrogen production and fuel cells

NASA Astrophysics Data System (ADS)

Elitzur, Shani; Rosenband, Valery; Gany, Alon

2016-11-01

Energy supply and waste management are among the most significant challenges in human spacecraft. Great efforts are invested in managing solid waste, recycling grey water and urine, cleaning the atmosphere, removing CO2, generating and saving energy, and making further use of components and products. This paper describes and investigates a concept for managing waste water and urine to simultaneously produce electric and heat energies as well as fresh water. It utilizes an original technique for aluminum activation to react spontaneously with water at room temperature to produce hydrogen on-site and on-demand. This reaction has further been proven to be effective also when using waste water and urine. Applying the hydrogen produced in a fuel cell, one obtains electric energy as well as fresh (drinking) water. The method was compared to the traditional energy production technology of the Space Shuttle, which is based on storing the fuel cell reactants, hydrogen and oxygen, in cryogenic tanks. It is shown that the alternative concept presented here may provide improved safety, compactness (reduction of more than one half of the volume of the hydrogen storage system), and management of waste liquids for energy generation and drinking water production. Nevertheless, it adds mass compared to the cryogenic hydrogen technology. It is concluded that the proposed method may be used as an emergency and backup power system as well as an additional hydrogen source for extended missions in human spacecraft.

Carbonate thermochemical cycle for the production of hydrogen

DOEpatents

Collins, Jack L [Knoxville, TN; Dole, Leslie R [Knoxville, TN; Ferrada, Juan J [Knoxville, TN; Forsberg, Charles W [Oak Ridge, TN; Haire, Marvin J [Oak Ridge, TN; Hunt, Rodney D [Oak Ridge, TN; Lewis, Jr, Benjamin E [Knoxville, TN; Wymer, Raymond G [Oak Ridge, TN

2010-02-23

The present invention is directed to a thermochemical method for the production of hydrogen from water. The method includes reacting a multi-valent metal oxide, water and a carbonate to produce an alkali metal-multi-valent metal oxide compound, carbon dioxide, and hydrogen.

Neutron Nucleic Acid Crystallography.

PubMed

Chatake, Toshiyuki

2016-01-01

The hydration shells surrounding nucleic acids and hydrogen-bonding networks involving water molecules and nucleic acids are essential interactions for the structural stability and function of nucleic acids. Water molecules in the hydration shells influence various conformations of DNA and RNA by specific hydrogen-bonding networks, which often contribute to the chemical reactivity and molecular recognition of nucleic acids. However, X-ray crystallography could not provide a complete description of structural information with respect to hydrogen bonds. Indeed, X-ray crystallography is a powerful tool for determining the locations of water molecules, i.e., the location of the oxygen atom of H2O; however, it is very difficult to determine the orientation of the water molecules, i.e., the orientation of the two hydrogen atoms of H2O, because X-ray scattering from the hydrogen atom is very small.Neutron crystallography is a specialized tool for determining the positions of hydrogen atoms. Neutrons are not diffracted by electrons, but are diffracted by atomic nuclei; accordingly, neutron scattering lengths of hydrogen and its isotopes are comparable to those of non-hydrogen atoms. Therefore, neutron crystallography can determine both of the locations and orientations of water molecules. This chapter describes the current status of neutron nucleic acid crystallographic research as well as the basic principles of neutron diffraction experiments performed on nucleic acid crystals: materials, crystallization, diffraction experiments, and structure determination.

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, T.J.; Whinnery, L.L.

1998-11-17

A novel composition is described comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen. 1 fig.

Recent Progress in Energy-Driven Water Splitting.

PubMed

Tee, Si Yin; Win, Khin Yin; Teo, Wee Siang; Koh, Leng-Duei; Liu, Shuhua; Teng, Choon Peng; Han, Ming-Yong

2017-05-01

Hydrogen is readily obtained from renewable and non-renewable resources via water splitting by using thermal, electrical, photonic and biochemical energy. The major hydrogen production is generated from thermal energy through steam reforming/gasification of fossil fuel. As the commonly used non-renewable resources will be depleted in the long run, there is great demand to utilize renewable energy resources for hydrogen production. Most of the renewable resources may be used to produce electricity for driving water splitting while challenges remain to improve cost-effectiveness. As the most abundant energy resource, the direct conversion of solar energy to hydrogen is considered the most sustainable energy production method without causing pollutions to the environment. In overall, this review briefly summarizes thermolytic, electrolytic, photolytic and biolytic water splitting. It highlights photonic and electrical driven water splitting together with photovoltaic-integrated solar-driven water electrolysis.

Recent Progress in Energy‐Driven Water Splitting

PubMed Central

Tee, Si Yin; Win, Khin Yin; Teo, Wee Siang; Koh, Leng‐Duei; Liu, Shuhua; Teng, Choon Peng

2017-01-01

Hydrogen is readily obtained from renewable and non‐renewable resources via water splitting by using thermal, electrical, photonic and biochemical energy. The major hydrogen production is generated from thermal energy through steam reforming/gasification of fossil fuel. As the commonly used non‐renewable resources will be depleted in the long run, there is great demand to utilize renewable energy resources for hydrogen production. Most of the renewable resources may be used to produce electricity for driving water splitting while challenges remain to improve cost‐effectiveness. As the most abundant energy resource, the direct conversion of solar energy to hydrogen is considered the most sustainable energy production method without causing pollutions to the environment. In overall, this review briefly summarizes thermolytic, electrolytic, photolytic and biolytic water splitting. It highlights photonic and electrical driven water splitting together with photovoltaic‐integrated solar‐driven water electrolysis. PMID:28546906

What Can Interfacial Water Molecules Tell Us About Solute Structure?

NASA Astrophysics Data System (ADS)

Willard, Adam

The molecular structure of bulk liquid water reflects a molecular tendency to engage in tetrahedrally coordinated hydrogen bonding. At a solute interface waters preferred three-dimensional hydrogen bonding network must conform to a locally anisotropy interfacial environment. Interfacial water molecules adopt configurations that balance water-solute and water-water interactions. The arrangements of interfacial water molecules, therefore encode information about the effective solute-water interactions. This solute-specific information is difficult to extract, however, because interfacial structure also reflects waters collective response to an anisotropic hydrogen bonding environment. Here I present a methodology for characterizing the molecular-level structure of liquid water interface from simulation data. This method can be used to explore waters static and/or dynamic response to a wide range of chemically and topologically heterogeneous solutes such as proteins.

Effect of species, life stage, and water temperature on the toxicity of hydrogen peroxide to fish

USGS Publications Warehouse

Rach, J.J.; Schreier, Theresa M.; Howe, G.E.; Redman, S.D.

1997-01-01

Hydrogen peroxide is a drug of low regulatory priority status that is effective in treating fish and fish eggs infected by fungi. However, only limited information is available to guide fish culturists in administering hydrogen peroxide to diseased fish. Laboratory tests were conducted to determine (1) the sensitivity of brown trout Salmo trutta, lake trout Salvelinus namaycush, fathead minnow Pimephales promelas, walleye Stizostedion vitreum, channel catfish Ictalurus punctatus, and bluegill Lepomis, machrochirus to hydrogen peroxide treatments; (2) the sensitivity of various life stages of rainbow trout Oncorhynchus mykiss to hydrogen peroxide treatments; and (3) the effect of water temperature on the acute toxicity of hydrogen peroxide to three fish species. Fish were exposed to hydrogen peroxide concentrations ranging from 100 to 5,000 mu L/L (ppm) for 15-min or 45-min treatments every other day for four consecutive treatments to determine the sensitivity of various species and life stages of fish. Except for walleye, most species of fish tested (less than or equal to 2 g) tolerated hydrogen peroxide of 1,000 mu L/L or greater. Walleyes were sensitive to hydrogen peroxide concentrations as low as 100 mu L/L. A correlation was found between the toxicity of hydrogen peroxide and the life stages of rainbow trout; larger fish were more sensitive. Generally, the toxicity of hydrogen peroxide increased for all species as water temperature increased. The results of these experiments demonstrate that it is important to consider the effects of species, life stage, and water temperature when conducting hydrogen peroxide treatments.

Mechanistic details for cobalt catalyzed photochemical hydrogen production in aqueous solution: Efficiencies of the photochemical and non-photochemical steps

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shan, Bing; Baine, Teera; Ma, Xuan Anh N.

2013-04-17

The use of sunlight to drive chemical reactions that lead to the reduction of water to produce hydrogen is a potential avenue of solar energy utilization. There are many individual steps that take place in this process. This paper reports the investigation of a particular system that involves light absorbing molecules, electron donating agents and a catalyst for water reduction to hydrogen. We evaluated the efficiency of the light induced formation of a strong electron donor, the use of this donor to reduce the catalyst and finally the efficiency of the catalyst to produce hydrogen from water. From this, themore » sources of loss of efficiency could be clearly identified and used in the design of better systems to produce hydrogen from water.« less

Process for the thermochemical production of hydrogen

DOEpatents

Norman, John H.; Russell, Jr., John L.; Porter, II, John T.; McCorkle, Kenneth H.; Roemer, Thomas S.; Sharp, Robert

1978-01-01

Hydrogen is thermochemically produced from water in a cycle wherein a first reaction produces hydrogen iodide and H.sub.2 SO.sub.4 by the reaction of iodine, sulfur dioxide and water under conditions which cause two distinct aqueous phases to be formed, i.e., a lighter sulfuric acid-bearing phase and a heavier hydrogen iodide-bearing phase. After separation of the two phases, the heavier phase containing most of the hydrogen iodide is treated, e.g., at a high temperature, to decompose the hydrogen iodide and recover hydrogen and iodine. The H.sub.2 SO.sub.4 is pyrolyzed to recover sulfur dioxide and produce oxygen.

Hydrogenation with monolith reactor under conditions of immiscible liquid phases

DOEpatents

Nordquist, Andrew Francis; Wilhelm, Frederick Carl; Waller, Francis Joseph; Machado, Reinaldo Mario

2002-01-01

The present invention relates to an improved for the hydrogenation of an immiscible mixture of an organic reactant in water. The immiscible mixture can result from the generation of water by the hydrogenation reaction itself or, by the addition of, water to the reactant prior to contact with the catalyst. The improvement resides in effecting the hydrogenation reaction in a monolith catalytic reactor from 100 to 800 cpi, at a superficial velocity of from 0.1 to 2 m/second in the absence of a cosolvent for the immiscible mixture. In a preferred embodiment, the hydrogenation is carried out using a monolith support which has a polymer network/carbon coating onto which a transition metal is deposited.

Water splitting: Taking cobalt in isolation

NASA Astrophysics Data System (ADS)

Wang, Aiqin; Zhang, Tao

2016-01-01

The sustainable production of hydrogen is key to the delivery of clean energy in a hydrogen economy; however, lower-cost alternatives to platinum electrocatalysts are needed. Now, isolated, earth-abundant cobalt atoms dispersed over nitrogen-doped graphene are shown to efficiently electrolyse water to generate hydrogen.

Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water

NASA Astrophysics Data System (ADS)

Cortright, R. D.; Davda, R. R.; Dumesic, J. A.

2002-08-01

Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose-which makes up the major energy reserves in plants and animals-to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water.

PubMed

Cortright, R D; Davda, R R; Dumesic, J A

2002-08-29

Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500 K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose -- which makes up the major energy reserves in plants and animals -- to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

Optimization of the water chemistry of the primary coolant at nuclear power plants with VVER

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barmin, L. F.; Kruglova, T. K.; Sinitsyn, V. P.

2005-01-15

Results of the use of automatic hydrogen-content meter for controlling the parameter of 'hydrogen' in the primary coolant circuit of the Kola nuclear power plant are presented. It is shown that the correlation between the 'hydrogen' parameter in the coolant and the 'hydrazine' parameter in the makeup water can be used for controlling the water chemistry of the primary coolant system, which should make it possible to optimize the water chemistry at different power levels.

Carbon-coated ceramic membrane reactor for the production of hydrogen by aqueous-phase reforming of sorbitol.

PubMed

Neira D'Angelo, M F; Ordomsky, V; Schouten, J C; van der Schaaf, J; Nijhuis, T A

2014-07-01

Hydrogen was produced by aqueous-phase reforming (APR) of sorbitol in a carbon-on-alumina tubular membrane reactor (4 nm pore size, 7 cm long, 3 mm internal diameter) that allows the hydrogen gas to permeate to the shell side, whereas the liquid remains in the tube side. The hydrophobic nature of the membrane serves to avoid water loss and to minimize the interaction between the ceramic support and water, thus reducing the risks of membrane degradation upon operation. The permeation of hydrogen is dominated by the diffusivity of the hydrogen in water. Thus, higher operation temperatures result in an increase of the flux of hydrogen. The differential pressure has a negative effect on the flux of hydrogen due to the presence of liquid in the larger pores. The membrane was suitable for use in APR, and yielded 2.5 times more hydrogen than a reference reactor (with no membrane). Removal of hydrogen through the membrane assists in the reaction by preventing its consumption in undesired reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SPE (tm) regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications

NASA Technical Reports Server (NTRS)

Mcelroy, J. F.

1990-01-01

Viewgraphs on SPE regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications are presented. Topics covered include: hydrogen-oxygen regenerative fuel cell energy storage system; electrochemical cell reactions; SPE cell voltage stability; passive water removal SPE fuel cell; fuel cell performance; SPE water electrolyzers; hydrophobic oxygen phase separator; hydrophilic/electrochemical hydrogen phase separator; and unitized regenerative fuel cell.

METHOD OF PURIFYING CATALYSTS

DOEpatents

Joris, G.G.

1958-09-01

It has been fuund that the presence of chlorine as an impurity adversely affects the performance of finely divided platinum catalysts such as are used in the isotopic exchange process for the production of beavy water. This chlorine impurity may be removed from these catalysts by treating the catalyst at an elevated temperature with dry hydrogen and then with wet hydrogen, having a hydrogen-water vapor volume of about 8: 1. This alternate treatment by dry hydrogen and wet hydrogen is continued until the chlorine is largely removed from the catalyst.

H2 spillover enhanced hydrogenation capability of TiO2 used for photocatalytic splitting of water: a traditional phenomenon for new applications.

PubMed

Zhu, Yingming; Liu, Dongsheng; Meng, Ming

2014-06-07

Black TiO2 was usually obtained via hydrogenation at high pressure and high temperature. Herein, we reported a facile hydrogenation of TiO2 in the presence of a small amount of Pt at relatively low temperature and atmospheric pressure. The hydrogen spillover from Pt to TiO2 accounts well for the greatly enhanced hydrogenation capability. The as-synthesized Pt/TiO2 exhibits remarkably improved photocatalytic activity for water splitting.

Simulating Asymmetric Top Impurities in Superfluid Clusters: A para-Water Dopant in para-Hydrogen.

PubMed

Zeng, Tao; Li, Hui; Roy, Pierre-Nicholas

2013-01-03

We present the first simulation study of bosonic clusters doped with an asymmetric top molecule. The path-integral Monte Carlo method with the latest methodological advance in treating rigid-body rotation [Noya, E. G.; Vega, C.; McBride, C. J. Chem. Phys.2011, 134, 054117] is employed to study a para-water impurity in para-hydrogen clusters with up to 20 para-hydrogen molecules. The growth pattern of the doped clusters is similar in nature to that of pure clusters. The para-water molecule appears to rotate freely in the cluster. The presence of para-water substantially quenches the superfluid response of para-hydrogen with respect to the space-fixed frame.

Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

NASA Technical Reports Server (NTRS)

Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

2014-01-01

Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

Water content and porosity effect on hydrogen radiolytic yields of geopolymers

NASA Astrophysics Data System (ADS)

Chupin, Frédéric; Dannoux-Papin, Adeline; Ngono Ravache, Yvette; d'Espinose de Lacaillerie, Jean-Baptiste

2017-10-01

The behavior of geopolymers under irradiation is a topic that has not been thoroughly investigated so far. However, if geopolymers are considered to be used as radioactive waste embedding matrices, their chemical and mechanical stability under ionizing radiation as well as low hydrogen production must be demonstrated. For that purpose, a particular focus is put on water radiolysis. Various formulations of geopolymers have been irradiated either with γ-rays (60Co source) or 95 MeV/amu 36Ar18+ ions beams and the hydrogen production has been quantified. This paper presents the results of radiolytic gas analysis in order to identify important structural parameters that influence confined water radiolysis. A correlation between geopolymers nature, water content on the one side, and the hydrogen radiolytic yield (G(H2)) on the other side, has been demonstrated. For both types of irradiations, a strong influence of the water content on the hydrogen radiolytic yield G(H2) is evidenced. The geopolymers porosity effect has been only highlighted under γ-rays irradiation.

Microstructure and hydrogen bonding in water-acetonitrile mixtures.

PubMed

Mountain, Raymond D

2010-12-16

The connection of hydrogen bonding between water and acetonitrile in determining the microheterogeneity of the liquid mixture is examined using NPT molecular dynamics simulations. Mixtures for six, rigid, three-site models for acetonitrile and one water model (SPC/E) were simulated to determine the amount of water-acetonitrile hydrogen bonding. Only one of the six acetonitrile models (TraPPE-UA) was able to reproduce both the liquid density and the experimental estimates of hydrogen bonding derived from Raman scattering of the CN stretch band or from NMR quadrupole relaxation measurements. A simple modification of the acetonitrile model parameters for the models that provided poor estimates produced hydrogen-bonding results consistent with experiments for two of the models. Of these, only one of the modified models also accurately determined the density of the mixtures. The self-diffusion coefficient of liquid acetonitrile provided a final winnowing of the modified model and the successful, unmodified model. The unmodified model is provisionally recommended for simulations of water-acetonitrile mixtures.

Sulphurous Mineral Waters: New Applications for Health

PubMed Central

Carbajo, Jose Manuel

2017-01-01

Sulphurous mineral waters have been traditionally used in medical hydrology as treatment for skin, respiratory, and musculoskeletal disorders. However, driven by recent intense research efforts, topical treatments are starting to show benefits for pulmonary hypertension, arterial hypertension, atherosclerosis, ischemia-reperfusion injury, heart failure, peptic ulcer, and acute and chronic inflammatory diseases. The beneficial effects of sulphurous mineral waters, sulphurous mud, or peloids made from sulphurous mineral water have been attributed to the presence of sulphur mainly in the form of hydrogen sulphide. This form is largely available in conditions of low pH when oxygen concentrations are also low. In the organism, small amounts of hydrogen sulphide are produced by some cells where they have numerous biological signalling functions. While high levels of hydrogen sulphide are extremely toxic, enzymes in the body are capable of detoxifying it by oxidation to harmless sulphate. Hence, low levels of hydrogen sulphide may be tolerated indefinitely. In this paper, we review the chemistry and actions of hydrogen sulphide in sulphurous mineral waters and its natural role in body physiology. This is followed by an update of available data on the impacts of exogenous hydrogen sulphide on the skin and internal cells and organs including new therapeutic possibilities of sulphurous mineral waters and their peloids. PMID:28484507

Water's hydrogen bonds in the hydrophobic effect: a simple model.

PubMed

Xu, Huafeng; Dill, Ken A

2005-12-15

We propose a simple analytical model to account for water's hydrogen bonds in the hydrophobic effect. It is based on computing a mean-field partition function for a water molecule in the first solvation shell around a solute molecule. The model treats the orientational restrictions from hydrogen bonding, and utilizes quantities that can be obtained from bulk water simulations. We illustrate the principles in a 2-dimensional Mercedes-Benz-like model. Our model gives good predictions for the heat capacity of hydrophobic solvation, reproduces the solvation energies and entropies at different temperatures with only one fitting parameter, and accounts for the solute size dependence of the hydrophobic effect. Our model supports the view that water's hydrogen bonding propensity determines the temperature dependence of the hydrophobic effect. It explains the puzzling experimental observation that dissolving a nonpolar solute in hot water has positive entropy.

A Simple, Low-cost, and Robust System to Measure the Volume of Hydrogen Evolved by Chemical Reactions with Aqueous Solutions

PubMed Central

Brack, Paul; Dann, Sandie; Wijayantha, K. G. Upul; Adcock, Paul; Foster, Simon

2016-01-01

There is a growing research interest in the development of portable systems which can deliver hydrogen on-demand to proton exchange membrane (PEM) hydrogen fuel cells. Researchers seeking to develop such systems require a method of measuring the generated hydrogen. Herein, we describe a simple, low-cost, and robust method to measure the hydrogen generated from the reaction of solids with aqueous solutions. The reactions are conducted in a conventional one-necked round-bottomed flask placed in a temperature controlled water bath. The hydrogen generated from the reaction in the flask is channeled through tubing into a water-filled inverted measuring cylinder. The water displaced from the measuring cylinder by the incoming gas is diverted into a beaker on a balance. The balance is connected to a computer, and the change in the mass reading of the balance over time is recorded using data collection and spreadsheet software programs. The data can then be approximately corrected for water vapor using the method described herein, and parameters such as the total hydrogen yield, the hydrogen generation rate, and the induction period can also be deduced. The size of the measuring cylinder and the resolution of the balance can be changed to adapt the setup to different hydrogen volumes and flow rates. PMID:27584581

Coupled jump rotational dynamics in aqueous nitrate solutions.

PubMed

Banerjee, Puja; Yashonath, Subramanian; Bagchi, Biman

2016-12-21

A nitrate ion (NO 3 - ) with its trigonal planar geometry and charges distributed among nitrogen and oxygen atoms can couple to the extensive hydrogen bond network of water to give rise to unique dynamical characteristics. We carry out detailed atomistic simulations and theoretical analyses to investigate these aspects and report certain interesting findings. We find that the nitrate ions in aqueous potassium nitrate solution exhibit large amplitude rotational jump motions that are coupled to the hydrogen bond rearrangement dynamics of the surrounding water molecules. The jump motion of nitrate ions bears certain similarities to the Laage-Hynes mechanism of rotational jump motions of tagged water molecules in neat liquid water. We perform a detailed atomic-level investigation of hydrogen bond rearrangement dynamics of water in aqueous KNO 3 solution to unearth two distinct mechanisms of hydrogen bond exchange that are instrumental to promote these jump motions of nitrate ions. As observed in an earlier study by Xie et al., in the first mechanism, after breaking a hydrogen bond with nitrate ion, water forms a new hydrogen bond with a water molecule, whereas the second mechanism involves just a switching of hydrogen bond between the two oxygen atoms of the same nitrate ion (W. J. Xie et al., J. Chem. Phys. 143, 224504 (2015)). The magnitude as well as nature of the reorientational jump of nitrate ion for the two mechanisms is different. In the first mechanism, nitrate ion predominantly undergoes out-of-plane rotation, while in the second mechanism, in-plane reorientation of NO 3 - is favourable. These have been deduced by computing the torque on the nitrate ion during the hydrogen bond switching event. We have defined and computed the time correlation function for coupled reorientational jump of nitrate and water and obtained the associated relaxation time which is also different for the two mechanisms. These results provide insight into the relation between the coupled reorientational jump dynamics of solute and solvent molecules.

Two-stage coal liquefaction without gas-phase hydrogen

DOEpatents

Stephens, H.P.

1986-06-05

A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

On-line hydrogen-isotope measurements of organic samples using elemental chromium: An extension for high temperature elemental-analyzer techniques

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B.; Meijer, Harro A.J.; Brand, Willi A.; Schimmelmann, Arndt

2015-01-01

The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while handling water as a bulk sample. The calibration of organic samples, commonly having high δ2H values, will benefit from the availability of suitably 2H-enriched reference waters, extending the VSMOW-SLAP scale above zero.

Density functional theory meta-GGA + U study of water incorporation in the metal-organic framework material Cu-BTC.

PubMed

Cockayne, Eric; Nelson, Eric B

2015-07-14

Water absorption in the metal-organic framework (MOF) material Cu-BTC, up to a concentration of 3.5 H2O per Cu ion, is studied via density functional theory at the meta-GGA + U level. The stable arrangements of water molecules show chains of hydrogen-bonded water molecules and a tendency to form closed cages at high concentration. Water clusters are stabilized primarily by a combination of water-water hydrogen bonding and Cu-water oxygen interactions. Stability is further enhanced by van der Waals interactions, electric field enhancement of water-water bonding, and hydrogen bonding of water to framework oxygens. We hypothesize that the tendency to form such stable clusters explains the particularly strong affinity of water to Cu-BTC and related MOFs with exposed metal sites.

The Conceptual Design of an Integrated Nuclearhydrogen Production Plant Using the Sulfur Cycle Water Decomposition System

NASA Technical Reports Server (NTRS)

Farbman, G. H.

1976-01-01

A hydrogen production plant was designed based on a hybrid electrolytic-thermochemical process for decomposing water. The sulfur cycle water decomposition system is driven by a very high temperature nuclear reactor that provides 1,283 K helium working gas. The plant is sized to approximately ten million standard cubic meters per day of electrolytically pure hydrogen and has an overall thermal efficiently of 45.2 percent. The economics of the plant were evaluated using ground rules which include a 1974 cost basis without escalation, financing structure and other economic factors. Taking into account capital, operation, maintenance and nuclear fuel cycle costs, the cost of product hydrogen was calculated at $5.96/std cu m for utility financing. These values are significantly lower than hydrogen costs from conventional water electrolysis plants and competitive with hydrogen from coal gasification plants.

Solar-hydrogen energy system for Pakistan

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lutfi, N.

1990-01-01

A solar-hydrogen energy system has been proposed for Pakistan as the best replacement for the present fossil fuel based energy system. It has been suggested to produce hydrogen via photovoltaic-electrolysis, utilizing the available non-agricultural sunny terrain in Baluchistan region. There will be a desalination plant for sea water desalination. The area under the photovoltaic panels with the availability of water would provide suitable environment for growing some cash crops. This would change the cast useless desert land into green productive farms. In order to show the quantitative benefits of the proposed system, future trends of important energy and economical parametersmore » have been studied with and without hydrogen introduction. The following parameters have been included: population, energy demand (fossil + hydrogen), energy production (fossil + hydrogen), gross national product, fossil energy imports, world energy prices, air pollution, quality of life, environmental savings due to hydrogen introduction, savings due to the higher utilization efficiency of hydrogen, by-product credit, agricultural income, income from hydrogen sale, photovoltaic cell area, total land area, water desalination plant capacity, capital investment, operating and maintenance cost, and total income from the system. The results indicate that adopting the solar-hydrogen energy system would eliminate the import dependency of fossil fuels, increase gross product per capita, reduce pollution, improve quality of life and establish a permanent and clean energy system. The total annual expenditure on the proposed system is less than the total income from the proposed system. The availability of water, the cash crop production, electricity and hydrogen would result in rapid development of Baluchistan, the largest province of Pakistan.« less

Molecular hydrogen alleviates motor deficits and muscle degeneration in mdx mice.

PubMed

Hasegawa, Satoru; Ito, Mikako; Fukami, Mayu; Hashimoto, Miki; Hirayama, Masaaki; Ohno, Kinji

2017-01-01

Duchenne muscular dystrophy (DMD) is a devastating muscle disease caused by a mutation in DMD encoding dystrophin. Oxidative stress accounts for dystrophic muscle pathologies in DMD. We examined the effects of molecular hydrogen in mdx mice, a model animal for DMD. The pregnant mother started to take supersaturated hydrogen water (>5 ppm) ad libitum from E15.5 up to weaning of the offspring. The mdx mice took supersaturated hydrogen water from weaning until age 10 or 24 weeks when they were sacrificed. Hydrogen water prevented abnormal body mass gain that is commonly observed in mdx mice. Hydrogen improved the spontaneous running distance that was estimated by a counter-equipped running-wheel, and extended the duration on the rota-rod. Plasma creatine kinase activities were decreased by hydrogen at ages 10 and 24 weeks. Hydrogen also decreased the number of central nuclei of muscle fibers at ages 10 and 24 weeks, and immunostaining for nitrotyrosine in gastrocnemius muscle at age 24 weeks. Additionally, hydrogen tended to increase protein expressions of antioxidant glutathione peroxidase 1, as well as anti-apoptotic Bcl-2, in skeletal muscle at age 10 weeks. Although molecular mechanisms of the diverse effects of hydrogen remain to be elucidated, hydrogen potentially improves muscular dystrophy in DMD patients.

Two-dimensional infrared spectroscopy of intermolecular hydrogen bonds in the condensed phase.

PubMed

Elsaesser, Thomas

2009-09-15

Hydrogen bonding plays a key role in the structural, physical, and chemical properties of liquids such as water and in macromolecular structures such as proteins. Vibrational spectroscopy is an important tool for understanding hydrogen bonding because it provides a way to observe local molecular geometries and their interaction with the environment. Linear vibrational spectroscopy has mapped characteristic changes of vibrational spectra and the occurrence of new bands that form upon hydrogen bonding. However, linear vibrational spectroscopy gives very limited insight into ultrafast dynamics of the underlying molecular interactions, such as the motions of hydrogen-bonded groups, energy dissipation and delocalization, and the fluctuations within hydrogen-bonded structures that occur in the ultrafast time domain. Nonlinear vibrational spectroscopy with its femtosecond time resolution can discern these dynamic processes in real time and has emerged as an important tool for unraveling molecular dynamics and for quantifying interactions that govern the vibrational and structural dynamics of hydrogen bonds. This Account reviews recent progress originating from third-order nonlinear methods of coherent multidimensional vibrational spectroscopy. Ultrafast dynamics of intermolecular hydrogen bonds are addressed for a number of prototype systems: hydrogen-bonded carboxylic acid dimers in an aprotic liquid environment, the disordered fluctuating hydrogen-bond network of liquid water, and DNA oligomers interacting with water. Cyclic carboxylic acid dimers display a rich scheme of vibrational couplings, resulting in OH stretching absorption bands with highly complex spectral envelopes. Two-dimensional spectroscopy of acetic acid dimers in a nonpolar liquid environment demonstrates that multiple Fermi resonances of the OH stretching mode with overtones and combination tones of fingerprint vibrations dominate both the 2D and linear absorption spectra. The coupling of the OH stretching mode with low-frequency hydrogen-bonding modes leads to additional progressions and coherent low-frequency hydrogen-bond motions in the subpicosecond time domain. In water, the 2D spectra reveal ultrafast spectral diffusion on a sub-100 fs time scale caused by the ultrafast structural fluctuations of the strongly coupled hydrogen-bond network. Librational motions play a key role for the ultrafast loss of structural memory. Spectral diffusion rates are enhanced by resonant transfer of OH stretching quanta between water molecules, typically occurring on a 100 fs time scale. In DNA oligomers, femtosecond nonlinear vibrational spectroscopy resolves NH and OH stretching bands in the highly congested infrared spectra of these molecules, which contain alternating adenine-thymine pairs. Studies at different levels of hydration reveal the spectral signatures of water molecules directly interacting with the phosphate groups of DNA and of a second water species forming a fluctuating environment around the DNA oligomers. We expect that the application of 2D infrared spectroscopy in an extended spectral range will reveal the intrinsic coupling between water and specific functional units of DNA.

Hydrogen-fueled engine

NASA Technical Reports Server (NTRS)

Laumann, E. A.; Reynolds, R. K. (Inventor)

1978-01-01

A hydrogen-oxygen fueled internal combustion engine is described, which utilizes an inert gas, such as argon, as a working fluid to increase the efficiency of the engine, eliminate pollution, and facilitate operation of a closed cycle energy system. In a system where sunlight or other intermittent energy source is available to separate hydrogen and oxygen from water, the oxygen and inert gas are taken into a diesel engine into which hydrogen is injected and ignited. The exhaust is cooled so that it contains only water and the inert gas. The inert gas in the exhaust is returned to the engine for use with fresh oxygen, while the water in the exhaust is returned to the intermittent energy source for reconversion to hydrogen and oxygen.

Advances of zeolite based membrane for hydrogen production via water gas shift reaction

NASA Astrophysics Data System (ADS)

Makertihartha, I. G. B. N.; Zunita, M.; Rizki, Z.; Dharmawijaya, P. T.

2017-07-01

Hydrogen is considered as a promising energy vector which can be obtained from various renewable sources. However, an efficient hydrogen production technology is still challenging. One technology to produce hydrogen with very high capacity with low cost is through water gas shift (WGS) reaction. Water gas shift reaction is an equilibrium reaction that produces hydrogen from syngas mixture by the introduction of steam. Conventional WGS reaction employs two or more reactors in series with inter-cooling to maximize conversion for a given volume of catalyst. Membrane reactor as new technology can cope several drawbacks of conventional reactor by removing reaction product and the reaction will favour towards product formation. Zeolite has properties namely high temperature, chemical resistant, and low price makes it suitable for membrane reactor applications. Moreover, it has been employed for years as hydrogen selective layer. This review paper is focusing on the development of membrane reactor for efficient water gas shift reaction to produce high purity hydrogen and carbon dioxide. Development of membrane reactor is discussed further related to its modification towards efficient reaction and separation from WGS reaction mixture. Moreover, zeolite framework suitable for WGS membrane reactor will be discussed more deeply.

Structures of water molecules in carbon nanotubes under electric fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winarto,; Takaiwa, Daisuke; Yamamoto, Eiji

2015-03-28

Carbon nanotubes (CNTs) are promising for water transport through membranes and for use as nano-pumps. The development of CNT-based nanofluidic devices, however, requires a better understanding of the properties of water molecules in CNTs because they can be very different from those in the bulk. Using all-atom molecular dynamics simulations, we investigate the effect of axial electric fields on the structure of water molecules in CNTs having diameters ranging from (7,7) to (10,10). The water dipole moments were aligned parallel to the electric field, which increases the density of water inside the CNTs and forms ordered ice-like structures. The electricmore » field induces the transition from liquid to ice nanotubes in a wide range of CNT diameters. Moreover, we found an increase in the lifetime of hydrogen bonds for water structures in the CNTs. Fast librational motion breaks some hydrogen bonds, but the molecular pairs do not separate and the hydrogen bonds reform. Thus, hydrogen bonds maintain the water structure in the CNTs, and the water molecules move collectively, decreasing the axial diffusion coefficient and permeation rate.« less

Nuclear driven water decomposition plant for hydrogen production

NASA Technical Reports Server (NTRS)

Parker, G. H.; Brecher, L. E.; Farbman, G. H.

1976-01-01

The conceptual design of a hydrogen production plant using a very-high-temperature nuclear reactor (VHTR) to energize a hybrid electrolytic-thermochemical system for water decomposition has been prepared. A graphite-moderated helium-cooled VHTR is used to produce 1850 F gas for electric power generation and 1600 F process heat for the water-decomposition process which uses sulfur compounds and promises performance superior to normal water electrolysis or other published thermochemical processes. The combined cycle operates at an overall thermal efficiency in excess of 45%, and the overall economics of hydrogen production by this plant have been evaluated predicated on a consistent set of economic ground rules. The conceptual design and evaluation efforts have indicated that development of this type of nuclear-driven water-decomposition plant will permit large-scale economic generation of hydrogen in the 1990s.

Experimental controls on D/H and 13C/12C ratios of kerogen, bitumen and oil during hydrous pyrolysis

USGS Publications Warehouse

Schimmelmann, A.; Boudou, J.-P.; Lewan, M.D.; Wintsch, R.P.

2001-01-01

Large isotopic transfers between water-derived hydrogen and organic hydrogen occurred during hydrous pyrolysis experiments of immature source rocks, in spite of only small changes in organic 13C/12C. Experiments at 330 ??C over 72 h using chips or powder containing kerogen types I and III identify the rock/water ratio as a main factor affecting ????D for water and organic hydrogen. Our data suggest that larger rock permeability and smaller rock grain size increase the H-isotopic transfer between water-derived hydrogen and thermally maturing organic matter. Increasing hydrostatic pressure may have a similar effect, but the evidence remains inconclusive. ?? 2001 Elsevier Science Ltd. All rights reserved.

Method of producing hydrogen. [KNO/sub 3/ and I/sub 2/

DOEpatents

Abraham, B.M.; Schreiner, F.

1975-12-30

Water is thermochemically decomposed to produce hydrogen by the following sequence of reactions. KNO/sub 3/ and I/sub 2/ are reacted to produce KI, NO and O/sub 2/, the NO and O/sub 2/ thus produced are reacted with water to form HNO/sub 3/, a hydrogen-containing iodide--NH/sub 4/I or HI--is formed from the HNO/sub 3/, and this iodide is thermally decomposed to produce hydrogen, all products of the reactions being recycled except hydrogen and oxygen. 2 claims, no drawings.

Hydrogen production by high-temperature water splitting using electron-conducting membranes

DOEpatents

Lee, Tae H.; Wang, Shuangyan; Dorris, Stephen E.; Balachandran, Uthamalingam

2004-04-27

A device and method for separating water into hydrogen and oxygen is disclosed. A first substantially gas impervious solid electron-conducting membrane for selectively passing hydrogen is provided and spaced from a second substantially gas impervious solid electron-conducting membrane for selectively passing oxygen. When steam is passed between the two membranes at disassociation temperatures the hydrogen from the disassociation of steam selectively and continuously passes through the first membrane and oxygen selectively and continuously passes through the second membrane, thereby continuously driving the disassociation of steam producing hydrogen and oxygen.

Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

NASA Astrophysics Data System (ADS)

Nielson, Kristine E.; Bowen, Gabriel J.

2010-03-01

Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

Hydrogen storage and evolution catalysed by metal hydride complexes.

PubMed

Fukuzumi, Shunichi; Suenobu, Tomoyoshi

2013-01-07

The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

Quantitative observations of hydrogen-induced, slow crack growth in a low alloy steel

NASA Technical Reports Server (NTRS)

Nelson, H. G.; Williams, D. P.

1973-01-01

Hydrogen-induced slow crack growth, da/dt, was studied in AISI-SAE 4130 low alloy steel in gaseous hydrogen and distilled water environments as a function of applied stress intensity, K, at various temperatures, hydrogen pressures, and alloy strength levels. At low values of K, da/dt was found to exhibit a strong exponential K dependence (Stage 1 growth) in both hydrogen and water. At intermediate values of K, da/dt exhibited a small but finite K dependence (Stage 2), with the Stage 2 slope being greater in hydrogen than in water. In hydrogen, at a constant K, (da/dt) sub 2 varied inversely with alloy strength level and varied essentially in the same complex manner with temperature and hydrogen pressure as noted previously. The results of this study provide support for most of the qualitative predictions of the lattice decohesion theory as recently modified by Oriani. The lack of quantitative agreement between data and theory and the inability of theory to explain the observed pressure dependence of slow crack growth are mentioned and possible rationalizations to account for these differences are presented.

Laboratory Studies of Hydrogen Gas Generation Using the Cobalt Chloride Catalyzed Sodium Borohydride-Water Reaction

DTIC Science & Technology

2015-07-01

already use hydrogen for weather balloons . Besides cost, hydrogen has other advantages over helium. Hydrogen has more lift than helium, so larger...of water vapor entering the gas stream, and avoid damaging the balloon /aerostat (aerostats typically have an operational temperature range of -50 to...Aerostats: “Gepard” Tethered Aerostats with Mobile Mooring Systems. Available at http://rosaerosystems.com/aero/obj7. Accessed June 4, 2015. 11

Hydrogen defects in α-Al2O3 and water weakening of sapphire and alumina ceramics between 600 and 1000°C: I. Infrared characterization of defects

USGS Publications Warehouse

Kronenberg, A.K.; Castaing, J.; Mitchell, T.E.; Kirby, S.H.

2000-01-01

Hydrogen impurities in materials influence their properties, including flow strength. α-Al2O3 single crystals and polycrystalline ceramics were annealed in supercritical water between 850 and 1025°C, under pressures in the range 1500–2000 MPa. A few specimens were further subjected to plastic deformation. Hydrogen penetration was examined using infrared absorption measurements of O–H bond vibrations, which revealed two kinds of hydrogen defects. In single crystals, defects are characterized by sharp O–H absorption bands assigned to interstitial protons. Hydrogen impurities of hydrothermally annealed ceramics and of all hydrothermally deformed specimens are characterized by broad O–H bands assigned to molecular water. The grain boundaries of hydrothermally annealed ceramics are severely damaged. The kinetics of hydrogen penetration is consistent with diffusion data.

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

NASA Astrophysics Data System (ADS)

Prisk, T. R.; Hoffmann, C.; Kolesnikov, A. I.; Mamontov, E.; Podlesnyak, A. A.; Wang, X.; Kent, P. R. C.; Anovitz, L. M.

2018-05-01

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factor reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10-100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

DOE PAGES

Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.; ...

2018-05-09

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS{sub 2} layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joshi, R. K., E-mail: r.joshi@unsw.edu.au, E-mail: alwarappan@cecri.res.in; Sahajwalla, V.; Shukla, S.

2016-01-15

Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS{sub 2}, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS{sub 2} layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS{sub 2} film resulted in hydrogen evolution. Our work shows thatmore » 2D MoS{sub 2} is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS{sub 2} shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS{sub 2} is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.« less

THEORETICAL TRANSIT SPECTRA FOR GJ 1214b AND OTHER 'SUPER-EARTHS'

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howe, Alex R.; Burrows, Adam S., E-mail: arhowe@astro.princeton.edu, E-mail: burrows@astro.princeton.edu

2012-09-10

We present new calculations of transit spectra of super-Earths that allow for atmospheres with arbitrary proportions of common molecular species and haze. We test this method with generic spectra, reproducing the expected systematics and absorption features, then apply it to the nearby super-Earth GJ 1214b, which has produced conflicting observational data, leaving the questions of a hydrogen-rich versus hydrogen-poor atmosphere and the water content of the atmosphere ambiguous. We present representative transit spectra for a range of classes of atmosphere models for GJ 1214b. Our analysis supports a hydrogen-rich atmosphere with a cloud or haze layer, although a hydrogen-poor modelmore » with {approx}<10% water is not ruled out. Several classes of models are ruled out, however, including hydrogen-rich atmospheres with no haze, hydrogen-rich atmospheres with a haze of {approx}0.01 {mu}m tholin particles, and hydrogen-poor atmospheres with major sources of absorption other than water. We propose an observational test to distinguish hydrogen-rich from hydrogen-poor atmospheres. Finally, we provide a library of theoretical transit spectra for super-Earths with a broad range of parameters to facilitate future comparison with anticipated data.« less

Exploring the possibility to store the mixed oxygen-hydrogen cluster in clathrate hydrate in molar ratio 1:2 (O2+2H2).

PubMed

Qin, Yan; Du, Qi-Shi; Xie, Neng-Zhong; Li, Jian-Xiu; Huang, Ri-Bo

2017-05-01

An interesting possibility is explored: storing the mixture of oxygen and hydrogen in clathrate hydrate in molar ratio 1:2. The interaction energies between oxygen, hydrogen, and clathrate hydrate are calculated using high level quantum chemical methods. The useful conclusion points from this study are summarized as follows. (1) The interaction energies of oxygen-hydrogen mixed cluster are larger than the energies of pure hydrogen molecular cluster. (2) The affinity of oxygen molecules with water molecules is larger than that of the hydrogen molecules with water molecules. (3) The dimension of O 2 -2H 2 interaction structure is smaller than the dimension of CO 2 -2H 2 interaction structure. (4) The escaping energy of oxygen molecules from the hydrate cell is larger than that of the hydrogen molecules. (5) The high affinity of the oxygen molecules with both the water molecules and the hydrogen molecules may promote the stability of oxygen-hydrogen mixture in the clathrate hydrate. Therefore it is possible to store the mixed (O 2 +2H 2 ) cluster in clathrate hydrate. Copyright © 2017 Elsevier Inc. All rights reserved.

Water Ice Abundance on Ceres

NASA Image and Video Library

2016-12-15

This frame from an animation shows dwarf planet Ceres overlaid with the concentration of hydrogen determined from data acquired by the gamma ray and neutron detector GRaND instrument aboard NASA Dawn spacecraft. The hydrogen is in the upper yard (or meter) of regolith, the loose surface material on Ceres. The color scale gives hydrogen content in water-equivalent units, which assumes all of the hydrogen is in the form of H2O. Blue indicates where hydrogen content is higher, near the poles, while red indicates lower content at lower latitudes. In reality, some of the hydrogen is in the form of water ice, while a portion of the hydrogen is in the form of hydrated minerals (such as OH, in serpentine group minerals). The color information is superimposed on shaded relief map for context. A second animation (Figure 2) compares the hydrogen content of Ceres' regolith with that of the giant asteroid Vesta, which Dawn orbited from 2011 to 2012. These data show Vesta is a much drier world, with a much lower percent of hydrogen in its regolith. Both maps were produced from data acquired by GRaND. Videos are available at http://photojournal.jpl.nasa.gov/catalog/PIA21081

The role of hydrogen in hot-salt stress corrosion cracking of titanium-aluminum alloys

NASA Technical Reports Server (NTRS)

Ondrejcin, R. S.

1971-01-01

Additional support is presented for the previously proposed role of hydrogen as an embrittling agent in hot-salt stress corrosion cracking of titanium-aluminum alloys. The main source of hydrogen formed during the reactions of titanium alloys with hot salt was identified as water associated with the salt. Hydrogen is produced by the reaction of an intermediate (hydrogen halide) with the alloy rather than from metal-water reactions. The fracture mode of precracked tensile specimens was ductile when the specimens were tested in air, and brittle when tests were made in high-pressure hydrogen. Stressed titanium-aluminum alloys also were cracked by bombardment with hydrogen ions produced in a proton accelerator. The approximate concentrations of the hydrogen ions in the alloys were calculated.

21 CFR 172.167 - Silver nitrate and hydrogen peroxide solution.

Code of Federal Regulations, 2010 CFR

2010-04-01

... agent in bottled water. (b) Hydrogen peroxide meets the specifications of the “Food Chemicals Codex... information on the availability of this material at NARA, call 202-741-6030 or go to: http://www.archives.gov... exceed 17 micrograms per kilogram in the treated bottled water, and the amount of hydrogen peroxide will...

Determination of the delta(2H/1H)of Water: RSIL Lab Code 1574

USGS Publications Warehouse

Revesz, Kinga; Coplen, Tyler B.

2008-01-01

Reston Stable Isotope Laboratory (RSIL) lab code 1574 describes a method used to determine the relative hydrogen isotope-ratio delta(2H,1H), abbreviated hereafter as d2H of water. The d2H measurement of water also is a component of the National Water Quality Laboratory (NWQL) schedules 1142 and 1172. The water is collected unfiltered in a 60-mL glass bottle and capped with a Polyseal cap. In the laboratory, the water sample is equilibrated with gaseous hydrogen using a platinum catalyst (Horita, 1988; Horita and others, 1989; Coplen and others, 1991). The reaction for the exchange of one hydrogen atom is shown in equation 1.

Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

NASA Astrophysics Data System (ADS)

Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

2008-02-01

Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10‰). Extrapolating the shock signature of the regrouped data to grains that experienced Martian meteorite-like shock pressures suggests that shock-induced water losses and hydrogen isotope enrichments could approach 1 wt.% H 2O and Δ D = + 100‰, respectively. If these values are valid, then impact shock effects could explain a substantial fraction of the low water contents and variable hydrogen isotope compositions of the Martian meteorite kaersutites.

Solar Water Splitting at λ=600 nm: A Step Closer to Sustainable Hydrogen Production.

PubMed

Zhang, Jinshui; Wang, Xinchen

2015-06-15

Overall water splitting with a semiconductor photocatalyst under visible-light irradiation is considered as a "dream reaction" in chemistry. The development of a 600 nm photocatalyst for solar water splitting highlighted here is not only an important milestone towards sustainable hydrogen production, but also a new starting point for artificial photosynthesis. STH=solar-to-hydrogen energy conversion efficiency. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen in Martian Meteorites

NASA Technical Reports Server (NTRS)

Peslier, A. H.; Hervig, R.; Irving, T.

2017-01-01

Most volatile studies of Mars have targeted its surface via spacecraft and rover data, and have evidenced surficial water in polar caps and the atmosphere, in the presence of river channels, and in the detection of water bearing minerals. The other focus of Martian volatile studies has been on Martian meteorites which are all from its crust. Most of these studies are on hydrous phases like apatite, a late-stage phase, i.e. crystallizing near the end of the differentiation sequence of Martian basalts and cumulates. Moreover, calculating the water content of the magma a phosphate crystallized from is not always possible, and yet is an essential step to estimate how much water was present in a parent magma and its source. Water, however, is primarily dissolved in the interiors of differentiated planets as hydrogen in lattice defects of nominally anhydrous minerals (olivine, pyroxene, feldspar) of the crust and mantle. This hydrogen has tremendous influence, even in trace quantities, on a planet's formation, geodynamics, cooling history and the origin of its volcanism and atmosphere as well as its potential for life. Studies of hydrogen in nominally anhydrous phases of Martian meteorites are rare. Measuring water contents and hydrogen isotopes in well-characterized nominally anhydrous minerals of Martian meteorites is the goal of our study. Our work aims at deciphering what influences the distribution and origin of hydrogen in Martian minerals, such as source, differentiation, degassing and shock.

Small-scale, hydrogen-oxidizing-denitrifying bioreactor for treatment of nitrate-contaminated drinking water.

PubMed

Smith, Richard L; Buckwalter, Seanne P; Repert, Deborah A; Miller, Daniel N

2005-05-01

Nitrate removal by hydrogen-coupled denitrification was examined using flow-through, packed-bed bioreactors to develop a small-scale, cost effective system for treating nitrate-contaminated drinking-water supplies. Nitrate removal was accomplished using a Rhodocyclus sp., strain HOD 5, isolated from a sole-source drinking-water aquifer. The autotrophic capacity of the purple non-sulfur photosynthetic bacterium made it particularly adept for this purpose. Initial tests used a commercial bioreactor filled with glass beads and countercurrent, non-sterile flow of an autotrophic, air-saturated, growth medium and hydrogen gas. Complete removal of 2 mM nitrate was achieved for more than 300 days of operation at a 2-h retention time. A low-cost hydrogen generator/bioreactor system was then constructed from readily available materials as a water treatment approach using the Rhodocyclus strain. After initial tests with the growth medium, the constructed system was tested using nitrate-amended drinking water obtained from fractured granite and sandstone aquifers, with moderate and low TDS loads, respectively. Incomplete nitrate removal was evident in both water types, with high-nitrite concentrations in the bioreactor output, due to a pH increase, which inhibited nitrite reduction. This was rectified by including carbon dioxide in the hydrogen stream. Additionally, complete nitrate removal was accomplished with wastewater-impacted surface water, with a concurrent decrease in dissolved organic carbon. The results of this study using three chemically distinct water supplies demonstrate that hydrogen-coupled denitrification can serve as the basis for small-scale remediation and that pilot-scale testing might be the next logical step.

Small-scale, hydrogen-oxidizing-denitrifying bioreactor for treatment of nitrate-contaminated drinking water

USGS Publications Warehouse

Smith, R.L.; Buckwalter, S.P.; Repert, D.A.; Miller, D.N.

2005-01-01

Nitrate removal by hydrogen-coupled denitrification was examined using flow-through, packed-bed bioreactors to develop a small-scale, cost effective system for treating nitrate-contaminated drinking-water supplies. Nitrate removal was accomplished using a Rhodocyclus sp., strain HOD 5, isolated from a sole-source drinking-water aquifer. The autotrophic capacity of the purple non-sulfur photosynthetic bacterium made it particularly adept for this purpose. Initial tests used a commercial bioreactor filled with glass beads and countercurrent, non-sterile flow of an autotrophic, air-saturated, growth medium and hydrogen gas. Complete removal of 2 mM nitrate was achieved for more than 300 days of operation at a 2-h retention time. A low-cost hydrogen generator/bioreactor system was then constructed from readily available materials as a water treatment approach using the Rhodocyclus strain. After initial tests with the growth medium, the constructed system was tested using nitrate-amended drinking water obtained from fractured granite and sandstone aquifers, with moderate and low TDS loads, respectively. Incomplete nitrate removal was evident in both water types, with high-nitrite concentrations in the bioreactor output, due to a pH increase, which inhibited nitrite reduction. This was rectified by including carbon dioxide in the hydrogen stream. Additionally, complete nitrate removal was accomplished with wastewater-impacted surface water, with a concurrent decrease in dissolved organic carbon. The results of this study using three chemically distinct water supplies demonstrate that hydrogen-coupled denitrification can serve as the basis for small-scale remediation and that pilot-scale testing might be the next logical step.

Sulfur Hydrogen Bonding in Isolated Monohydrates: Furfuryl Mercaptan versus Furfuryl Alcohol.

PubMed

Juanes, Marcos; Lesarri, Alberto; Pinacho, Ruth; Charro, Elena; Rubio, José E; Enríquez, Lourdes; Jaraíz, Martín

2018-05-02

The hydrogen bonds involving sulfur in the furfuryl mercaptan monohydrate are compared with the interactions originating from the hydroxyl group in furfuryl alcohol. The dimers with water were created in a supersonic jet expansion and characterized using microwave spectroscopy and supporting molecular orbital calculations. In furfuryl alcohol-water, a single isomer is observed, in which the water molecule forms an insertion complex with two simultaneous hydrogen bonds to the alcohol (O-H⋅⋅⋅O w ) and the ring oxygen (O w -H⋅⋅⋅O r ). When the alcohol is replaced by a thiol group in furfuryl mercaptan-water, two isomers are observed, with the thiol group preferentially behaving as proton donor to water. The first isomer is topologically equivalent to the alcohol analog but the stronger hydrogen bond is now established by water and the ring oxygen, assisted by a thiol S-H⋅⋅⋅O w hydrogen bond. In the second isomer the sulfur group accepts a proton from water, forming a O w -H⋅⋅⋅S hydrogen bond. Binding energies for the mercaptan-water dimer are predicted around 12 kJ mol -1 weaker than in the alcohol hydrate (B3LYP-D3(BJ)). The non-covalent interactions in the furfuryl dimers are dominantly electrostatic according to a SAPT(0) energy decomposition, but with increasing dispersion components in the mercaptan dimers, which are larger for the isomer with the weaker O w -H⋅⋅⋅S interaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Onset of hydrogen bonded collective network of water in 1,4-dioxane.

PubMed

Luong, Trung Quan; Verma, Pramod Kumar; Mitra, Rajib Kumar; Havenith, Martina

2011-12-22

We have studied the evolution of water hydrogen bonded collective network dynamics in mixtures of 1,4-dioxane (Dx) as the mole fraction of water (X(w)) increases from 0.005 to 0.54. The inter- and intramolecular vibrations of water have been observed using terahertz time domain spectroscopy (THz-TDS) in the frequency range 0.4-1.4 THz (13-47 cm(-1)) and Fourier transform infrared (FTIR) spectroscopy in the far-infrared (30-650 cm(-1)) and mid-infrared (3000-3700 cm(-1)) regions. These results have been correlated with the reactivity of water in these mixtures as determined by kinetic studies of the solvolysis reaction of benzoyl chloride (BzCl). Our studies show an onset of intermolecular hydrogen bonded water network dynamics beyond X(w) ≥ 0.1. At the same concentration, we observe a rapid increase of the rate constant of solvolysis of BzCl in water-Dx mixtures. Our results establish a correlation between the onset of collective hydrogen bonded network with the solvation dynamics and the activity of clustered water.

Hydrogen sulfide emission in sewer networks: a two-phase modeling approach to the sulfur cycle.

PubMed

Yongsiri, C; Vollertsen, J; Hvitved-Jacobsen, T

2004-01-01

Wherever transport of anaerobic wastewater occurs, potential problems associated with hydrogen sulfide in relation to odor nuisance, health risk and corrosion exist. Improved understanding of prediction of hydrogen sulfide emission into the sewer atmosphere is needed for better evaluation of such problems in sewer networks. A two-phase model for emission of hydrogen sulfide along stretches of gravity sewers is presented to estimate the occurrence of both sulfide in the water phase and hydrogen sulfide in the sewer atmosphere. The model takes into account air-water mass transfer of hydrogen sulfide and interactions with other processes in the sulfur cycle. Various emission scenarios are simulated to illustrate the release characteristics of hydrogen sulfide.

Hydrogen production by high temperature water splitting using electron conducting membranes

DOEpatents

Balachandran, Uthamalingam; Wang, Shuangyan; Dorris, Stephen E.; Lee, Tae H.

2006-08-08

A device and method for separating water into hydrogen and oxygen is disclosed. A first substantially gas impervious solid electron-conducting membrane for selectively passing protons or hydrogen is provided and spaced from a second substantially gas impervious solid electron-conducting membrane for selectively passing oxygen. When steam is passed between the two membranes at dissociation temperatures the hydrogen from the dissociation of steam selectively and continuously passes through the first membrane and oxygen selectively and continuously passes through the second membrane, thereby continuously driving the dissociation of steam producing hydrogen and oxygen. The oxygen is thereafter reacted with methane to produce syngas which optimally may be reacted in a water gas shift reaction to produce CO₂ and H₂.

On the cooperativity of association and reference energy scales in thermodynamic perturbation theory

NASA Astrophysics Data System (ADS)

Marshall, Bennett D.

2016-11-01

Equations of state for hydrogen bonding fluids are typically described by two energy scales. A short range highly directional hydrogen bonding energy scale as well as a reference energy scale which accounts for dispersion and orientationally averaged multi-pole attractions. These energy scales are always treated independently. In recent years, extensive first principles quantum mechanics calculations on small water clusters have shown that both hydrogen bond and reference energy scales depend on the number of incident hydrogen bonds of the water molecule. In this work, we propose a new methodology to couple the reference energy scale to the degree of hydrogen bonding in the fluid. We demonstrate the utility of the new approach by showing that it gives improved predictions of water-hydrocarbon mutual solubilities.

The interaction of radiation-generated radicals with myoglobin in aqueous solution—V. The indirect action of 2-methyl-2-hydroxypropyl radicals on oxymyoglobin

NASA Astrophysics Data System (ADS)

Whitburn, Kevin D.; Hoffman, Morton Z.

The interaction of radiation-generated 2-methyl-2-hydroxypropyl radicals (derived from t-butyl alcohol) with oxymyoglobin has been examined at pH 7.3. In N 2O-saturated solutions, oxymyoglobin is converted to the ferri and ferryl derivatives of myoglobin; the production of ferrylmyoglobin is essentially eliminated when catalase is present in solution during irradiation. In deaerated solutions containing catalase, oxymyoglobin is converted to both ferro- and ferrimyoglobin during irradiation. When added O 2 is initially present, all compositional changes occur after irradiation; the presence of catalase diminishes, but does not eliminate, the extent of these postirradiation conversions of oxymyoglobin to the ferri and ferryl derivatives. These observations are interpreted in terms of the scavenging of the 2-methyl-2-hydroxypropyl radicals by O 2 to generate their peroxy analogs, which causes a displacement of the equilibrium between oxy- and ferromyoglobin. The peroxy radicals decay to produce H 2O 2, an organic peroxide, and other products. These peroxides subsequently react with ferromyoglobin to produce the ferryl form; the rate of the reaction increases with decreasing [O 2] as [ferromyoglobin] increases. This reaction is sufficiently fast in deaerated solution that substantial conversion of ferromyoglobin to ferrylmyoglobin occurs during the time of irradiation. The formation of the ferryl derivative in the presence of unconverted ferromyoglobin drives a concurrent synproportion reaction which produces ferrimyoglobin. Overall, no direct interaction of 2-methyl-2-hydroxypropyl radicals, nor their peroxy analogs, with myoglobin is indicated; all reactivity is accountable by the peroxide products of these radicals.

Crystal water as the mol-ecular glue for obtaining different co-crystal ratios: the case of gallic acid tris-caffeine hexa-hydrate.

PubMed

Vella-Zarb, L; Baisch, U

2018-04-01

The crystal structure of the hexa-hydrate co-crystal of gallic acid and caffeine, C 7 H 6 O 5 ·3C 8 H 10 N 4 O 2 ·6H 2 O or GAL3CAF·6H 2 O , is a remarkable example of the importance of hydrate water acting as structural glue to facilitate the crystallization of two components of different stoichiometries and thus to compensate an imbalance of hydrogen-bond donors and acceptors. The water mol-ecules provide the additional hydrogen bonds required to form a crystalline solid. Whereas the majority of hydrogen bonds forming the inter-molecular network between gallic acid and caffeine are formed by crystal water, only one direct classical hydrogen bond between two mol-ecules is formed between the carb-oxy-lic oxygen of gallic acid and the carbonyl oxygen of caffeine with d ( D ⋯ A ) = 2.672 (2) Å. All other hydrogen bonds either involve crystal water or utilize protonated carbon atoms as donors.

Cosolvent effect on the dynamics of water in aqueous binary mixtures

NASA Astrophysics Data System (ADS)

Zhang, Xia; Zhang, Lu; Jin, Tan; Zhang, Qiang; Zhuang, Wei

2018-04-01

Water rotational dynamics in the mixtures of water and amphiphilic molecules, such as acetone and dimethyl sulfoxide (DMSO), measured by femtosecond infrared, often vary non-monotonically as the amphiphilic molecule's molar fraction changes from 0 to 1. Recent study has attributed the non-ideal water rotation with concentration in DMSO-water mixtures to different microscopic hydrophilic-hydrophobic segregation structure in water-rich and water-poor mixtures. Interestingly, the acetone molecule has very similar molecular structure to DMSO, but the extremum of the water rotational time in the DMSO-water mixtures significantly shifts to lower concentration and the rotation of water is much faster than those in acetone-water mixtures. The simulation results here shows that the non-ideal rotational dynamics of water in both mixtures are due to the frame rotation during the interval of hydrogen bond (HB) switchings. A turnover of the frame rotation with concentration takes place as the structure transition of mixture from the hydrogen bond percolation structure to the hydrophobic percolation structure. The weak acetone-water hydrogen bond strengthens the hydrophobic aggregation and accelerates the relaxation of the hydrogen bond, so that the structure transition takes places at lower concentration and the rotation of water is faster in acetone-water mixture than in DMSO-water mixture. A generally microscopic picture on the mixing effect on the water dynamics in binary aqueous mixtures is presented here.

Hydrogen peroxide kinetics in water radiolysis

NASA Astrophysics Data System (ADS)

Iwamatsu, Kazuhiro; Sundin, Sara; LaVerne, Jay A.

2018-04-01

The kinetics of the formation and reaction of hydrogen peroxide in the long time γ- radiolysis of water is examined using a combination of experiment with model calculations. Escape yields of hydrogen peroxide on the microsecond time scale are easily measured with added radical scavengers even with substantial amounts of initial added hydrogen peroxide. The γ-radiolysis of aqueous hydrogen peroxide solutions without added radical scavengers reach a steady state limiting concentration of hydrogen peroxide with increasing dose, and that limit is directly proportional to the initial concentration of added hydrogen peroxide. The dose necessary to reach that limiting hydrogen peroxide concentration is also proportional to the initial concentration, but dose rate has a very small effect. The addition of molecular hydrogen to aqueous solutions of hydrogen peroxide leads to a decrease in the high dose limiting hydrogen peroxide concentration that is linear with the initial hydrogen concentration, but the amount of decrease is not stoichiometric. Proton irradiations of solutions with added hydrogen peroxide and hydrogen are more difficult to predict because of the decreased yields of radicals; however, with a substantial increase in dose rate there is a sufficient decrease in radical yields that hydrogen addition has little effect on hydrogen peroxide decay.

A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ohmura, Ryo; Ripmeester, John A.

2011-02-01

Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO2 molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.

On-site manufacture of propellant oxygen from lunar resources

NASA Technical Reports Server (NTRS)

Rosenberg, Sanders D.

1992-01-01

The Aerojet Carbothermal Process for the manufacture of oxygen from lunar resources has three essential steps: the reduction of silicate with methane to form carbon monoxide and hydrogen; the reduction of carbon monoxide with hydrogen to form methane and water; and the electrolysis of water to form oxygen and hydrogen. This cyclic process does not depend upon the presence of water or water precursors in the lunar materials; it will produce oxygen from silicates regardless of their precise composition and fine structure. Research on the first step of the process was initiated by determining some of the operating conditions required to reduce igneous rock with carbon and silicon carbide. The initial phase of research on the second step is completed; quantitative conversion of carbon monoxide and hydrogen to methane and water was achieved with a nickel-on-kieselguhr catalyst. The equipment used in and the results obtained from these process studies are reported in detail.

Hybrid bio-photo-electro-chemical cells for solar water splitting

PubMed Central

Pinhassi, Roy I.; Kallmann, Dan; Saper, Gadiel; Dotan, Hen; Linkov, Artyom; Kay, Asaf; Liveanu, Varda; Schuster, Gadi; Adir, Noam; Rothschild, Avner

2016-01-01

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm−2. Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel. PMID:27550091

Hybrid bio-photo-electro-chemical cells for solar water splitting.

PubMed

Pinhassi, Roy I; Kallmann, Dan; Saper, Gadiel; Dotan, Hen; Linkov, Artyom; Kay, Asaf; Liveanu, Varda; Schuster, Gadi; Adir, Noam; Rothschild, Avner

2016-08-23

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm(-2). Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel.

HYBRID SULFUR PROCESS REFERENCE DESIGN AND COST ANALYSIS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorensek, M.; Summers, W.; Boltrunis, C.

2009-05-12

This report documents a detailed study to determine the expected efficiency and product costs for producing hydrogen via water-splitting using energy from an advanced nuclear reactor. It was determined that the overall efficiency from nuclear heat to hydrogen is high, and the cost of hydrogen is competitive under a high energy cost scenario. It would require over 40% more nuclear energy to generate an equivalent amount of hydrogen using conventional water-cooled nuclear reactors combined with water electrolysis compared to the proposed plant design described herein. There is a great deal of interest worldwide in reducing dependence on fossil fuels, whilemore » also minimizing the impact of the energy sector on global climate change. One potential opportunity to contribute to this effort is to replace the use of fossil fuels for hydrogen production by the use of water-splitting powered by nuclear energy. Hydrogen production is required for fertilizer (e.g. ammonia) production, oil refining, synfuels production, and other important industrial applications. It is typically produced by reacting natural gas, naphtha or coal with steam, which consumes significant amounts of energy and produces carbon dioxide as a byproduct. In the future, hydrogen could also be used as a transportation fuel, replacing petroleum. New processes are being developed that would permit hydrogen to be produced from water using only heat or a combination of heat and electricity produced by advanced, high temperature nuclear reactors. The U.S. Department of Energy (DOE) is developing these processes under a program known as the Nuclear Hydrogen Initiative (NHI). The Republic of South Africa (RSA) also is interested in developing advanced high temperature nuclear reactors and related chemical processes that could produce hydrogen fuel via water-splitting. This report focuses on the analysis of a nuclear hydrogen production system that combines the Pebble Bed Modular Reactor (PBMR), under development by PBMR (Pty.) Ltd. in the RSA, with the Hybrid Sulfur (HyS) Process, under development by the Savannah River National Laboratory (SRNL) in the US as part of the NHI. This work was performed by SRNL, Westinghouse Electric Company, Shaw, PBMR (Pty) Ltd., and Technology Insights under a Technical Consulting Agreement (TCA). Westinghouse Electric, serving as the lead for the PBMR process heat application team, established a cost-shared TCA with SRNL to prepare an updated HyS thermochemical water-splitting process flowsheet, a nuclear hydrogen plant preconceptual design and a cost estimate, including the cost of hydrogen production. SRNL was funded by DOE under the NHI program, and the Westinghouse team was self-funded. The results of this work are presented in this Final Report. Appendices have been attached to provide a detailed source of information in order to document the work under the TCA contract.« less

High-Yield Hydrogen Production from Starch and Water by a Synthetic Enzymatic Pathway

PubMed Central

Zhang, Y.-H. Percival; Evans, Barbara R.; Mielenz, Jonathan R.; Hopkins, Robert C.; Adams, Michael W.W.

2007-01-01

Background The future hydrogen economy offers a compelling energy vision, but there are four main obstacles: hydrogen production, storage, and distribution, as well as fuel cells. Hydrogen production from inexpensive abundant renewable biomass can produce cheaper hydrogen, decrease reliance on fossil fuels, and achieve zero net greenhouse gas emissions, but current chemical and biological means suffer from low hydrogen yields and/or severe reaction conditions. Methodology/Principal Findings Here we demonstrate a synthetic enzymatic pathway consisting of 13 enzymes for producing hydrogen from starch and water. The stoichiometric reaction is C6H10O5 (l)+7 H2O (l)→12 H2 (g)+6 CO2 (g). The overall process is spontaneous and unidirectional because of a negative Gibbs free energy and separation of the gaseous products with the aqueous reactants. Conclusions Enzymatic hydrogen production from starch and water mediated by 13 enzymes occurred at 30°C as expected, and the hydrogen yields were much higher than the theoretical limit (4 H2/glucose) of anaerobic fermentations. Significance The unique features, such as mild reaction conditions (30°C and atmospheric pressure), high hydrogen yields, likely low production costs ($∼2/kg H2), and a high energy-density carrier starch (14.8 H2-based mass%), provide great potential for mobile applications. With technology improvements and integration with fuel cells, this technology also solves the challenges associated with hydrogen storage, distribution, and infrastructure in the hydrogen economy. PMID:17520015

How to Make a Helium Atmosphere

NASA Image and Video Library

2015-06-11

This diagram illustrates how hypothetical helium atmospheres might form. These would be on planets about the mass of Neptune, or smaller, which orbit tightly to their stars, whipping around in just days. They are thought to have cores of water or rock, surrounded by thick atmospheres of gas. Radiation from their nearby stars would boil off hydrogen and helium, but because hydrogen is lighter, more hydrogen would escape. It's also possible that planetary bodies, such as asteroids, could impact the planet, sending hydrogen out into space. Over time, the atmospheres would become enriched in helium. With less hydrogen in the planets' atmospheres, the concentration of methane and water would go down. Both water and methane consist in part of hydrogen. Eventually, billions of years later (a "Gyr" equals one billion years), the abundances of the water and methane would be greatly reduced. Since hydrogen would not be abundant, the carbon would be forced to pair with oxygen, forming carbon monoxide. NASA's Spitzer Space Telescope observed a proposed helium planet, GJ 436b, with these traits: it lacks methane, and appears to contain carbon monoxide. Future observations are needed to detect helium itself in the atmospheres of these planets, and confirm this theory. http://photojournal.jpl.nasa.gov/catalog/PIA19345

Hydrogen in drinking water attenuates noise-induced hearing loss in guinea pigs.

PubMed

Lin, Ying; Kashio, Akinori; Sakamoto, Takashi; Suzukawa, Keigo; Kakigi, Akinobu; Yamasoba, Tatsuya

2011-01-03

It has been shown that molecular hydrogen acts as a therapeutic and preventive antioxidant by selectively reducing the hydroxyl radical, the most cytotoxic of the reactive oxygen species. In the present study, we tested the hypothesis that acoustic damage in guinea pigs can be attenuated by the consumption of molecular hydrogen. Guinea pigs received normal water or hydrogen-rich water for 14 days before they were exposed to 115 dB SPL 4-kHz octave band noise for 3h. Animals in each group underwent measurements for auditory brainstem response (ABR) or distortion-product otoacoustic emissions (DPOAEs) before the treatment (baseline) and immediately, 1, 3, 7, and 14 days after noise exposure. The ABR thresholds at 2 and 4 kHz were significantly better on post-noise days 1, 3, and 14 in hydrogen-treated animals when compared to the normal water-treated controls. Compared to the controls, the hydrogen-treated animals showed greater amplitude of DPOAE input/output growth functions during the recovery process, with statistical significance detected on post-noise days 3 and 7. These findings suggest that hydrogen can facilitate the recovery of hair cell function and attenuate noise-induced temporary hearing loss. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Hydrogen production from carbonaceous material

DOEpatents

Lackner, Klaus S.; Ziock, Hans J.; Harrison, Douglas P.

2004-09-14

Hydrogen is produced from solid or liquid carbon-containing fuels in a two-step process. The fuel is gasified with hydrogen in a hydrogenation reaction to produce a methane-rich gaseous reaction product, which is then reacted with water and calcium oxide in a hydrogen production and carbonation reaction to produce hydrogen and calcium carbonate. The calcium carbonate may be continuously removed from the hydrogen production and carbonation reaction zone and calcined to regenerate calcium oxide, which may be reintroduced into the hydrogen production and carbonation reaction zone. Hydrogen produced in the hydrogen production and carbonation reaction is more than sufficient both to provide the energy necessary for the calcination reaction and also to sustain the hydrogenation of the coal in the gasification reaction. The excess hydrogen is available for energy production or other purposes. Substantially all of the carbon introduced as fuel ultimately emerges from the invention process in a stream of substantially pure carbon dioxide. The water necessary for the hydrogen production and carbonation reaction may be introduced into both the gasification and hydrogen production and carbonation reactions, and allocated so as transfer the exothermic heat of reaction of the gasification reaction to the endothermic hydrogen production and carbonation reaction.

Hydrogen bonding and transportation properties of water confined in the single-walled carbon nanotube in the pulse-field

NASA Astrophysics Data System (ADS)

Zhou, Min; Hu, Ying; Liu, Jian-chuan; Cheng, Ke; Jia, Guo-zhu

2017-10-01

In this paper, molecular dynamics simulations were performed to investigate the transportation and hydrogen bonding dynamics of water confined in (6, 6) single-walled carbon nanotube (SWCNT) in the absence and presence of time-dependent pulse-field. The effects of pulse-field range from microwave to ultraviolet frequency on the diffusivity and hydrogen bonding of confined water were analyzed. The significant confinement effect due to the narrow space inside SWCNT was observed.

Toward prediction of alkane/water partition coefficients.

PubMed

Toulmin, Anita; Wood, J Matthew; Kenny, Peter W

2008-07-10

Partition coefficients were measured for 47 compounds in the hexadecane/water ( P hxd) and 1-octanol/water ( P oct) systems. Some types of hydrogen bond acceptor presented by these compounds to the partitioning systems are not well represented in the literature of alkane/water partitioning. The difference, DeltalogP, between logP oct and logP hxd is a measure of the hydrogen bonding potential of a molecule and is identified as a target for predictive modeling. Minimized molecular electrostatic potential ( V min) was shown to be an effective predictor of the contribution of hydrogen bond acceptors to DeltalogP. Carbonyl oxygen atoms were found to be stronger hydrogen bond acceptors for their electrostatic potential than heteroaromatic nitrogen or oxygen bound to hypervalent sulfur or nitrogen. Values of V min calculated for hydrogen-bonded complexes were used to explore polarization effects. Predicted logP hxd and DeltalogP were shown to be more effective than logP oct for modeling brain penetration for a data set of 18 compounds.

Solar hydrogen: harvesting light and heat from sun (Presentation Recording)

NASA Astrophysics Data System (ADS)

Guo, Liejin; Jing, Dengwei

2015-09-01

My research group in the State Key Laboratory of Multiphase Flow in Power Engineering (SKLMF), Xi'an Jiaotong University has been focusing on renewable energy, especially solar hydrogen, for about 20 years. In this presentation, I will present the most recent progress in our group on solar hydrogen production using light and heat. Firstly, "cheap" photoelectrochemical and photocatalytic water splitting, including both nanostructured materials and pilot-scale demonstration in our group for light-driven solar hydrogen (artificial photosynthesis) will be introduced. Then I will make a deep introduction to the achievements on the thermal-driven solar hydrogen, i.e., biomass/coal gasification in supercritical water for large-scale and low-cost hydrogen production using concentrated solar light.

Recent Progress in Metal‐Organic Frameworks for Applications in Electrocatalytic and Photocatalytic Water Splitting

PubMed Central

Wang, Wei; Xu, Xiaomin; Zhou, Wei

2017-01-01

The development of clean and renewable energy materials as alternatives to fossil fuels is foreseen as a potential solution to the crucial problems of environmental pollution and energy shortages. Hydrogen is an ideal energy material for the future, and water splitting using solar/electrical energy is one way to generate hydrogen. Metal‐organic frameworks (MOFs) are a class of porous materials with unique properties that have received rapidly growing attention in recent years for applications in water splitting due to their remarkable design flexibility, ultra‐large surface‐to‐volume ratios and tunable pore channels. This review focuses on recent progress in the application of MOFs in electrocatalytic and photocatalytic water splitting for hydrogen generation, including both oxygen and hydrogen evolution. It starts with the fundamentals of electrocatalytic and photocatalytic water splitting and the related factors to determine the catalytic activity. The recent progress in the exploitation of MOFs for water splitting is then summarized, and strategies for designing MOF‐based catalysts for electrocatalytic and photocatalytic water splitting are presented. Finally, major challenges in the field of water splitting are highlighted, and some perspectives of MOF‐based catalysts for water splitting are proposed. PMID:28435777

Hydrogen storage methods.

PubMed

Züttel, Andreas

2004-04-01

Hydrogen exhibits the highest heating value per mass of all chemical fuels. Furthermore, hydrogen is regenerative and environmentally friendly. There are two reasons why hydrogen is not the major fuel of today's energy consumption. First of all, hydrogen is just an energy carrier. And, although it is the most abundant element in the universe, it has to be produced, since on earth it only occurs in the form of water and hydrocarbons. This implies that we have to pay for the energy, which results in a difficult economic dilemma because ever since the industrial revolution we have become used to consuming energy for free. The second difficulty with hydrogen as an energy carrier is its low critical temperature of 33 K (i.e. hydrogen is a gas at ambient temperature). For mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage material is crucial. Hydrogen can be stored using six different methods and phenomena: (1) high-pressure gas cylinders (up to 800 bar), (2) liquid hydrogen in cryogenic tanks (at 21 K), (3) adsorbed hydrogen on materials with a large specific surface area (at T<100 K), (4) absorbed on interstitial sites in a host metal (at ambient pressure and temperature), (5) chemically bonded in covalent and ionic compounds (at ambient pressure), or (6) through oxidation of reactive metals, e.g. Li, Na, Mg, Al, Zn with water. The most common storage systems are high-pressure gas cylinders with a maximum pressure of 20 MPa (200 bar). New lightweight composite cylinders have been developed which are able to withstand pressures up to 80 MPa (800 bar) and therefore the hydrogen gas can reach a volumetric density of 36 kg.m(-3), approximately half as much as in its liquid state. Liquid hydrogen is stored in cryogenic tanks at 21.2 K and ambient pressure. Due to the low critical temperature of hydrogen (33 K), liquid hydrogen can only be stored in open systems. The volumetric density of liquid hydrogen is 70.8 kg.m(-3), and large volumes, where the thermal losses are small, can cause hydrogen to reach a system mass ratio close to one. The highest volumetric densities of hydrogen are found in metal hydrides. Many metals and alloys are capable of reversibly absorbing large amounts of hydrogen. Charging can be done using molecular hydrogen gas or hydrogen atoms from an electrolyte. The group one, two and three light metals (e.g. Li, Mg, B, Al) can combine with hydrogen to form a large variety of metal-hydrogen complexes. These are especially interesting because of their light weight and because of the number of hydrogen atoms per metal atom, which is two in many cases. Hydrogen can also be stored indirectly in reactive metals such as Li, Na, Al or Zn. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Since water is the product of the combustion of hydrogen with either oxygen or air, it can be recycled in a closed loop and react with the metal. Finally, the metal hydroxides can be thermally reduced to metals in a solar furnace. This paper reviews the various storage methods for hydrogen and highlights their potential for improvement and their physical limitations.

Hydrogen storage methods

NASA Astrophysics Data System (ADS)

Züttel, Andreas

Hydrogen exhibits the highest heating value per mass of all chemical fuels. Furthermore, hydrogen is regenerative and environmentally friendly. There are two reasons why hydrogen is not the major fuel of today's energy consumption. First of all, hydrogen is just an energy carrier. And, although it is the most abundant element in the universe, it has to be produced, since on earth it only occurs in the form of water and hydrocarbons. This implies that we have to pay for the energy, which results in a difficult economic dilemma because ever since the industrial revolution we have become used to consuming energy for free. The second difficulty with hydrogen as an energy carrier is its low critical temperature of 33 K (i.e. hydrogen is a gas at ambient temperature). For mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage material is crucial. Hydrogen can be stored using six different methods and phenomena: (1) high-pressure gas cylinders (up to 800 bar), (2) liquid hydrogen in cryogenic tanks (at 21 K), (3) adsorbed hydrogen on materials with a large specific surface area (at T<100 K), (4) absorbed on interstitial sites in a host metal (at ambient pressure and temperature), (5) chemically bonded in covalent and ionic compounds (at ambient pressure), or (6) through oxidation of reactive metals, e.g. Li, Na, Mg, Al, Zn with water. The most common storage systems are high-pressure gas cylinders with a maximum pressure of 20 MPa (200 bar). New lightweight composite cylinders have been developed which are able to withstand pressures up to 80 MPa (800 bar) and therefore the hydrogen gas can reach a volumetric density of 36 kg.m-3, approximately half as much as in its liquid state. Liquid hydrogen is stored in cryogenic tanks at 21.2 K and ambient pressure. Due to the low critical temperature of hydrogen (33 K), liquid hydrogen can only be stored in open systems. The volumetric density of liquid hydrogen is 70.8 kg.m-3, and large volumes, where the thermal losses are small, can cause hydrogen to reach a system mass ratio close to one. The highest volumetric densities of hydrogen are found in metal hydrides. Many metals and alloys are capable of reversibly absorbing large amounts of hydrogen. Charging can be done using molecular hydrogen gas or hydrogen atoms from an electrolyte. The group one, two and three light metals (e.g. Li, Mg, B, Al) can combine with hydrogen to form a large variety of metal-hydrogen complexes. These are especially interesting because of their light weight and because of the number of hydrogen atoms per metal atom, which is two in many cases. Hydrogen can also be stored indirectly in reactive metals such as Li, Na, Al or Zn. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Since water is the product of the combustion of hydrogen with either oxygen or air, it can be recycled in a closed loop and react with the metal. Finally, the metal hydroxides can be thermally reduced to metals in a solar furnace. This paper reviews the various storage methods for hydrogen and highlights their potential for improvement and their physical limitations.

Thermochemical Production of Hydrogen from Water.

ERIC Educational Resources Information Center

Bamberger, C. E.; And Others

1978-01-01

Discusses the possible advantages of decomposing water by means of thermochemical cycles. Explains that, if energy consumption can be minimized, this method is capable of producing hydrogen more efficiently than electrolysis. (GA)

Binuclear Phthalocyanines as Model Electrocatalysts for the Reduction of Oxygen.

DTIC Science & Technology

1985-05-01

solution, in which case the final product is Co(II)Pc. Aqueous acid addition (under nitrogen) to Co(I)Pc (in DCB/OH-) yields Co(II)Pc and presumably hydrogen ...little doubt, given the tendency for Co(I) to reduce aqueous acid to hydrogen [101, that hydrogen is produced in this reaction, though it was not proven...reduction occurs in water by a 2-electron process to hydrogen peroxide or a 4-electron process to water. This latter process must be catalysed on a

Hydrogen speciation in hydrated layers on nuclear waste glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aines, R.D.; Weed, H.C.; Bates, J.K.

1987-01-15

The hydration of an outer layer on nuclear waste glasses is known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 & 165, and PNL 76-68), which were leached at 90{sup 0}C (all glasses) or hydrated in a vapor-saturated atmosphere at 202{sup 0}C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. Molecular water was foundmore » in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. Using the known molar absorptivities of water and hydroxyl in silica-rich glass the vapor-phase layer contained 4.8 moles/liter of molecular water, and 0.6 moles water in the form hydroxyl. A 15 {mu}m layer on SRL-131 glass formed by leaching at 90{sup 0}C contained a total of 4.9 moles/liter of water, 2/3 of which was as hydroxyl. The unreacted bulk glass contains about 0.018 moles/liter water, all as hydroxyl. The amount of hydrogen added to the SRL-131 glass was about 70% of the original Na + Li content, not the 300% that would result from alkali=hydronium ion interdiffusion. If all the hydrogen is then assumed to be added as the result of alkali-H{sup +} interdiffusion, the molecular water observed may have formed from condensation of the original hydroxyl groups.« less

Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy.

PubMed

Stiopkin, Igor V; Weeraman, Champika; Pieniazek, Piotr A; Shalhout, Fadel Y; Skinner, James L; Benderskii, Alexander V

2011-06-08

The air-water interface is perhaps the most common liquid interface. It covers more than 70 per cent of the Earth's surface and strongly affects atmospheric, aerosol and environmental chemistry. The air-water interface has also attracted much interest as a model system that allows rigorous tests of theory, with one fundamental question being just how thin it is. Theoretical studies have suggested a surprisingly short 'healing length' of about 3 ångströms (1 Å = 0.1 nm), with the bulk-phase properties of water recovered within the top few monolayers. However, direct experimental evidence has been elusive owing to the difficulty of depth-profiling the liquid surface on the ångström scale. Most physical, chemical and biological properties of water, such as viscosity, solvation, wetting and the hydrophobic effect, are determined by its hydrogen-bond network. This can be probed by observing the lineshape of the OH-stretch mode, the frequency shift of which is related to the hydrogen-bond strength. Here we report a combined experimental and theoretical study of the air-water interface using surface-selective heterodyne-detected vibrational sum frequency spectroscopy to focus on the 'free OD' transition found only in the topmost water layer. By using deuterated water and isotopic dilution to reveal the vibrational coupling mechanism, we find that the free OD stretch is affected only by intramolecular coupling to the stretching of the other OD group on the same molecule. The other OD stretch frequency indicates the strength of one of the first hydrogen bonds encountered at the surface; this is the donor hydrogen bond of the water molecule straddling the interface, which we find to be only slightly weaker than bulk-phase water hydrogen bonds. We infer from this observation a remarkably fast onset of bulk-phase behaviour on crossing from the air into the water phase.

Sensitivity of hydrogen bonds of DNA and RNA to hydration, as gauged by 1JNH measurements in ethanol-water mixtures.

PubMed

Manalo, Marlon N; Kong, Xiangming; LiWang, Andy

2007-04-01

Hydrogen-bond lengths of nucleic acids are (1) longer in DNA than in RNA, and (2) sequence dependent. The physicochemical basis for these variations in hydrogen-bond lengths is unknown, however. Here, the notion that hydration plays a significant role in nucleic acid hydrogen-bond lengths is tested. Watson-Crick N1...N3 hydrogen-bond lengths of several DNA and RNA duplexes are gauged using imino 1J(NH) measurements, and ethanol is used as a cosolvent to lower water activity. We find that 1J(NH) values of DNA and RNA become less negative with added ethanol, which suggests that mild dehydration reduces hydrogen-bond lengths even as the overall thermal stabilities of these duplexes decrease. The 1J(NH) of DNA are increased in 8 mol% ethanol to those of RNA in water, which suggests that the greater hydration of DNA plays a significant role in its longer hydrogen bonds. The data also suggest that ethanol-induced dehydration is greater for the more hydrated G:C base pairs and thereby results in greater hydrogen-bond shortening than for the less hydrated A:T/U base pairs of DNA and RNA.

Energetics of proton release on the first oxidation step in the water-oxidizing enzyme.

PubMed

Saito, Keisuke; Rutherford, A William; Ishikita, Hiroshi

2015-10-07

In photosystem II (PSII), the Mn4CaO5 cluster catalyses the water splitting reaction. The crystal structure of PSII shows the presence of a hydrogen-bonded water molecule directly linked to O4. Here we show the detailed properties of the H-bonds associated with the Mn4CaO5 cluster using a quantum mechanical/molecular mechanical approach. When O4 is taken as a μ-hydroxo bridge acting as a hydrogen-bond donor to water539 (W539), the S0 redox state best describes the unusually short O4-OW539 distance (2.5 Å) seen in the crystal structure. We find that in S1, O4 easily releases the proton into a chain of eight strongly hydrogen-bonded water molecules. The corresponding hydrogen-bond network is absent for O5 in S1. The present study suggests that the O4-water chain could facilitate the initial deprotonation event in PSII. This unexpected insight is likely to be of real relevance to mechanistic models for water oxidation.

Hydration effect on ion exchange resin irradiated by swift heavy ions and gamma rays

NASA Astrophysics Data System (ADS)

Boughattas, I.; Labed, V.; Gerenton, A.; Ngono-Ravache, Y.; Dannoux-Papin, A.

2018-06-01

Gamma radiolysis of ion exchange resins (IER) is widely studied since the sixties, as a function of different parameters (resin type, dose, atmosphere, water content …). However, to our knowledge, there are very few data concerning hydrogen emission from anionic and cationic resins irradiated at high Linear Energy Transfers (LET). In the present work, we focus on the influence of hydration on hydrogen emission, in anionic and cationic resins irradiated under inert atmosphere using Swift Heavy Ions (SHI) and gamma irradiations. The radiation chemical yield of molecular hydrogen is nonlinear with water content for both resins. The molecular hydrogen production depends first on the water form in IER (free or linked) and second on the solubility of degradation products. Three steps have been observed: at lower water content where G(H2) is stable, at 50%, G(H2) increases due to reactions between water radiolytic species and the resin functional groups and at high water content, G(H2) decreases probably due to its accumulation in water and its consumption by hydroxyl radicals in the supernatant.

Fuel Production from Seawater and Fuel Cells Using Seawater.

PubMed

Fukuzumi, Shunichi; Lee, Yong-Min; Nam, Wonwoo

2017-11-23

Seawater is the most abundant resource on our planet and fuel production from seawater has the notable advantage that it would not compete with growing demands for pure water. This Review focuses on the production of fuels from seawater and their direct use in fuel cells. Electrolysis of seawater under appropriate conditions affords hydrogen and dioxygen with 100 % faradaic efficiency without oxidation of chloride. Photoelectrocatalytic production of hydrogen from seawater provides a promising way to produce hydrogen with low cost and high efficiency. Microbial solar cells (MSCs) that use biofilms produced in seawater can generate electricity from sunlight without additional fuel because the products of photosynthesis can be utilized as electrode reactants, whereas the electrode products can be utilized as photosynthetic reactants. Another important source for hydrogen is hydrogen sulfide, which is abundantly found in Black Sea deep water. Hydrogen produced by electrolysis of Black Sea deep water can also be used in hydrogen fuel cells. Production of a fuel and its direct use in a fuel cell has been made possible for the first time by a combination of photocatalytic production of hydrogen peroxide from seawater and dioxygen in the air and its direct use in one-compartment hydrogen peroxide fuel cells to obtain electric power. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atom-bond electronegativity equalization method fused into molecular mechanics. I. A seven-site fluctuating charge and flexible body water potential function for water clusters.

PubMed

Yang, Zhong-Zhi; Wu, Yang; Zhao, Dong-Xia

2004-02-08

Recently, experimental and theoretical studies on the water system are very active and noticeable. A transferable intermolecular potential seven points approach including fluctuation charges and flexible body (ABEEM-7P) based on a combination of the atom-bond electronegativity equalization and molecular mechanics (ABEEM/MM), and its application to small water clusters are explored and tested in this paper. The consistent combination of ABEEM and molecular mechanics (MM) is to take the ABEEM charges of atoms, bonds, and lone-pair electrons into the intermolecular electrostatic interaction term in molecular mechanics. To examine the charge transfer we have used two models coming from the charge constraint types: one is a charge neutrality constraint on whole water system and the other is on each water molecule. Compared with previous water force fields, the ABEEM-7P model has two characters: (1) the ABEEM-7P model not only presents the electrostatic interaction of atoms, bonds and lone-pair electrons and their changing in respond to different ambient environment but also introduces "the hydrogen bond interaction region" in which a new parameter k(lp,H)(R(lp,H)) is used to describe the electrostatic interaction of the lone-pair electron and the hydrogen atom which can form the hydrogen bond; (2) nonrigid but flexible water body permitting the vibration of the bond length and angle is allowed due to the combination of ABEEM and molecular mechanics, and for van der Waals interaction the ABEEM-7P model takes an all atom-atom interaction, i.e., oxygen-oxygen, hydrogen-hydrogen, oxygen-hydrogen interaction into account. The ABEEM-7P model based on ABEEM/MM gives quite accurate predictions for gas-phase state properties of the small water clusters (H(2)O)(n) (n=2-6), such as optimized geometries, monomer dipole moments, vibrational frequencies, and cluster interaction energies. Due to its explicit description of charges and the hydrogen bond, the ABEEM-7P model will be applied to discuss properties of liquid water, ice, aqueous solutions, and biological systems.

Storing Renewable Energy in the Hydrogen Cycle.

PubMed

Züttel, Andreas; Callini, Elsa; Kato, Shunsuke; Atakli, Züleyha Özlem Kocabas

2015-01-01

An energy economy based on renewable energy requires massive energy storage, approx. half of the annual energy consumption. Therefore, the production of a synthetic energy carrier, e.g. hydrogen, is necessary. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines is a closed cycle. Electrolysis splits water into hydrogen and oxygen and represents a mature technology in the power range up to 100 kW. However, the major technological challenge is to build electrolyzers in the power range of several MW producing high purity hydrogen with a high efficiency. After the production of hydrogen, large scale and safe hydrogen storage is required. Hydrogen is stored either as a molecule or as an atom in the case of hydrides. The maximum volumetric hydrogen density of a molecular hydrogen storage is limited to the density of liquid hydrogen. In a complex hydride the hydrogen density is limited to 20 mass% and 150 kg/m(3) which corresponds to twice the density of liquid hydrogen. Current research focuses on the investigation of new storage materials based on combinations of complex hydrides with amides and the understanding of the hydrogen sorption mechanism in order to better control the reaction for the hydrogen storage applications.

The corrosion behavior of Alloy 52 weld metal in cyclic hydrogenated and oxygenated water chemistry in high temperature aqueous environment

NASA Astrophysics Data System (ADS)

Xu, Jian; Shoji, Tetsuo

2015-06-01

The corrosion behavior of Alloy 52 weld metal in cyclic hydrogenated and oxygenated water chemistry in high temperature water is studied by in situ monitoring corrosion potential (Ecorr), contact electric resistance (CER) and electrochemical impedance measurements (EIS), and ex situ scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis. The Ecorr and film resistance show large change when the environment is changed from hydrogenated water to oxygenated water and changeable with changing environment while the morphology and composition only show obvious distinction in the first cycle. The main factor controlling the electric/electrochemical properties of the oxide film is Ecorr.

Water's Interfacial Hydrogen Bonding Structure Reveals the Effective Strength of Surface-Water Interactions.

PubMed

Shin, Sucheol; Willard, Adam P

2018-06-05

We combine all-atom molecular dynamics simulations with a mean field model of interfacial hydrogen bonding to analyze the effect of surface-water interactions on the structural and energetic properties of the liquid water interface. We show that the molecular structure of water at a weakly interacting ( i.e., hydrophobic) surface is resistant to change unless the strength of surface-water interactions are above a certain threshold. We find that below this threshold water's interfacial structure is homogeneous and insensitive to the details of the disordered surface, however, above this threshold water's interfacial structure is heterogeneous. Despite this heterogeneity, we demonstrate that the equilibrium distribution of molecular orientations can be used to quantify the energetic component of the surface-water interactions that contribute specifically to modifying the interfacial hydrogen bonding network. We identify this specific energetic component as a new measure of hydrophilicity, which we refer to as the intrinsic hydropathy.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, Carlos E.

1980-01-01

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, C.E.

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Hydrogen Purification and Recycling for an Integrated Oxygen Recovery System Architecture

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Greenwood, Zachary; Wall, Terry; Miller, Lee; Wheeler, Ray

2016-01-01

The United States Atmosphere Revitalization life support system on the International Space Station (ISS) performs several services for the crew including oxygen generation, trace contaminant control, carbon dioxide (CO2) removal, and oxygen recovery. Oxygen recovery is performed using a Sabatier reactor developed by Hamilton Sundstrand, wherein CO2 is reduced with hydrogen in a catalytic reactor to produce methane and water. The water product is purified in the Water Purification Assembly and recycled to the Oxygen Generation Assembly (OGA) to provide O2 to the crew. This architecture results in a theoretical maximum oxygen recovery from CO2 of approximately 54% due to the loss of reactant hydrogen in Sabatier-produced methane that is currently vented outside of ISS. Plasma Methane Pyrolysis technology (PPA), developed by Umpqua Research Company, provides the capability to further close the Atmosphere Revitalization oxygen loop by recovering hydrogen from Sabatier-produced methane. A key aspect of this technology approach is to purify the hydrogen from the PPA product stream which includes acetylene, unreacted methane and byproduct water and carbon monoxide. In 2015, four sub-scale hydrogen separation systems were delivered to NASA for evaluation. These included two electrolysis single-cell hydrogen purification cell stacks developed by Sustainable Innovations, LLC, a sorbent-based hydrogen purification unit using microwave power for sorbent regeneration developed by Umpqua Research Company, and a LaNi4.6Sn0.4 metal hydride produced by Hydrogen Consultants, Inc. Here we report the results of these evaluations, discuss potential architecture options, and propose future work.

Hydrogen Purification and Recycling for an Integrated Oxygen Recovery System Architecture

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Greenwood, Zachary; Wall, Terry; Nur, Mononita; Wheeler, Richard R., Jr.; Preston, Joshua; Molter, Trent

2016-01-01

The United States Atmosphere Revitalization life support system on the International Space Station (ISS) performs several services for the crew including oxygen generation, trace contaminant control, carbon dioxide (CO2) removal, and oxygen recovery. Oxygen recovery is performed using a Sabatier reactor developed by Hamilton Sundstrand, wherein CO2 is reduced with hydrogen in a catalytic reactor to produce methane and water. The water product is purified in the Water Purification Assembly and recycled to the Oxygen Generation Assembly (OGA) to provide O2 to the crew. This architecture results in a theoretical maximum oxygen recovery from CO2 of approx.54% due to the loss of reactant hydrogen in Sabatier-produced methane that is currently vented outside of ISS. Plasma Pyrolysis Assembly (PPA) technology, developed by Umpqua Research Company, provides the capability to further close the Atmosphere Revitalization oxygen loop by recovering hydrogen from Sabatier-produced methane. A key aspect of this technology approach is the need to purify the hydrogen from the PPA product stream which includes acetylene, unreacted methane and byproduct water and carbon monoxide. In 2015, four sub-scale hydrogen separation systems were delivered to NASA for evaluation. These included two electrolysis single-cell hydrogen purification cell stacks developed by Sustainable Innovations, LLC, a sorbent-based hydrogen purification unit using microwave power for sorbent regeneration developed by Umpqua Research Company, and a LaNi4.6Sn0.4 metal hydride produced by Hydrogen Consultants, Inc. Here we report the results of these evaluations to-date, discuss potential architecture options, and propose future work.

New Photocatalysts for Hydrogen Production; Nuevos Fotocatalizadores para la Producción de Hidrógeno

DOE PAGES

García, Abraham; Cotto, María; Duconge, José; ...

2014-06-10

The use of hydrogen as replacement for fossil fuels, on which we depend today, is a matter of great relevance. The sustainable generation of hydrogen as fuel is relevant from an environmental and economic point of view. In this study we have explored new synthetic routes for developing new photocatalysts to be used in water splitting, for hydrogen production. Different techniques have been used to produce hydrogen, such as electrolysis, even though these processes have been found to be energetically non suitable. In this research various photocatalytic materials were presented as possible alternatives for using in water splitting processes. Characterizationmore » of the new synthesized materials has been done by using different experimental techniques including Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), surface area BET, and X-ray Diffraction (XRD). The efficiency of the synthesized photocatalysts was determined by evaluating the hydrogen evolution by the photocatalytic water splitting reaction.« less

Materials for the scavenging of hydrogen at high temperatures

DOEpatents

Shepodd, T.J.; Phillip, B.L.

1997-12-30

A hydrogen getter composition is described comprising a double or triple bonded hydrocarbon with a high melting point useful for removing hydrogen gas, to partial pressures below 0.01 torr, from enclosed spaces and particularly from vessels used for transporting or containing fluids at elevated temperatures. The hydrogen getter compositions disclosed herein and their reaction products will neither melt nor char at temperatures in excess of 100 C. They possess significant advantages over conventional hydrogen getters, namely low risk of fire or explosion, no requirement for high temperature activation or operation, the ability to absorb hydrogen even in the presence of contaminants such as water, water vapor, common atmospheric gases and oil mists and are designed to be disposed within the confines of the apparatus. These getter materials can be mixed with binders, such as fluoropolymers, which permit the getter material to be fabricated into useful shapes and/or impart desirable properties such as water repellency or impermeability to various gases. 7 figs.

Materials for the scavanging of hydrogen at high temperatures

DOEpatents

Shepodd, Timothy J.; Phillip, Bradley L.

1997-01-01

A hydrogen getter composition comprising a double or triple bonded hydrocarbon with a high melting point useful for removing hydrogen gas, to partial pressures below 0.01 torr, from enclosed spaces and particularly from vessels used for transporting or containing fluids at elevated temperatures. The hydrogen getter compositions disclosed herein and their reaction products will neither melt nor char at temperatures in excess of 100.degree. C. They possess significant advantages over conventional hydrogen getters, namely low risk of fire or explosion, no requirement for high temperature activation or operation, the ability to absorb hydrogen even in the presence of contaminants such as water, water vapor, common atmospheric gases and oil mists and are designed to be disposed within the confines of the apparatus. These getter materials can be mixed with binders, such as fluropolymers, which permit the getter material to be fabricated into useful shapes and/or impart desirable properties such as water repellency or impermeability to various gases.

Materials for the scavanging of hydrogen at high temperatures

DOEpatents

Shepodd, Timothy J.; Phillip, Bradley L.

1997-01-01

A hydrogen getter composition comprising a double or triple bonded hydrocarbon with a high melting point useful for removing hydrogen gas, to partial pressures below 0.01 torr, from enclosed spaces and particularly from vessels used for transporting or containing fluids at elevated temperatures. The hydrogen getter compostions disclosed herein and their reaction products will neither melt nor char at temperatures in excess of 100C. They possess significant advantages over conventional hydrogen getters, namely low risk of fire or explosion, no requirement for high temperature activation or operation, the ability to absorb hydrogen even in the presence of contaminants such as water, water vapor, common atmospheric gases and oil mists and are designed to be disposed within the confines of the apparatus. These getter materials can be mixed with binders, such as fluropolymers, which permit the getter material to be fabricated into useful shapes and/or impart desirable properties such as water repellency or impermeability to various gases.

Materials for the scavenging of hydrogen at high temperatures

DOEpatents

Shepodd, T.J.; Phillip, B.L.

1997-04-29

A hydrogen getter composition is described comprising a double or triple bonded hydrocarbon with a high melting point useful for removing hydrogen gas, to partial pressures below 0.01 torr, from enclosed spaces and particularly from vessels used for transporting or containing fluids at elevated temperatures. The hydrogen getter compositions disclosed herein and their reaction products will neither melt nor char at temperatures in excess of 100C. They possess significant advantages over conventional hydrogen getters, namely low risk of fire or explosion, no requirement for high temperature activation or operation, the ability to absorb hydrogen even in the presence of contaminants such as water, water vapor, common atmospheric gases and oil mists and are designed to be disposed within the confines of the apparatus. These getter materials can be mixed with binders, such as fluoropolymers, which permit the getter material to be fabricated into useful shapes and/or impart desirable properties such as water repellency or impermeability to various gases. 7 figs.

Water splitting on semiconductor catalysts under visible-light irradiation.

PubMed

Navarro Yerga, Rufino M; Alvarez Galván, M Consuelo; del Valle, F; Villoria de la Mano, José A; Fierro, José L G

2009-01-01

Sustainable hydrogen production is a key target for the development of alternative, future energy systems that will provide a clean and affordable energy supply. The Sun is a source of silent and precious energy that is distributed fairly all over the Earth daily. However, its tremendous potential as a clean, safe, and economical energy source cannot be exploited unless the energy is accumulated or converted into more useful forms. The conversion of solar energy into hydrogen via the water-splitting process, assisted by photo-semiconductor catalysts, is one of the most promising technologies for the future because large quantities of hydrogen can potentially be generated in a clean and sustainable manner. This Minireview provides an overview of the principles, approaches, and research progress on solar hydrogen production via the water-splitting reaction on photo-semiconductor catalysts. It presents a survey of the advances made over the last decades in the development of catalysts for photochemical water splitting under visible-light irradiation. The Minireview also analyzes the energy requirements and main factors that determine the activity of photocatalysts in the conversion of water into hydrogen and oxygen using sunlight. Remarkable progress has been made since the pioneering work by Fujishima and Honda in 1972, but he development of photocatalysts with improved efficiencies for hydrogen production from water using solar energy still faces major challenges. Research strategies and approaches adopted in the search for active and efficient photocatalysts, for example through new materials and synthesis methods, are presented and analyzed.

Orientation hydrogen-bonding effect on vibronic spectra of isoquinoline in water solvent: Franck-Condon simulation and interpretation

NASA Astrophysics Data System (ADS)

Liu, Yu-Hui; Wang, Shi-Ming; Wang, Chen-Wen; Zhu, Chaoyuan; Han, Ke-Li; Lin, Sheng-Hsien

2016-10-01

The excited-state orientation hydrogen-bonding dynamics, and vibronic spectra of isoquinoline (IQ) and its cationic form IQc in water have been investigated at the time-dependent density functional theory quantum chemistry level plus Franck-Condon simulation and interpretation. The excited-state orientation hydrogen bond strengthening has been found in IQ:H2O complex due to the charge redistribution upon excitation; this is interpreted by simulated 1:1 mixed absorption spectra of free IQ and IQ:H2O complex having best agreement with experimental results. Conversely, the orientation hydrogen bond in IQc:H2O complex would be strongly weakening in the S1 state and this is interpreted by simulated absorption spectra of free IQc having best agreement with experimental results. By performing Franck-Condon simulation, it reveals that several important vibrational normal modes with frequencies about 1250 cm-1 involving the wagging motion of the hydrogen atoms are very sensitive to the formation of the orientation hydrogen bond for the IQ/IQc:H2O complex and this is confirmed by damped Franck-Condon simulation with free IQ/IQc in water. However, the emission spectra of the IQ and IQc in water have been found differently. Upon the excitation, the simulated fluorescence of IQ in water is dominated by the IQ:H2O complex; thus hydrogen bond between IQ and H2O is much easier to form in the S1 state. While the weakened hydrogen bond in IQc:H2O complex is probably cleaved upon the laser pulse because the simulated emission spectrum of the free IQc is in better agreement with the experimental results.

Chemically Modified Metal Oxide Nanostructure for Photoelectrochemical Water Splitting

NASA Astrophysics Data System (ADS)

Wang, Gongming

Hydrogen gas is chemical fuel with high energy density, and represents a clean, renewable and carbon-free burning fuel, which has the potential to solve the more and more urgent energy crisis in today's society. Inspired by natural photosynthesis, artificial photosynthesis to generate hydrogen energy has attracted a lot of attentions in the field of chemistry, physics and material. Photoelectrochemical water splitting based on semiconductors represents a green and low cost method to generate hydrogen fuel. However, the current overall efficiency of solar to hydrogen is quite low, due to some intrinsic limitations such as bandgap, diffusion distance, carrier lifetime and photostability of semiconductors. Although nanostructured semiconductors can improve their photoelectrochemical water splitting performance to some extent, by increasing electrolyte accessible area and shortening minority carrier diffusion distance, nanostructure engineering cannot change their intrinsic electronic properties. Recent development in chemically modified nanostructures such as surface catalyst decoration, element doping, plasmonic modification and interfacial hetero-junction design have led to significant advancement in the photoelectrochemical water splitting, by improving surface reaction kinetics and charge separation, transportation and collection efficiency. In this thesis, I will give a detailed discussion on the chemically modified metal oxide nanostructures for photoelectrocemical hydrogen generation, with a focus on the element doping, hydrogen treatment and catalyst modification. I have demonstrated nitrogen doping on ZnO and Ti doping on hematite can improve their photoelectrochemical performance. In addition, we found hydrogen treatment is a general and effective method to improve the photocatalytic performance, by increasing their carrier desities. Hydrogen treatment has been demonstrated on TiO2, WO3 and BiVO4. In the end, we also used electrochemical catalyt to modify these metal oxide photoelectrode for waste water treatment and chemical fuel generation.

Hydrogen bonded structure, polarity, molecular motion and frequency fluctuations at liquid-vapor interface of a water-methanol mixture: an ab initio molecular dynamics study.

PubMed

Choudhuri, Jyoti Roy; Chandra, Amalendu

2014-10-07

We have performed ab initio molecular dynamics simulations of a liquid-vapor interfacial system consisting of a mixture of water and methanol molecules. Detailed results are obtained for the structural and dynamical properties of the bulk and interfacial regions of the mixture. Among structural properties, we have looked at the inhomogeneous density profiles of water and methanol molecules, hydrogen bond distributions and also the orientational profiles of bulk and interfacial molecules. The methanol molecules are found to have a higher propensity to be at the interface than water molecules. It is found that the interfacial molecules show preference for specific orientations so as to form water-methanol hydrogen bonds at the interface with the hydrophobic methyl group pointing towards the vapor side. It is also found that for both types of molecules, the dipole moment decreases at the interface. It is also found that the local electric field of water influences the dipole moment of methanol molecules. Among the dynamical properties, we have calculated the diffusion, orientational relaxation, hydrogen bond dynamics, and vibrational frequency fluctuations in bulk and interfacial regions. It is found that the diffusion and orientation relaxation of the interfacial molecules are faster than those of the bulk. However, the hydrogen bond lifetimes are longer at the interface which can be correlated with the time scales found from the decay of frequency time correlations. The slower hydrogen bond dynamics for the interfacial molecules with respect to bulk can be attributed to diminished cooperative effects at the interface due to reduced density and number of hydrogen bonds.

Species measurements in a hypersonic, hydrogen-air, combustion wake

NASA Technical Reports Server (NTRS)

Skinner, K. A.; Stalker, R. J.

1995-01-01

A continuously sampling, time-of-flight mass spectrometer has been used to measure relative species concentrations in a two-dimensional, hydrogen-air combustion wake at mainstream Mach numbers exceeding 5. The experiments, which were conducted in a free piston shock tunnel, yielded distributions of hydrogen, oxygen, nitrogen, water and nitric oxide at stagnation enthalpies ranging from 5.6 MJ kg(exp -1) to 1.2 MJ kg(exp -1) and at a distance of approximately 100 times the thickness of the initial hydrogen jet. The amount of hydrogen that was mixed in stoichiometric proportions was approximately independent of the stagnation enthalpy, in spite of the fact that the proportion of hydrogen in the wake increased with stagnation enthalpy. Roughly 50 percent of the mixed hydrogen underwent combustion at the highest enthalpy. The proportion of hydrogen reacting to water could be approximately predicted using reaction rates based on mainstream temperatures.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grachev, S.A.; Chakchir, B.A.; Ryabykh, L.D.

The feasibility of radiation sterilization was studied on ephedrine hydrochloride, atropine sulfate, scopolamine hydrobromide, strychnine nitrate, morphine hydrochloride, codeine phosphate, proserine, cysteamine hydrochloride, and unithiol in form of injectable solutions and as powders. It was shown that the sterilizing dose of radioactivity results in a breakdown of the solutions as shown by changes in the pH, color, and loss of biological activity. Alkaloid powders exhibited no changes after radiation sterilization. Deaerated solutions were also stable to the radiation but such solutions could not be prepared easily under industrial conditions. Temperature had no effect on the stability of test samples exceptmore » for very low temperatures. (JPRS)« less

Hollow fiber membranes for advanced life support systems. [permeable capillaries for medical filtration

NASA Technical Reports Server (NTRS)

Roebelen, G. J., Jr.; Lysaght, M. J.

1977-01-01

This paper describes an investigation of the practicability of utilizing hollow fiber membranes in vehicular and portable life support system applications. A preliminary screening of potential advanced life support applications resulted in the selection of five applications for feasibility study and testing. As a result of the feasibility study and testing, three applications, heat rejection, deaeration, and bacteria filtration, were chosen for breadboard development testing. Breadboard hardware has been manufactured and tested, and the physical properties of the three hollow fiber membrane assemblies applicable to use aboard future spacecraft have been characterized.

Innovative Strategy on Hydrogen Evolution Reaction Utilizing Activated Liquid Water

NASA Astrophysics Data System (ADS)

Hwang, Bing-Joe; Chen, Hsiao-Chien; Mai, Fu-Der; Tsai, Hui-Yen; Yang, Chih-Ping; Rick, John; Liu, Yu-Chuan

2015-11-01

Splitting water for hydrogen production using light, or electrical energy, is the most developed ‘green technique’. For increasing efficiency in hydrogen production, currently, the most exciting and thriving strategies are focused on efficient and inexpensive catalysts. Here, we report an innovative idea for efficient hydrogen evolution reaction (HER) utilizing plasmon-activated liquid water with reduced hydrogen-bonded structure by hot electron transfer. This strategy is effective for all HERs in acidic, basic and neutral systems, photocatalytic system with a g-C3N4 (graphite carbon nitride) electrode, as well as in an inert system with an ITO (indium tin oxide) electrode. Compared to deionized water, the efficiency of HER increases by 48% based on activated water ex situ on a Pt electrode. Increase in energy efficiency from activated water is 18% at a specific current yield of -20 mA in situ on a nanoscale-granulated Au electrode. Moreover, the onset potential of -0.023 V vs RHE was very close to the thermodynamic potential of the HER (0 V). The measured current density at the corresponding overpotential for HER in an acidic system was higher than any data previously reported in the literature. This approach establishes a new vista in clean green energy production.

Temperature dependence of the evaporation lengthscale for water confined between two hydrophobic plates.

PubMed

Djikaev, Yuri S; Ruckenstein, Eli

2015-07-01

Liquid water in a hydrophobic confinement is the object of high interest in physicochemical sciences. Confined between two macroscopic hydrophobic surfaces, liquid water transforms into vapor if the distance between surfaces is smaller than a critical separation, referred to as the evaporation lengthscale. To investigate the temperature dependence of the evaporation lengthscale of water confined between two hydrophobic parallel plates, we use the combination of the density functional theory (DFT) with the probabilistic hydrogen bond (PHB) model for water-water hydrogen bonding. The PHB model provides an analytic expression for the average number of hydrogen bonds per water molecule as a function of its distance to a hydrophobic surface and its curvature. Knowing this expression, one can implement the effect of hydrogen bonding between water molecules on their interaction with the hydrophobe into DFT, which is then employed to determine the distribution of water molecules between two macroscopic hydrophobic plates at various interplate distances and various temperatures. For water confined between hydrophobic plates, our results suggest the evaporation lengthscale to be of the order of several nanometers and a linearly increasing function of temperature from T=293 K to T=333 K, qualitatively consistent with previous results. Copyright © 2015 Elsevier Inc. All rights reserved.

Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J., E-mail: saykally@berkeley.edu

While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure.more » The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.« less

Investigating the Counteracting Effect of Trehalose on Urea-Induced Protein Denaturation Using Molecular Dynamics Simulation.

PubMed

Paul, Subrata; Paul, Sandip

2015-08-27

Molecular dynamics simulations are performed to investigate the counteracting effect of trehalose against urea-induced denaturation of S-peptide analogue. The calculations of Cα root-mean-square deviation, radius of gyration, and solvent-accessible surface area reveal that the peptide loses its native structure in aqueous 8 M urea solution at 310 K and that this unfolding process is prevented in the presence of trehalose. Interestingly, the native structure of the peptide in ternary mixed urea/trehalose solution is similar to that in the pure water system. The estimation of helical percentage of peptide residues as well as peptide-peptide intramolecular hydrogen bond number for different systems also support the above findings. Decomposition of protein-urea total interaction energy into electrostatic and van der Waals contributions shows that the presence of trehalose molecules makes the latter contribution unfavorable without affecting the former. These observations are further supported by preferential interaction calculations. Furthermore, the hydrogen bond analyses show that with the addition of urea molecules to the peptide-water system, the formation of peptide-urea hydrogen bonds takes place at the expense of peptide-water hydrogen bonds. In ternary mixed osmolytes system, because of formation of a considerable amount of peptide-trehalose hydrogen bonds, some urea molecules are excluded from the peptide surface. This essentially reduces the interaction between peptide and urea molecules, and because of this, we notice a reduction in the number of peptide-urea hydrogen bonds. Interestingly, the total number of peptide-solution species hydrogen bonds in the pure water system is very similar to that for the mixed osmolytes system. From these observations we infer that in the ternary solution, peptide-solution species hydrogen bonds are shared by water, urea, and trehalose molecules. The presence of trehalose in the mixed osmolyte system causes a significant reduction in the translational dynamics of water molecules. We discuss these results to understand the molecular explanation of trehalose's counteracting ability on urea-induced protein denaturation.

Process for obtaining liquid fuel-oil and/or gaseous hydrocarbons from solid carbonaceous feed stocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hollaway, J.W.

1978-02-28

A process for forming a fuel-oil from coal is disclosed. The coal is treated in a low temperature carbonization retort to give coke, coal-gas and tar-oil. The coke is converted to water-gas which is then synthesized in a Fischer-Tropsch synthesizer to form fuel-oil. The tar-oil is hydrogenated in a hydro-treater by hydrogen produced from the coal-gas. Hydrogen is produced from coal-gas either in a thermal cracking chamber or by reforming the methane content to hydrogen and passing the resultant hydrogen/carbon monoxide mixture through a water-gas shift reactor and a carbon dioxide scrubber.

Study of thermal scattering for organic tissues through molecular dynamics

NASA Astrophysics Data System (ADS)

Ramos, Ricardo; Cantargi, Florencia; Marquez Damian, Jose Ignacio; Gonçalves-Carralves, Manuel Sztejnberg

2017-09-01

Boron Neutron Capture Therapy (BNCT) is an experimental therapy for tumors which is based on the nuclear reaction that occurs when 10B is irradiated with thermal neutrons. Calculations for BNCT with Monte Carlo N-Particle (MCNP) take into account the thermal scattering treatment for hydrogen bound in bulk water for any organic tissue. However, in these tissues, hydrogen is also present in macromolecules (protein, lipids, etc.) and in confined water. Thermal scattering cross section for hydrogen in an organic tissue can be determined by calculating the scattering law S(α,β). This function can be obtained with the nuclear data processing system NJOY from the vibrational frequency spectrum of an atom in a molecular system. We performed calculations of the frequency spectrum from molecular dynamics simulations using the program GROMACS. Systems composed of a peptide in a water box were considered, with different proportions of water molecules. All-atom potentials for modeling this molecules were used in order to represent the internal vibrational normal modes for the atoms of hydrogen. The results showed several internal normal modes that in the case of hydrogen bound in bulk water do not appear.

Thermochemical generation of hydrogen and oxygen from water

DOEpatents

Robinson, Paul R.; Bamberger, Carlos E.

1981-01-01

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Thermochemical generation of hydrogen and oxygen from water

DOEpatents

Robinson, Paul R.; Bamberger, Carlos E.

1982-01-01

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

NREL Establishes World Record for Solar Hydrogen Production | News | News |

Science.gov Websites

acid/water solution (electrolyte) where the water-splitting reaction occurs to form hydrogen and oxygen efficiency and to partially protect the critical underlying layers from the corrosive electrolyte solution

Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Groundwater Samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Brady D.; Moran, James J.; Nims, Megan K.

Report summarizing stable oxygen and hydrogen isotope analysis of two groundwater samples from the B-Complex. Results from analyses were compared to perched water and pore water analyses performed previously.

[Hydrogen and oxygen isotopes of lake water and geothermal spring water in arid area of south Tibet].

PubMed

Xiao, Ke; Shen, Li-Cheng; Wang, Peng

2014-08-01

The condition of water cycles in Tibet Plateau is a complex process, and the hydrogen and oxygen isotopes contain important information of this process. Based on the analysis of isotopic composition of freshwater lake, saltwater lake and geothermal water in the southern Tibetan Plateau, this study investigated water cycling, composition and variation of hydrogen and oxygen isotopes and the influencing factors in the study area. The study found that the mean values of delta18O and deltaD in Daggyaima lake water (-17.0 per thousand for delta18O and -138. 6 per thousand for deltaD), Langcuo lake water (-6.4 per thousand for delta18O and -87.4 per thousand for deltaD) and Dagejia geothermal water (-19.2 per thousand for delta18 and -158.2 per thousand for deltaD) all showed negative delta18O and deltaD values in Tibetan Plateau by the influence of altitude effects. Lake water and geothermal water were influenced by evaporation effects in inland arid area, and the slope of evaporation line was less than 8. Deuterium excess parameters of lake water and geothermal water were all negative. The temperature of geothermal reservoirs in Dagejia geothermal field was high,and oxygen shift existed in the relationship of hydrogen and oxygen isotopes.

Photosynthetic water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenbaum, E.

1981-01-01

The photosynthetic unit of hydrogen evolution, the turnover time of photosynthetic hydrogen production, and hydrogenic photosynthesis are discussed in the section on previous work. Recent results are given on simultaneous photoproduction of hydrogen and oxygen, kinetic studies, microscopic marine algae-seaweeds, and oxygen profiles.

Multisample conversion of water to hydrogen by zinc for stable isotope determination

USGS Publications Warehouse

Kendall, C.; Coplen, T.B.

1985-01-01

Two techniques for the conversion of water to hydrogen for stable isotope ratio determination have been developed that are especially suited for automated multisample analysis. Both procedures involve reaction of zinc shot with a water sample at 450 ??C. in one method designed for water samples in bottles, the water is put in capillaries and is reduced by zinc in reaction vessels; overall savings in sample preparation labor of 75% have been realized over the standard uranium reduction technique. The second technique is for waters evolved under vacuum and is a sealed-tube method employing 9 mm o.d. quartz tubing. Problems inherent with zinc reduction include surface inhomogeneity of the zinc and exchange of hydrogen both with the zinc and with the glass walls of the vessels. For best results, water/zinc and water/glass surface area ratios of vessels should be kept as large as possible.

Photocatalysts Based on Cobalt-Chelating Conjugated Polymers for Hydrogen Evolution from Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lianwei; Hadt, Ryan G.; Yao, Shiyu

Developing photocatalytic systems for water splitting to generate oxygen and hydrogen is one of the biggest chemical challenges in solar energy utilization. In this work, we report the first example of heterogeneous photocatalysts for hydrogen evolution based on in-chain cobalt-chelating conjugated polymers. Four conjugated polymers chelated with earth abundant cobalt ions were synthesized and found to evolve hydrogen photocatalytically from water. These polymers are designed to combine functions of the conjugated backbone as light-harvesting antenna and electron transfer conduit with the in-chain bipyridyl chelated transition metal centers as catalytic active sites. In addition, these polymers are soluble in organic solvents,more » enabling effective interactions with the substrates as well as detailed characterization. We also found a polymer-dependent optimal cobalt chelating concentration at which the highest photocatalytic hydrogen production (PHP) activity can be achieved.« less

Method and apparatus for hydrogen production from water

NASA Technical Reports Server (NTRS)

Muradov, Nazim Z. (Inventor)

2012-01-01

A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH.sub.4. The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.

DOE Office of Scientific and Technical Information (OSTI.GOV)

García, Abraham; Cotto, María; Duconge, José

The use of hydrogen as replacement for fossil fuels, on which we depend today, is a matter of great relevance. The sustainable generation of hydrogen as fuel is relevant from an environmental and economic point of view. In this study we have explored new synthetic routes for developing new photocatalysts to be used in water splitting, for hydrogen production. Different techniques have been used to produce hydrogen, such as electrolysis, even though these processes have been found to be energetically non suitable. In this research various photocatalytic materials were presented as possible alternatives for using in water splitting processes. Characterizationmore » of the new synthesized materials has been done by using different experimental techniques including Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), surface area BET, and X-ray Diffraction (XRD). The efficiency of the synthesized photocatalysts was determined by evaluating the hydrogen evolution by the photocatalytic water splitting reaction.« less

Mechanism of conformational coupling in SecA: Key role of hydrogen-bonding networks and water interactions.

PubMed

Milenkovic, Stefan; Bondar, Ana-Nicoleta

2016-02-01

SecA uses the energy yielded by the binding and hydrolysis of adenosine triphosphate (ATP) to push secretory pre-proteins across the plasma membrane in bacteria. Hydrolysis of ATP occurs at the nucleotide-binding site, which contains the conserved carboxylate groups of the DEAD-box helicases. Although crystal structures provide valuable snapshots of SecA along its reaction cycle, the mechanism that ensures conformational coupling between the nucleotide-binding site and the other domains of SecA remains unclear. The observation that SecA contains numerous hydrogen-bonding groups raises important questions about the role of hydrogen-bonding networks and hydrogen-bond dynamics in long-distance conformational couplings. To address these questions, we explored the molecular dynamics of SecA from three different organisms, with and without bound nucleotide, in water. By computing two-dimensional hydrogen-bonding maps we identify networks of hydrogen bonds that connect the nucleotide-binding site to remote regions of the protein, and sites in the protein that respond to specific perturbations. We find that the nucleotide-binding site of ADP-bound SecA has a preferred geometry whereby the first two carboxylates of the DEAD motif bridge via hydrogen-bonding water. Simulations of a mutant with perturbed ATP hydrolysis highlight the water-bridged geometry as a key structural element of the reaction path. Copyright © 2015. Published by Elsevier B.V.

Bioelectrochemical production of hydrogen in an innovative pressure-retarded osmosis/microbial electrolysis cell system: experiments and modeling.

PubMed

Yuan, Heyang; Lu, Yaobin; Abu-Reesh, Ibrahim M; He, Zhen

2015-01-01

While microbial electrolysis cells (MECs) can simultaneously produce bioelectrochemical hydrogen and treat wastewater, they consume considerable energy to overcome the unfavorable thermodynamics, which is not sustainable and economically feasible in practical applications. This study presents a proof-of-concept system in which hydrogen can be produced in an MEC powered by theoretically predicated energy from pressure-retarded osmosis (PRO). The system consists of a PRO unit that extracts high-quality water and generates electricity from water osmosis, and an MEC for organic removal and hydrogen production. The feasibility of the system was demonstrated using simulated PRO performance (in terms of energy production and effluent quality) and experimental MEC results (e.g., hydrogen production and organic removal). The PRO and MEC models were proven to be valid. The model predicted that the PRO unit could produce 485 mL of clean water and 579 J of energy with 600 mL of draw solution (0.8 M of NaCl). The amount of the predicated energy was applied to the MEC by a power supply, which drove the MEC to remove 93.7 % of the organic compounds and produce 32.8 mL of H2 experimentally. Increasing the PRO influent volume and draw concentration could produce more energy for the MEC operation, and correspondingly increase the MEC hydraulic retention time (HRT) and total hydrogen production. The models predicted that at an external voltage of 0.9 V, the MEC energy consumption reached the maximum PRO energy production. With a higher external voltage, the MEC energy consumption would exceed the PRO energy production, leading to negative effects on both organic removal and hydrogen production. The PRO-MEC system holds great promise in addressing water-energy nexus through organic removal, hydrogen production, and water recovery: (1) the PRO unit can reduce the volume of wastewater and extract clean water; (2) the PRO effluents can be further treated by the MEC; and (3) the osmotic energy harvested from the PRO unit can be applied to the MEC for sustainable bioelectrochemical hydrogen production.

Integrated hydrocarbon reforming system and controls

DOEpatents

Clawson, Lawrence G.; Dorson, Matthew H.; Mitchell, William L.; Nowicki, Brian J.; Thijssen, Johannes; Davis, Robert; Papile, Christopher; Rumsey, Jennifer W.; Longo, Nathan; Cross, III, James C.; Rizzo, Vincent; Kleeburg, Gunther; Rindone, Michael; Block, Stephen G.; Sun, Maria; Morriseau, Brian D.; Hagan, Mark R.; Bowers, Brian

2003-11-04

A hydrocarbon reformer system including a first reactor configured to generate hydrogen-rich reformate by carrying out at least one of a non-catalytic thermal partial oxidation, a catalytic partial oxidation, a steam reforming, and any combinations thereof, a second reactor in fluid communication with the first reactor to receive the hydrogen-rich reformate, and having a catalyst for promoting a water gas shift reaction in the hydrogen-rich reformate, and a heat exchanger having a first mass of two-phase water therein and configured to exchange heat between the two-phase water and the hydrogen-rich reformate in the second reactor, the heat exchanger being in fluid communication with the first reactor so as to supply steam to the first reactor as a reactant is disclosed. The disclosed reformer includes an auxiliary reactor configured to generate heated water/steam and being in fluid communication with the heat exchanger of the second reactor to supply the heated water/steam to the heat exchanger.

Computer simulations of local anesthetic mechanisms: Quantum chemical investigation of procaine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Jeremy C; Bondar, A.N.; Suhai, Sandor

2007-02-01

A description at the atomic level of detail of the interaction between local anesthetics, lipid membranes and membrane proteins, is essential for understanding the mechanism of local anesthesia. The importance of performing computer simulations to decipher the mechanism of local anesthesia is discussed here in the context of the current status of understanding of the local anesthetics action. As a first step towards accurate simulations of the interaction between local anesthetics, proteins, lipid and water molecules, here we use quantum mechanical methods to assess the charge distribution and structural properties of procaine in the presence and in the absence ofmore » water molecules. The calculations indicate that, in the absence of hydrogen-bonding water molecules, protonated procaine strongly prefers a compact structure enabled by intramolecular hydrogen bonding. In the presence of water molecules the torsional energy pro?le of procaine is modified, and hydrogen bonding to water molecules is favored relative to intra-molecular hydrogen bonding.« less

Design of a microbial fuel cell and its transition to microbial electrolytic cell for hydrogen production by electrohydrogenesis.

PubMed

Gupta, Pratima; Parkhey, Piyush; Joshi, Komal; Mahilkar, Anjali

2013-10-01

Anaerobic bacteria were isolated from industrial wastewater and soil samples and tested for exoelectrogenic activity by current production in double chambered microbial fuel cell (MFC), which was further transitioned into a single chambered microbial electrolytic cell to test hydrogen production by electrohydrogenesis. Of all the cultures, the isolate from industrial water sample showed the maximum values for current = 0.161 mA, current density = 108.57 mA/m2 and power density = 48.85 mW/m2 with graphite electrode. Maximum voltage across the cell, however, was reported by the isolate from sewage water sample (506 mv) with copper as electrode. Tap water with KMnO4 was the best cathodic electrolyte as the highest values for all the measured MFC parameters were reported with it. Once the exoelectrogenic activity of the isolates was confirmed by current production, these were tested for hydrogen production in a single chambered microbial electrolytic cell (MEC) modified from the MFC. Hydrogen production was reported positive from co-culture of isolates of both the water samples and co-culture of one soil and one water sample. The maximum rate and yield of hydrogen production was 0.18 m3H2/m3/d and 3.2 mol H2/mol glucose respectively with total hydrogen production of 42.4 mL and energy recovery of 57.4%. Cumulative hydrogen production for a five day cycle of MEC operation was 0.16 m3H2/m3/d.

Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reactedmore » CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.« less

A molecular molybdenum-oxo catalyst for generating hydrogen from water.

PubMed

Karunadasa, Hemamala I; Chang, Christopher J; Long, Jeffrey R

2010-04-29

A growing awareness of issues related to anthropogenic climate change and an increase in global energy demand have made the search for viable carbon-neutral sources of renewable energy one of the most important challenges in science today. The chemical community is therefore seeking efficient and inexpensive catalysts that can produce large quantities of hydrogen gas from water. Here we identify a molybdenum-oxo complex that can catalytically generate gaseous hydrogen either from water at neutral pH or from sea water. This work shows that high-valency metal-oxo species can be used to create reduction catalysts that are robust and functional in water, a concept that has broad implications for the design of 'green' and sustainable chemistry cycles.

A two-dimensional hydrogen-bonded water layer in the structure of a cobalt(III) cubane complex.

PubMed

Qi, Ji; Zhai, Xiang-Sheng; Zhu, Hong-Lin; Lin, Jian-Li

2014-02-01

A tetranuclear Co(III) oxide complex with cubane topology, tetrakis(2,2'-bipyridine-κ(2)N,N')di-μ2-carbonato-κ(4)O:O'-tetra-μ3-oxido-tetracobalt(III) pentadecahydrate, [Co4(CO3)2O4(C10H8N2)4]·15H2O, with an unbounded hydrogen-bonded water layer, has been synthesized by reaction of CoCO3 and 2,2'-bipyridine. The solvent water molecules form a hydrogen-bonded net with tetrameric and pentameric water clusters as subunits. The Co4O4 cubane-like cores are sandwiched between the water layers, which are further stacked into a three-dimensional metallo-supramolecular network.

Hydrogen bonding directed self-assembly of small-molecule amphiphiles in water.

PubMed

Xu, Jiang-Fei; Niu, Li-Ya; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

2014-08-01

Compounds comprising one or two quadruply hydrogen bonding units, 2-ureido-4[1H]-pyrimidinone (UPy) and tris(tetraethylene glycol monomethyl ether) moieties, were reported to form highly stable hydrogen-bonded assemblies in water. Compound 1, containing one UPy, assembles into vesicles, and compound 2, containing two UPy units, forms micelles. The aggregates disassemble reversibly when the solution pH is raised to 9.0 or above. The results demonstrate the utility of hydrogen bonding to direct the self-assembly of small-molecule building blocks in aqueous media.

Cation–hydroxide–water coadsorption inhibits the alkaline hydrogen oxidation reaction

DOE PAGES

Chung, Hoon Taek; Martinez, Ulises; Matanovic, Ivana; ...

2016-10-24

Rotating disk electrode voltammograms and infrared reflection absorption spectra indicate that the hydrogen oxidation reaction of platinum in 0.1 M tetramethylammonium hydroxide solution is adversely impacted by time-dependent and potential-driven cation–hydroxide–water coadsorption. Impedance analysis suggests that the hydrogen oxidation reaction inhibition is mainly caused by the hydrogen diffusion barrier of the coadsorbed trilayer rather than intuitive catalyst site blocking by the adsorbed cation species. Finally, these results give useful insights on how to design ionomeric binders for advanced alkaline membrane fuel cells.

Polymeric carbon nitride for solar hydrogen production.

PubMed

Li, Xiaobo; Masters, Anthony F; Maschmeyer, Thomas

2017-07-04

If solar hydrogen production from water is to be a realistic candidate for industrial hydrogen production, the development of photocatalysts, which avoid the use of expensive and/or toxic elements is highly desirable from a scalability, cost and environmental perspective. Metal-free polymeric carbon nitride is an attractive material that can absorb visible light and produce hydrogen from water. This article reviews recent developments in polymeric carbon nitride as used in photocatalysis and then develops the discussion focusing on the three primary processes of a photocatalytic reaction: light-harvesting, carrier generation/separation/transportation and surface reactions.

Hydrogen production by the decomposition of water

DOEpatents

Hollabaugh, Charles M.; Bowman, Melvin G.

1981-01-01

How to produce hydrogen from water was a problem addressed by this invention. The solution employs a combined electrolytical-thermochemical sulfuric acid process. Additionally, high purity sulfuric acid can be produced in the process. Water and SO.sub.2 react in electrolyzer (12) so that hydrogen is produced at the cathode and sulfuric acid is produced at the anode. Then the sulfuric acid is reacted with a particular compound M.sub.r X.sub.s so as to form at least one water insoluble sulfate and at least one water insoluble oxide of molybdenum, tungsten, or boron. Water is removed by filtration; and the sulfate is decomposed in the presence of the oxide in sulfate decomposition zone (21), thus forming SO.sub.3 and reforming M.sub.r X.sub.s. The M.sub.r X.sub.s is recycled to sulfate formation zone (16). If desired, the SO.sub.3 can be decomposed to SO.sub.2 and O.sub.2 ; and the SO.sub.2 can be recycled to electrolyzer (12) to provide a cycle for producing hydrogen.

Using advanced oxidation treatment for biofilm inactivation by varying water vapor content in air plasma

NASA Astrophysics Data System (ADS)

Ryota, Suganuma; Koichi, Yasuoka

2015-09-01

Biofilms are caused by environmental degradation in food factories and medical facilities. The inactivation of biofilms involves making them react with chemicals including chlorine, hydrogen peroxide, and ozone, although inactivation using chemicals has a potential problem because of the hazardous properties of the residual substance and hydrogen peroxide, which have slow reaction velocity. We successfully performed an advanced oxidation process (AOP) using air plasma. Hydrogen peroxide and ozone, which were used for the formation of OH radicals in our experiment, were generated by varying the amount of water vapor supplied to the plasma. By varying the content of the water included in the air, the main product was changed from air plasma. When we increased the water content in the air, hydrogen peroxide was produced, while ozone peroxide was produced when we decreased the water content in the air. By varying the amount of water vapor, we realized a 99.9% reduction in the amount of bacteria in the biofilm when we discharged humidified air only. This work was supported by JSPS KAKENHI Grant Number 25630104.

Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

PubMed

Anglada, Josep M; Gonzalez, Javier

2009-12-07

The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

On-site generation of hydrogen from ethanol

DOT National Transportation Integrated Search

2008-01-01

Supercritical water is a synergistic, non-catalytic media for the reformation of crude ethanol feedstocks into hydrogen. The kinetics of the supercritical water reformation of ethanol was experimentally studied in a tubular reactor made of Inconel 62...

Anti-reflective nanoporous silicon for efficient hydrogen production

DOEpatents

Oh, Jihun; Branz, Howard M

2014-05-20

Exemplary embodiments are disclosed of anti-reflective nanoporous silicon for efficient hydrogen production by photoelectrolysis of water. A nanoporous black Si is disclosed as an efficient photocathode for H.sub.2 production from water splitting half-reaction.

The onsite manufacture of propellant oxygen from lunar resources

NASA Technical Reports Server (NTRS)

Rosenberg, Sanders D.; Beegle, Robert L., Jr.; Guter, Gerald A.; Miller, Frederick E.; Rothenberg, Michael

1992-01-01

The Aerojet carbothermal process for the manufacture of oxygen from lunar materials has three essential steps: the reduction of silicate with methane to form carbon monoxide and hydrogen; the reduction of carbon monoxide with hydrogen to form methane and water; and the electrolysis of water to form hydrogen and oxygen. The reactions and the overall process are shown. It is shown with laboratory experimentation that the carbothermal process is feasible. Natural silicates can be reduced with carbon or methane. The important products are carbon monoxide, metal, and slag. The carbon monoxide can be completely reduced to form methane and water. The water can be electrolyzed to produce hydrogen and oxygen. A preliminary engineering study shows that the operation of plants using this process for the manufacture of propellant oxygen has a large economic advantage when the cost of the plant and its operation is compared to the cost of delivering oxygen from Earth.

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

USGS Publications Warehouse

O'Neil, J.R.; Kharaka, Y.K.

1976-01-01

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

Cryopumping of hydrogen in vacuum chambers is aided by catalytic oxidation of hydrogen

NASA Technical Reports Server (NTRS)

Childs, J. H.; Grobman, J.; Rayle, W.

1964-01-01

Vacuum test facilities are required for high speed cryopumping of gaseous hydrogen at low pressures. One method involves the catalytic oxidation of hydrogen and condensation of the resulting water on a liquid nitrogen-cooled surface.

Effect Of Water On Permeation By Hydrogen

NASA Technical Reports Server (NTRS)

Tomazic, William A.; Hulligan, David

1988-01-01

Water vapor in working fluid equilibrates with permeability-reducing oxides in metal parts. Report describes study of effects of water on permeation of heater-head tubes by hydrogen in Stirling engine. Experiments performed to determine minimum concentration of oxygen and/or oxygen-bearing gas maintaining oxide coverage adequate for low permeability. Tests showed 750 ppm or more of water effective in maintaining stable, low permeability.

Hydrogen generation from water using Mg nanopowder produced by arc plasma method.

PubMed

Uda, Masahiro; Okuyama, Hideo; Suzuki, Tohru S; Sakka, Yoshio

2012-04-01

We report that hydrogen gas can be easily produced from water at room temperature using a Mg nanopowder (30-1000 nm particles, average diameter 265 nm). The Mg nanopowder was produced by dc arc melting of a Mg ingot in a chamber with mixed-gas atmosphere (20% N 2 -80% Ar) at 0.1 MPa using custom-built nanopowder production equipment. The Mg nanopowder was passivated with a gas mixture of 1% O 2 in Ar for 12 h in the final step of the synthesis, after which the nanopowder could be safely handled in ambient air. The nanopowder vigorously reacted with water at room temperature, producing 110 ml of hydrogen gas per 1 g of powder in 600 s. This amount corresponds to 11% of the hydrogen that could be generated by the stoichiometric reaction between Mg and water. Mg(OH) 2 flakes formed on the surface of the Mg particles as a result of this reaction. They easily peeled off, and the generation of hydrogen continued until all the Mg was consumed.

Hydrogen bonding in water clusters and their ionized counterparts.

PubMed

Neela, Y Indra; Mahadevi, A Subha; Sastry, G Narahari

2010-12-30

Ab initio and DFT computations were carried out on four distinct hydrogen-bonded arrangements of water clusters (H(2)O)(n), n = 2-20, represented as W1D, W2D, W2DH, and W3D. The variation in the strength of hydrogen bond as a function of the chain length is studied. In all the four cases, there is a substantial cooperative interaction, albeit in different degrees. The effect of basis set superposition error (BSSE) on the complexation energy of water clusters has been analyzed. Atoms in molecules (AIM) analysis performed to evaluate the nature of the hydrogen bonding shows a high correlation between hydrogen bond strength and the trends in complexation energy. Solvated water clusters exhibit lower complexation energies compared to corresponding gas-phase geometries on PCM (polarized continuum model) optimization. The feasibility of stripping an electron or addition of an electron increases dramatically as the cluster size increases. Although W3D caged structures are stable for neutral clusters, the helical W2DH arrangement appeared to be an optimal choice for its ionized counterparts.

Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

USGS Publications Warehouse

Coplen, Tyler B.; Qi, Haiping

2010-01-01

An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ2H reproducibility (1& sigma; standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen

Hydrogen isotopes in individual amino acids reflect differentiated pools of hydrogen from food and water in Escherichia coli.

PubMed

Fogel, Marilyn L; Griffin, Patrick L; Newsome, Seth D

2016-08-09

Hydrogen isotope (δ(2)H) analysis is widely used in animal ecology to study continental-scale movement because δ(2)H can trace precipitation and climate. To understand the biochemical underpinnings of how hydrogen is incorporated into biomolecules, we measured the δ(2)H of individual amino acids (AAs) in Escherichia coli cultured in glucose-based or complex tryptone-based media in waters with δ(2)H values ranging from -55‰ to +1,070‰. The δ(2)H values of AAs in tryptone spanned a range of ∼250‰. In E. coli grown on glucose, the range of δ(2)H among AAs was nearly 200‰. The relative distributions of δ(2)H of AAs were upheld in cultures grown in enriched waters. In E. coli grown on tryptone, the δ(2)H of nonessential AAs varied linearly with the δ(2)H of media water, whereas δ(2)H of essential AAs was nearly identical to δ(2)H in diet. Model calculations determined that as much as 46% of hydrogen in some nonessential AAs originated from water, whereas no more than 12% of hydrogen in essential AAs originated from water. These findings demonstrate that δ(2)H can route directly at the molecular level. We conclude that the patterns and distributions in δ(2)H of AAs are determined through biosynthetic reactions, suggesting that δ(2)H could become a new biosignature for studying novel microbial pathways. Our results also show that δ(2)H of AAs in an organism's tissues provides a dual tracer for food and environmental (e.g., drinking) water.

Hydrogen isotopes in individual amino acids reflect differentiated pools of hydrogen from food and water in Escherichia coli

PubMed Central

Fogel, Marilyn L.; Griffin, Patrick L.; Newsome, Seth D.

2016-01-01

Hydrogen isotope (δ2H) analysis is widely used in animal ecology to study continental-scale movement because δ2H can trace precipitation and climate. To understand the biochemical underpinnings of how hydrogen is incorporated into biomolecules, we measured the δ2H of individual amino acids (AAs) in Escherichia coli cultured in glucose-based or complex tryptone-based media in waters with δ2H values ranging from −55‰ to +1,070‰. The δ2H values of AAs in tryptone spanned a range of ∼250‰. In E. coli grown on glucose, the range of δ2H among AAs was nearly 200‰. The relative distributions of δ2H of AAs were upheld in cultures grown in enriched waters. In E. coli grown on tryptone, the δ2H of nonessential AAs varied linearly with the δ2H of media water, whereas δ2H of essential AAs was nearly identical to δ2H in diet. Model calculations determined that as much as 46% of hydrogen in some nonessential AAs originated from water, whereas no more than 12% of hydrogen in essential AAs originated from water. These findings demonstrate that δ2H can route directly at the molecular level. We conclude that the patterns and distributions in δ2H of AAs are determined through biosynthetic reactions, suggesting that δ2H could become a new biosignature for studying novel microbial pathways. Our results also show that δ2H of AAs in an organism’s tissues provides a dual tracer for food and environmental (e.g., drinking) water. PMID:27444017

Rapid Diffusion and Nanosegregation of Hydrogen in Magnesium Alloys from Exposure to Water.

PubMed

Brady, Michael P; Ievlev, Anton V; Fayek, Mostafa; Leonard, Donovan N; Frith, Matthew G; Meyer, Harry M; Ramirez-Cuesta, Anibal J; Daemen, Luke L; Cheng, Yongqiang; Guo, Wei; Poplawsky, Jonathan D; Ovchinnikova, Olga S; Thomson, Jeffrey; Anovitz, Lawrence M; Rother, Gernot; Shin, Dongwon; Song, Guang-Ling; Davis, Bruce

2017-11-01

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2 O/D isotopic tracer and H 2 O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at room temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2-3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2 . These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.

Rapid Diffusion and Nanosegregation of Hydrogen in Magnesium Alloys from Exposure to Water

DOE PAGES

Brady, Michael P.; Ievlev, Anton V.; Fayek, Mostafa; ...

2017-10-10

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2O/D isotopic tracer and H 2O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at roommore » temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2–3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2. These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.« less

Hydrogen Production Cost Analysis | Hydrogen and Fuel Cells | NREL

Science.gov Websites

Analysis Hydrogen Production Cost Analysis This interactive map displays the results of a 2011 NREL analysis on the cost of hydrogen from electrolysis at potential sites across the United States. NREL analyzed the cost of hydrogen production via wind-based water electrolysis at 42 potential sites in 11

MELCOR Model of the Spent Fuel Pool of Fukushima Dai-ichi Unit 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carbajo, Juan J

2012-01-01

Unit 4 of the Fukushima Dai-ichi Nuclear Power Plant suffered a hydrogen explosion at 6:00 am on March 15, 2011, exactly 3.64 days after the earthquake hit the plant and the off-site power was lost. The earthquake occurred on March 11 at 2:47 pm. Since the reactor of this Unit 4 was defueled on November 29, 2010, and all its fuel was stored in the spent fuel pool (SFP4), it was first believed that the explosion was caused by hydrogen generated by the spent fuel, in particular, by the recently discharged core. The hypothetical scenario was: power was lost, coolingmore » to the SFP4 water was lost, pool water heated/boiled, water level decreased, fuel was uncovered, hot Zircaloy reacted with steam, hydrogen was generated and accumulated above the pool, and the explosion occurred. Recent analyses of the radioisotopes present in the water of the SFP4 and underwater video indicated that this scenario did not occur - the fuel in this pool was not damaged and was never uncovered the hydrogen of the explosion was apparently generated in Unit 3 and transported through exhaust ducts that shared the same chimney with Unit 4. This paper will try to answer the following questions: Could that hypothetical scenario in the SFP4 had occurred? Could the spent fuel in the SPF4 generate enough hydrogen to produce the explosion that occurred 3.64 days after the earthquake? Given the magnitude of the explosion, it was estimated that at least 150 kg of hydrogen had to be generated. As part of the investigations of this accident, MELCOR models of the SFP4 were prepared and a series of calculations were completed. The latest version of MELCOR, version 2.1 (Ref. 1), was employed in these calculations. The spent fuel pool option for BWR fuel was selected in MELCOR. The MELCOR model of the SFP4 consists of a total of 1535 fuel assemblies out of which 548 assemblies are from the core defueled on Nov. 29, 2010, 783 assemblies are older assemblies, and 204 are new/fresh assemblies. The total decay heat of the fuel in the pool was, at the time of the accident, 2.284 MWt, of which 1.872 MWt were from the 548 assemblies of the last core discharged and 0.412 MWt were from the older 783 assemblies. These decay heat values were calculated at Oak Ridge National Laboratory using the ORIGEN2.2 code (Ref. 2) - they agree with values reported elsewhere (Ref. 3). The pool dimensions are 9.9 m x 12.2 m x 11.8 m (height), and with the water level at 11.5 m, the pool volume is 1389 m3, of which only 1240 m3 is water, as some volume is taken by the fuel and by the fuel racks. The initial water temperature of the SFP4 was assumed to be 301 K. The fuel racks are made of an aluminum alloy but are modeled in MELCOR with stainless steel and B4C. MELCOR calculations were completed for different initial water levels: 11.5 m (pool almost full, water is only 0.3 m below the top rim), 4.4577 m (top of the racks), 4.2 m, and 4.026 m (top of the active fuel). A calculation was also completed for a rapid loss of water due to a leak at the bottom of the pool, with the fuel rapidly uncovered and oxidized in air. Results of these calculations are shown in the enclosed Table I. The calculation with the initial water level at 11.5 m (full pool) takes 11 days for the water to boil down to the top of the fuel racks, 11.5 days for the fuel to be uncovered, 14.65 days to generate 150 kg of hydrogen and 19 days for the pool to be completely dry. The calculation with the initial water level at 4.4577 m, takes 1.1 days to uncover the fuel and 4.17 days to generate 150 kg of hydrogen. The calculation with the initial water level at 4.02 m takes 3.63 days to generate 150 kg of hydrogen this is exactly the time when the actual explosion occurred in Unit 4. Finally, fuel oxidation in air after the pool drained the water in 20 minutes, generates only 10 kg of hydrogen this is because very little steam is available and Zircaloy (Zr) oxidation with the oxygen of the air does not generate hydrogen. MELCOR calculated water levels and hydrogen generated in the SFP4 as a function of time for initial water levels of 4.457 m, 4.2 m and 4.02 m are shown in Figs. 1 and 2. Water levels increase at the beginning due to the expansion of the water during the heat-up from 301 K to 373 K. Boiling occurs after the water temperature reaches 373 K. The total amount of hydrogen generated is ~2000 kg, this amount includes hydrogen generated from Zr, which is the largest amount (~1580 kg), from stainless steel (~360 kg), and from B4C (~60 kg). In theory, it is possible to generate up to 3.4 kg of hydrogen per assembly (from oxidation of Zr in the fuel cladding and box), or a total of 4,525 kg from the hot 1331 assemblies stored in the SFP4. The hydrogen generated from oxidation of steel and B4C will be additional. So the answers to the questions are YES according to these MELCOR calculations, enough hydrogen (150 kg) could be generated in the SFP4 3.64 days after the earthquake to produce ...« less

The change in hydrogen bond strength accompanying charge rearrangement: Implications for enzymatic catalysis

PubMed Central

Shan, Shu-ou; Herschlag, Daniel

1996-01-01

The equilibrium for formation of the intramolecular hydrogen bond (KHB) in a series of substituted salicylate monoanions was investigated as a function of ΔpKa, the difference between the pKa values of the hydrogen bond donor and acceptor, in both water and dimethyl sulfoxide. The dependence of log KHB upon ΔpKa is linear in both solvents, but is steeper in dimethyl sulfoxide (slope = 0.73) than in water (slope = 0.05). Thus, hydrogen bond strength can undergo substantially larger increases in nonaqueous media than aqueous solutions as the charge density on the donor or acceptor atom increases. These results support a general mechanism for enzymatic catalysis, in which hydrogen bonding to a substrate is strengthened as charge rearranges in going from the ground state to the transition state; the strengthening of the hydrogen bond would be greater in a nonaqueous enzymatic active site than in water, thus providing a rate enhancement for an enzymatic reaction relative to the solution reaction. We suggest that binding energy of an enzyme is used to fix the substrate in the low-dielectric active site, where the strengthening of the hydrogen bond in the course of a reaction is increased. PMID:8962076

MISCIBILITY CALCULATIONS FOR WATER AND HYDROGEN IN GIANT PLANETS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soubiran, François; Militzer, Burkhard

2015-06-20

We present results from ab initio simulations of liquid water–hydrogen mixtures in the range from 2 to 70 GPa and from 1000 to 6000 K, covering conditions in the interiors of ice giant planets and parts of the outer envelope of gas giant planets. In addition to computing the pressure and the internal energy, we derive the Gibbs free energy by performing a thermodynamic integration. For all conditions under consideration, our simulations predict hydrogen and water to mix in all proportions. The thermodynamic behavior of the mixture can be well described with an ideal mixing approximation. We suggest that amore » substantial fraction of water and hydrogen in giant planets may occur in homogeneously mixed form rather than in separate layers. The extent of mixing depends on the planet’s interior dynamics and its conditions of formation, in particular on how much hydrogen was present when icy planetesimals were delivered. Based on our results, we do not predict water–hydrogen mixtures to phase separate during any stage of the evolution of giant planets. We also show that the hydrogen content of an exoplanet is much higher if the mixed interior is assumed.« less

Hydrogen production from solar energy

NASA Technical Reports Server (NTRS)

Eisenstadt, M. M.; Cox, K. E.

1975-01-01

Three alternatives for hydrogen production from solar energy have been analyzed on both efficiency and economic grounds. The analysis shows that the alternative using solar energy followed by thermochemical decomposition of water to produce hydrogen is the optimum one. The other schemes considered were the direct conversion of solar energy to electricity by silicon cells and water electrolysis, and the use of solar energy to power a vapor cycle followed by electrical generation and electrolysis. The capital cost of hydrogen via the thermochemical alternative was estimated at $575/kW of hydrogen output or $3.15/million Btu. Although this cost appears high when compared with hydrogen from other primary energy sources or from fossil fuel, environmental and social costs which favor solar energy may prove this scheme feasible in the future.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, C.E.; Robinson, P.R.

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, Carlos E.; Robinson, Paul R.

1980-01-01

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Water-induced ethanol dewetting transition.

PubMed

Ren, Xiuping; Zhou, Bo; Wang, Chunlei

2012-07-14

The dewetting transitions of two hydrophobic plates immersed in pure water, aqueous ethanol solutions with concentrations from 25% to 90%, and pure ethanol were investigated by molecular dynamics simulations, where the dewetting transition was analogous to a first-order phase transition from liquid to vapor. It was found that the dewetting transitions occurred except that in the pure ethanol system. Although the ethanol molecules prefer to locate in the vicinity of the two plates, the inter-plate region is unfavorable for water molecules, due to losing more than one hydrogen bond. Moreover, each inter-plate water molecule forms hydrogen bonds on average with about two ethanol molecules. These intermolecular hydrogen bonds cause water and ethanol to cooperatively fill or exit the inter-plate region. Thus, water molecules play a more important role in the inter-plate filling/empty process, and induce the ethanol dewetting transition. Our results provide insight into the effect of water on the ethanol dewetting phenomena.

Inferences on hydrogen bond networks in water from isopermitive frequency investigations.

PubMed

Geethu, P M; Ranganathan, Venketesh T; Satapathy, Dillip K Kumar

2018-06-26

Intermolecular hydrogen bonds play a crucial role in determining the unique characteristics of liquid water. We present low-frequency (1 Hz - 40 MHz) dielectric spectroscopic investigations on water in the presence and absence of added solutes at different temperatures from 10°C to 60°C. The intersection points of temperature dependent permittivity contours at the vicinity of isopermitive frequency (IPF) in water are recorded and its properties are presumed to be related to the extent of hydrogen bond networks in water. IPF is defined as the frequency at which the relative permittivity of water is almost independent of temperature. The set of intersection points of temperature dependent permittivity contours at the vicinity of IPF are characterized by the mean (M_IPF) and root-mean-square deviation/standard deviation (σ_IPF ) associated with IPF. The tunability of M_IPF by the addition of NaCl salt emphasizes the strong correlation between the concentration of ions in water and the M_IPF . The σ_IPF is surmised to be related to the orientational correlations of water dipoles as well as to the intermolecular hydrogen bond networks in water. Further, alterations in σ_IPF is observed with the addition of kosmotropic and chaotropic solutes into water and are thought to arise due to the restructuring of hydrogen bond networks in water in presence of added solutes. Notably, the solute induced reconfiguration of hydrogen bond networks in water or often-discussed structure making/breaking effects of the added solutes in water can be inferred, albeit qualitatively, by examining the M_IPF and σ_IPF. Further, the Gaussian deconvoluted OH-stretching modes present in the Raman Spectra of water and aqueous solutions of IPA and DMF strongly endorses the structural rearrangements occurring in water in presence of kosmotropes and chaotropes and are in-line with the results derived from the root-mean-square deviation in IPF. . © 2018 IOP Publishing Ltd.

The origins of femtomolar protein-ligand binding: hydrogen-bond cooperativity and desolvation energetics in the biotin-(strept)avidin binding site.

PubMed

DeChancie, Jason; Houk, K N

2007-05-02

The unusually strong reversible binding of biotin by avidin and streptavidin has been investigated by density functional and MP2 ab initio quantum mechanical methods. The solvation of biotin by water has also been studied through QM/MM/MC calculations. The ureido moiety of biotin in the bound state hydrogen bonds to five residues, three to the carbonyl oxygen and one for each--NH group. These five hydrogen bonds act cooperatively, leading to stabilization that is larger than the sum of individual hydrogen-bonding energies. The charged aspartate is the key residue that provides the driving force for cooperativity in the hydrogen-bonding network for both avidin and streptavidin by greatly polarizing the urea of biotin. If the residue is removed, the network is disrupted, and the attenuation of the energetic contributions from the neighboring residues results in significant reduction of cooperative interactions. Aspartate is directly hydrogen-bonded with biotin in streptavidin and is one residue removed in avidin. The hydrogen-bonding groups in streptavidin are computed to give larger cooperative hydrogen-bonding effects than avidin. However, the net gain in electrostatic binding energy is predicted to favor the avidin-bicyclic urea complex due to the relatively large penalty for desolvation of the streptavidin binding site (specifically expulsion of bound water molecules). QM/MM/MC calculations involving biotin and the ureido moiety in aqueous solution, featuring PDDG/PM3, show that water interactions with the bicyclic urea are much weaker than (strept)avidin interactions due to relatively low polarization of the urea group in water.

Exhaled breath condensate pH in mechanically ventilated patients.

PubMed

Nannini, L J; Quintana, R; Bagilet, D H; Druetta, M; Ramírez, M; Nieto, R; Guelman Greta, G

2013-12-01

In this prospective clinical trial we aimed to answer if spontaneous exhaled breath condensate (EBC) in the trap of the expiratory arm of the ventilator could replace EBC collected by coolant chamber standardized with Argon as an inert gas. Second, if EBC pH could predict ventilator associated pneumonia (VAP) and mortality. We included 34 critically ill patients (males = 26), aged = 54.85 ± 19.86 (mean ± SD) yrs, that required mechanical ventilation due to non-pulmonary direct cause (APACHE II score = 23.58 ± 14.7; PaO(2)/FiO(2) = 240.00 ± 98.29). ICU with 9 beds from a regional teaching hospital. The patients were followed up until development of VAP, successful weaning or death. There were significant differences between mean EBC pH from the 4 procedures with the exception of spontaneous EBC de-aerated with Argon (n = 79; 6.74 ± 0.28) and coolant chamber deaerated with Argon (n = 79; 6.70 ± 0.36; p = NS by Tukey's Multiple Comparison Test). However, none of the procedures were extrapolated between each other according to Bland & Altman method. The mean EBC pH from the trap without Argon was 6.50 ± 0.28. From the total of 34 patients, 22 survived and were discharged and 12 patients died in the ICU. Spontaneous EBC pH could not be extrapolated to EBC pH from coolant chamber and it did not change in subjects who dead, neither subject with VAP in comparison with baseline data. The lack of other biomarker in EBC and the lack of a control group determinate the need for further studies in this setting. Copyright © 2012 Elsevier España, S.L. and SEMICYUC. All rights reserved.

Prospects for pipeline delivery of hydrogen as a fuel and as a chemical feedstock

NASA Technical Reports Server (NTRS)

Gregory, D. P.; Biederman, N. P.; Darrow, K. G., Jr.; Konopka, A. J.; Wurm, J.

1976-01-01

The possibility of using hydrogen for storing and carrying energy obtained from nonfossil sources such as nuclear and solar energy is examined. According to the method proposed, these nonfossil raw energy sources will be used to obtain hydrogen from water by three basically distinct routes: (1) electrical generation followed by electrolysis; (2) thermochemical decomposition; and (3) direct neutron or ultraviolet irradiation of hydrogen bearing molecules. The hydrogen obtained will be transmitted in long-distance pipelines, and distributed to all energy-consuming sectors. As a fuel gas, hydrogen has many qualities similar to natural gas and with only minor modifications, it can be transmitted and distributed in the same equipment, and can be burned in the same appliances as natural gas. Hydrogen can also be used as a clean fuel (water is the only combustion product) for automobiles, fleet vehicles, and aircraft.

Improved Electrolytic Hydrogen Peroxide Generator

NASA Technical Reports Server (NTRS)

James, Patrick I.

2005-01-01

An improved apparatus for the electrolytic generation of hydrogen peroxide dissolved in water has been developed. The apparatus is a prototype of H2O2 generators for the safe and effective sterilization of water, sterilization of equipment in contact with water, and other applications in which there is need for hydrogen peroxide at low concentration as an oxidant. Potential applications for electrolytic H2O2 generators include purification of water for drinking and for use in industrial processes, sanitation for hospitals and biotechnological industries, inhibition and removal of biofouling in heat exchangers, cooling towers, filtration units, and the treatment of wastewater by use of advanced oxidation processes that are promoted by H2O2.

Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

DOE PAGES

Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.; ...

2017-11-26

The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300–360 °C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N 2 gas. Lastly, results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.

Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.

The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300–360 °C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N 2 gas. Lastly, results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.

Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.

The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300-360°C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N2 gas. Results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.

Thermochemical generation of hydrogen and oxygen from water. [NaMnO/sub 2/ and TiO/sub 2/

DOEpatents

Robinson, P.R.; Bamberger, C.E.

1980-02-08

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO/sub 2/) and titanium dioxide (TiO/sub 2/) to form sodium titanate (Na/sub 2/TiO/sub 3/), manganese (II) titanate (MnTiO/sub 3/) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Slow Strain Rate Testing for Hydrogen Embrittlement Susceptibility of Alloy 718 in Substitute Ocean Water

NASA Astrophysics Data System (ADS)

LaCoursiere, M. P.; Aidun, D. K.; Morrison, D. J.

2017-05-01

The hydrogen embrittlement susceptibility of near-peak-aged UNS N07718 (Alloy 718) was evaluated by performing slow strain rate tests at room temperature in air and substitute ocean water. Tests in substitute ocean water were accomplished in an environmental cell that enabled in situ cathodic charging under an applied potential of -1.1 V versus SCE. Some specimens were cathodically precharged for 4 or 16 weeks at the same potential in a 3.5 wt.% NaCl-distilled water solution at 50 °C. Unprecharged specimens tested in substitute ocean water exhibited only moderate embrittlement with plastic strain to failure decreasing by about 20% compared to unprecharged specimens tested in air. However, precharged specimens exhibited significant embrittlement with plastic strain to failure decreasing by about 70%. Test environment (air or substitute ocean water with in situ charging) and precharge time (4 or 16 weeks) had little effect on the results of the precharged specimens. Fracture surfaces of precharged specimens were typical of hydrogen embrittlement and consisted of an outer brittle ring related to the region in which hydrogen infused during precharging, a finely dimpled transition zone probably related to the region where hydrogen was drawn in by dislocation transport, and a central highly dimpled ductile region. Fracture surfaces of unprecharged specimens tested in substitute ocean water consisted of a finely dimpled outer ring and heavily dimpled central region typical of ductile fracture.

Tensile properties of ADI material in water and gaseous environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajnovic, Dragan, E-mail: draganr@uns.ac.rs; Balos, Sebastian; Sidjanin, Leposava

2015-03-15

Austempered ductile iron (ADI) is an advanced type of heat treated ductile iron, having comparable mechanical properties as forged steels. However, it was found that in contact with water the mechanical properties of austempered ductile irons decrease, especially their ductility. Despite considerable scientific attention, the cause of this phenomenon remains unclear. Some authors suggested that hydrogen or small atom chemisorption causes the weakening of the surface atomic bonds. To get additional reliable data of that phenomenon, in this paper, two different types of austempered ductile irons were tensile tested in various environments, such as: argon, helium, hydrogen gas and water.more » It was found that only the hydrogen gas and water gave a statistically significant decrease in mechanical properties, i.e. cause embrittlement. Furthermore, the fracture surface analysis revealed that the morphology of the embrittled zone near the specimen surface shares similarities to the fatigue micro-containing striation-like lines, which indicates that the morphology of the brittle zone may be caused by cyclic local-chemisorption, micro-embrittlement and local-fracture. - Highlights: • In contact with water and other liquids the ADI suddenly exhibits embrittlement. • The embrittlement is more pronounced in water than in the gaseous hydrogen. • The hydrogen chemisorption into ADI surface causes the formation of a brittle zone. • The ADI austempered at lower temperatures (300 °C) is more resistant to embrittlement.« less

Direct thermal water splitting by concentrated solar radiation for hydrogen production. Phase O: Proof of concept experiment

NASA Technical Reports Server (NTRS)

Genequand, P.

1980-01-01

The direct production of hydrogen from water and solar energy concentrated into a high temperature aperture is described. A solar powered reactor able to dissociate water vapor and to separate the reaction product at high temperature was developed, and direct water splitting has been achieved in a laboratory reactor. Water vapor and radiative heating from a carbon dioxide laser are fed into the reactor, and water vapor enriched in hydrogen and water vapor enriched in oxygen are produced. The enriched water vapors are separated through a separation membrane, a small disc of zirconium dioxide heated to a range of 1800 k to 2800 k. To avoid water vapor condensation within the reactor, the total pressure within the reactor was limited to 0.15 torr. A few modifications would enable the reactor to be operated at an increased pressure of a few torrs. More substantial modifications would allow for a reaction pressure of 0.1 atmosphere.

Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

NASA Astrophysics Data System (ADS)

Marin, Timothy W.; Janik, Ireneusz; Bartels, David M.; Chipman, Daniel M.

2017-05-01

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381 °C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. Using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.

Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

DOE PAGES

Marin, Timothy W.; Janik, Ireneusz; Bartels, David M.; ...

2017-05-17

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381°C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as themore » water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. As a result, using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.« less

Water Hydrogen-Bonding Network Structure and Dynamics at Phospholipid Multibilayer Surface: Femtosecond Mid-IR Pump-Probe Spectroscopy.

PubMed

Kundu, Achintya; Błasiak, Bartosz; Lim, Joon-Hyung; Kwak, Kyungwon; Cho, Minhaeng

2016-03-03

The water hydrogen-bonding network at a lipid bilayer surface is crucial to understanding membrane structures and its functional activities. With a phospholipid multibilayer mimicking a biological membrane, we study the temperature dependence of water hydrogen-bonding structure, distribution, and dynamics at a lipid multibilayer surface using femtosecond mid-IR pump-probe spectroscopy. We observe two distinguished vibrational lifetime components. The fast component (0.6 ps) is associated with water interacting with a phosphate part, whereas the slow component (1.9 ps) is with bulk-like choline-associated water. With increasing temperature, the vibrational lifetime of phosphate-associated water remains constant though its relative fraction dramatically increases. The OD stretch vibrational lifetime of choline-bound water slows down in a sigmoidal fashion with respect to temperature, indicating a noticeable change of the water environment upon the phase transition. The water structure and dynamics are thus shown to be in quantitative correlation with the structural change of liquid multibilayer upon the gel-to-liquid crystal phase transition.

Water in the Active Site of Ketosteroid Isomerase

PubMed Central

Hanoian, Philip; Hammes-Schiffer, Sharon

2011-01-01

Classical molecular dynamics simulations were utilized to investigate the structural and dynamical properties of water in the active site of ketosteroid isomerase (KSI) to provide insight into the role of these water molecules in the enzyme-catalyzed reaction. This reaction is thought to proceed via a dienolate intermediate that is stabilized by hydrogen bonding with residues Tyr16 and Asp103. A comparative study was performed for the wild-type (WT) KSI and the Y16F, Y16S, and Y16F/Y32F/Y57F (FFF) mutants. These systems were studied with three different bound ligands: equilenin, which is an intermediate analog, and the intermediate states of two steroid substrates. Several distinct water occupation sites were identified in the active site of KSI for the WT and mutant systems. Three additional sites were identified in the Y16S mutant that were not occupied in WT KSI or the other mutants studied. The number of water molecules directly hydrogen bonded to the ligand oxygen was approximately two waters in the Y16S mutant, one water in the Y16F and FFF mutants, and intermittent hydrogen bonding of one water molecule in WT KSI. The molecular dynamics trajectories of the Y16F and FFF mutants reproduced the small conformational changes of residue 16 observed in the crystal structures of these two mutants. Quantum mechanical/molecular mechanical calculations of 1H NMR chemical shifts of the protons in the active site hydrogen-bonding network suggest that the presence of water in the active site does not prevent the formation of short hydrogen bonds with far-downfield chemical shifts. The molecular dynamics simulations indicate that the active site water molecules exchange much more frequently for WT KSI and the FFF mutant than for the Y16F and Y16S mutants. This difference is most likely due to the hydrogen-bonding interaction between Tyr57 and an active site water molecule that is persistent in the Y16F and Y16S mutants but absent in the FFF mutant and significantly less probable in WT KSI. PMID:21710970

The Role of Water in the Storage of Hydrogen in Metals

NASA Technical Reports Server (NTRS)

Hampton, Michael D.; Lomness, Janice K.; Giannuzzi, Lucille A.

2001-01-01

One major problem with the use of hydrogen is safe and efficient storage. In the pure form, bulky and heavy containers are required greatly reducing the efficiency of its use. Safety is also a great concern. Storage of hydrogen in the form of a metal hydride offers distinct advantages both in terms of volumetric efficiency and in terms of safety. As a result, an enormous amount of research is currently being done on metal-hydrogen systems. Practical application of these systems to storage of hydrogen can only occur when they are very well understood. In this paper, the preliminary results of a study of the surfaces of magnesium nickel alloys will be presented. Alloys that have been rendered totally unreactive with hydrogen as well as those that have been activated with liquid water and with water vapor were studied. Data obtained from XPS (X-ray Photoelectron Spectrometer) analysis, with samples held in vacuum for the shortest possible time to minimize the hydroxide degradation will be presented. Furthermore, TEM data on samples prepared in a new way that largely protects the surface from the high vacuum will be discussed.

Conformers and hydrogen bonds in cytidine 5‧-diphosphocholine sodium single crystals grown from a mixture of ethanol and water

NASA Astrophysics Data System (ADS)

Du, Zhenxing; Hu, Yanan; Wang, Pei; Zhou, Jingwei; Xiong, Jian; Ying, Hanjie; Bai, Jianxin

2011-01-01

The molecular structure of cytidine 5'-diphosphocholine sodium (CDPC) grown from a mixture of ethanol and water was determined by X-ray diffraction (XRD). CDPC was found to have an orthorhombic structure with confirmed lattice parameters of a = 6.978 Å, b = 12.406 Å and c = 29.326 Å. This nucleotide coenzyme was highly folded and net-like. Each crystallographic unit consisted of one sodium atom, one pyrophosphate group, one cytosine group, one coordinated water molecule, one pentose molecule, and three lattice water molecules. The interspaces of neighboring CDPC molecules were filled with water molecules and methyl groups. Although the coordinated water was connected to sodium atoms, the lattice water molecules formed chair-shaped water hexamers. The hydrogen bonds which played an important role in maintaining the structure included O sbnd H···O, N sbnd H···O and C sbnd H···O and ranged in length from 2.682 (17) to 3.349 (17) Å. Fourier transform infrared spectroscopy (FTIR) showed a broad absorption in the 400-2000 cm -1 region characteristic of short hydrogen bonds. So for industrial crystallization, methods which could eliminate the influence of hydrogen bonds should be taken, and it would be beneficial for the process of crystallization.

Influence of Cholesterol on the Dynamics of Hydration in Phospholipid Bilayers.

PubMed

Elola, M Dolores; Rodriguez, Javier

2018-06-07

We investigate the dynamics of interfacial waters in dipalmitoylphosphatidylcholine (DPPC) bilayers upon the addition of cholesterol, by molecular dynamics simulations. Our data reveal that the inclusion of cholesterol modifies the membrane aqueous interfacial dynamics: waters diffuse faster, their rotational decay time is shorter, and the DPPC/water hydrogen bond dynamics relaxes faster than in the pure DPPC membrane. The observed acceleration of the translational water dynamics agrees with recent experimental results, in which, by means of NMR techniques, an increment of the surface water diffusivity is measured upon the addition of cholesterol. A microscopic analysis of the lipid/water hydrogen bond network at the interfacial region suggests that the mechanism underlying the observed water mobility enhancement is given by the rupture of a fraction of interlipid water bridge hydrogen bonds connecting two different DPPC molecules, concomitant to the formation of new lipid/solvent bonds, whose dynamics is faster than that of the former. The consideration of a simple two-state model for the decay of the hydrogen bond correlation function yielded excellent results, obtaining two well-separated characteristic time scales: a slow one (∼250 ps) associated with bonds linking two DPPC molecules, and a fast one (∼15 ps), related to DPPC/solvent bonds.

40 CFR 415.420 - Applicability; description of the hydrogen cyanide production subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... hydrogen cyanide production subcategory. 415.420 Section 415.420 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Hydrogen Cyanide Production Subcategory § 415.420 Applicability; description of the hydrogen cyanide production subcategory. This subpart applies to discharges to waters of the United States...

40 CFR 415.420 - Applicability; description of the hydrogen cyanide production subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... hydrogen cyanide production subcategory. 415.420 Section 415.420 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Hydrogen Cyanide Production Subcategory § 415.420 Applicability; description of the hydrogen cyanide production subcategory. This subpart applies to discharges to waters of the United States...

40 CFR 415.420 - Applicability; description of the hydrogen cyanide production subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... hydrogen cyanide production subcategory. 415.420 Section 415.420 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Hydrogen Cyanide Production Subcategory § 415.420 Applicability; description of the hydrogen cyanide production subcategory. This subpart applies to discharges to waters of the United States...

40 CFR 415.420 - Applicability; description of the hydrogen cyanide production subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... hydrogen cyanide production subcategory. 415.420 Section 415.420 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Hydrogen Cyanide Production Subcategory § 415.420 Applicability; description of the hydrogen cyanide production subcategory. This subpart applies to discharges to waters of the United States...

40 CFR 415.420 - Applicability; description of the hydrogen cyanide production subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... hydrogen cyanide production subcategory. 415.420 Section 415.420 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Hydrogen Cyanide Production Subcategory § 415.420 Applicability; description of the hydrogen cyanide production subcategory. This subpart applies to discharges to waters of the United States...

Photocatalytic hydrogen generation from water under visible light using core/shell nano-catalysts.

PubMed

Wang, X; Shih, K; Li, X Y

2010-01-01

A microemulsion technique was employed to synthesize nano-sized photocatalysts with a core (CdS)/shell (ZnS) structure. The primary particles of the photocatalysts were around 10 nm, and the mean size of the catalyst clusters in water was about 100 nm. The band gaps of the catalysts ranged from 2.25 to 2.46 eV. The experiments of photocatalytic H(2) generation showed that the catalysts (CdS)(x)/(ZnS)(1-x) with x ranging from 0.1 to 1 were able to produce hydrogen from water photolysis under visible light. The catalyst with x=0.9 had the highest rate of hydrogen production. The catalyst loading density also influenced the photo-hydrogen production rate, and the best catalyst concentration in water was 1 g L(-1). The stability of the nano-catalysts in terms of size, morphology and activity was satisfactory during an extended test period for a specific hydrogen production rate of 2.38 mmol g(-1) L(-1) h(-1) and a quantum yield of 16.1% under visible light (165 W Xe lamp, lambda>420 nm). The results demonstrate that the (CdS)/(ZnS) core/shell nano-particles are a novel photo-catalyst for renewable hydrogen generation from water under visible light. This is attributable to the large band-gap ZnS shell that separates the electron/hole pairs generated by the CdS core and hence reduces their recombinations.

Review of the methods to form hydrogen peroxide in electrical discharge plasma with liquid water

NASA Astrophysics Data System (ADS)

Locke, Bruce R.; Shih, Kai-Yuan

2011-06-01

This paper presents a review of the literature dealing with the formation of hydrogen peroxide from plasma processes. Energy yields for hydrogen peroxide generation by plasma from water span approximately three orders of magnitude from 4 × 10-2 to 80 g kWh-1. A wide range of plasma processes from rf to pulsed, ac, and dc discharges directly in the liquid phase have similar energy yields and may thus be limited by radical quenching processes at the plasma-liquid interface. Reactor modification using discharges in bubbles and discharges over the liquid phase can provide modest improvements in energy yield over direct discharge in the liquid, but the interpretation is complicated by additional chemical reactions of gas phase components such as ozone and nitrogen oxides. The highest efficiency plasma process utilizes liquid water droplets that may enhance efficiency by sequestering hydrogen peroxide in the liquid and by suppressing decomposition reactions by radicals from the gas and at the interface. Kinetic simulations of water vapor reported in the literature suggest that plasma generation of hydrogen peroxide should approach 45% of the thermodynamics limit, and this fact coupled with experimental studies demonstrating improvements with the presence of the condensed liquid phase suggest that further improvements in energy yield may be possible. Plasma generation of hydrogen peroxide directly from water compares favorably with a number of other methods including electron beam, ultrasound, electrochemical and photochemical methods, and other chemical processes.

Water in polymer membranes. 4. Raman scattering from cellulose acetate films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherer, J.R.; Bailey, G.F.; Kint, S.

Raman scattering was observed from thin film optical waveguides of cellulose acetate exposed to water vapor from 0% to 100% relative humidity (RH), and from dilute solutions of water in methyl acetate. Spectra of cellulose acetate (CA398, 39.8% acetyl) at low RH and cellulose triacetate (CTA) at low and high RH are consistent with the presence of water monomers that are weakly hydrogen bonded to acetyl C=O groups. Differences between the spectra of water in CA398 and CTA at low RH are attributed to sequential hydrogen bonding involving OH groups in CA398. At high RH, CA398 and CTA (to amore » lesser extent) show bands attributed to water/water interactions that are similar to those found in sequentially hydrogen-bonded hydrates. CA398 films that are annealed at high temperatures exhibit decreased water/water interactions at high RH. Exposure of CA398 films to D/sub 2/O converts > 90% of all polymer OH groups to OD groups. This indicates that water is accessible to nearly all regions of the polymer containing OH groups. Annealing does not alter this accessibility but does reduce the total water content by roughly half, at 100% RH. Hydrogen-bonded C=O groups are associated with a band centered at 1731 cm/sup -1/ which increases in intensity with increasing water content in the film but does not shift in frequency. 38 references, 16 figures, 1 table.« less

Hydrogen Generator

NASA Technical Reports Server (NTRS)

1983-01-01

A unit for producing hydrogen on site is used by a New Jersey Electric Company. The hydrogen is used as a coolant for the station's large generator; on-site production eliminates the need for weekly hydrogen deliveries. High purity hydrogen is generated by water electrolysis. The electrolyte is solid plastic and the control system is electronic. The technology was originally developed for the Gemini spacecraft.

Development of non-bonded interaction parameters between graphene and water using particle swarm optimization.

PubMed

Bejagam, Karteek K; Singh, Samrendra; Deshmukh, Sanket A

2018-05-05

New Lennard-Jones parameters have been developed to describe the interactions between atomistic model of graphene, represented by REBO potential, and five commonly used all-atom water models, namely SPC, SPC/E, SPC/Fw, SPC/Fd, and TIP3P/Fs by employing particle swarm optimization (PSO) method. These new parameters were optimized to reproduce the macroscopic contact angle of water on a graphene sheet. The calculated line tension was in the order of 10 -11 J/m for the droplets of all water models. Our molecular dynamics simulations indicate the preferential orientation of water molecules near graphene-water interface with one OH bond pointing toward the graphene surface. Detailed analysis of simulation trajectories reveals the presence of water molecules with ≤∼1, ∼2, and ∼4 hydrogen bonds at the surface of air-water interface, graphene-water interface, and bulk region of the water droplet, respectively. Presence of water molecules with ≤∼1 and ∼2 hydrogen bonds suggest the existence of water clusters of different sizes at these interfaces. The trends observed in the libration, bending, and stretching bands of the vibrational spectra are closely associated with these structural features of water. The inhomogeneity in hydrogen bond network of water at the air-water and graphene-water interface is manifested by broadening of the peaks in the libration band for water present at these interfaces. The stretching band for the molecules in water droplet shows a blue shift as compared to the pure bulk water, which conjecture the presence of weaker hydrogen bond network in a droplet. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Site-specific binding of a water molecule to the sulfa drugs sulfamethoxazole and sulfisoxazole: a laser-desorption isomer-specific UV and IR study.

PubMed

Uhlemann, Thomas; Seidel, Sebastian; Müller, Christian W

2018-03-07

To determine the preferred water molecule binding sites of the polybasic sulfa drugs sulfamethoxazole (SMX) and sulfisoxazole (SIX), we have studied their monomers and monohydrated complexes through laser-desorption conformer-specific UV and IR spectroscopy. Both the SMX and SIX monomer adopt a single conformer in the molecular beam. On the basis of their conformer-specific IR spectra in the NH stretch region, these conformers were assigned to the SMX and SIX global minimum structures, both exhibiting a staggered sulfonamide group and an intramolecular C-HO[double bond, length as m-dash]S hydrogen bond. The SMX-H 2 O and SIX-H 2 O complexes each adopt a single isomer in the molecular beam. Their isomeric structures were determined based on their isomer-specific IR spectra in the NH/OH stretch region. Quantum Theory of Atoms in Molecules analysis of the calculated electron densities revealed that in the SMX-H 2 O complex the water molecule donates an O-HN hydrogen bond to the heterocycle nitrogen atom and accepts an N-HO hydrogen bond from the sulfonamide NH group. In the SIX-H 2 O complex, however, the water molecule does not bind to the heterocycle but instead donates an O-HO[double bond, length as m-dash]S hydrogen bond to the sulfonamide group and accepts an N-HO hydrogen bond from the sulfonamide NH group. Both water complexes are additionally stabilized by a C ph -HOH 2 hydrogen bond. Interacting Quantum Atoms analysis suggests that all intermolecular hydrogen bonds are dominated by the short-range exchange-correlation contribution.

Electronic origin of the dependence of hydrogen bond strengths on nearest-neighbor and next-nearest-neighbor hydrogen bonds in polyhedral water clusters (H 2 O) n , n = 8, 20 and 24

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iwata, Suehiro; Akase, Dai; Aida, Misako

2016-01-01

The relative stability and the characteristics of the hydrogen bond networks in the cubic cages of (H2O)8, dodecahedral cages of (H2O)20,and tetrakaidodecahedral cages of (H2O)24 are studied. The charge-transfer and dispersion interaction terms of every pair of the hydrogen bonds are evaluated by using the perturbation theory based on the locally-projected molecular orbital (LPMO PT). Every water molecule and every hydrogen-bonded pair in polyhedral clusters are classified by the types of the adjacent molecules and hydrogen bonds. The relative binding energies among the polyhedral clusters are grouped by these classifications. The necessary condition for the stable conformers and the rulesmore » of the ordering of the relative stability among the isomers are derived from the analysis. The O–O distances and the pair-wise charge-transfer terms are dependent not only on the types of the hydrogen donor and acceptor waters but also on the types of the adjacent waters. This dependence is analyzed with Mulliken’s charge-transfer theory. The work is partially supported by the Grant-in-Aid for Science Research of JSPS (SI, DA, MA). SSX was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Battelle operates the Pacific Northwest National Laboratory for the US Department of Energy.« less

Hydrogen at the Lunar Terminator

NASA Astrophysics Data System (ADS)

Livengood, T. A.; Chin, G.; Sagdeev, R. Z.; Mitrofanov, I. G.; Boynton, W. V.; Evans, L. G.; Litvak, M. L.; McClanahan, T. P.; Sanin, A. B.; Starr, R. D.; Su, J. J.

2015-10-01

Suppression of the Moon's naturally occurring epithermal neutron leakage flux near the equatorial dawn terminator is consistent with the presence of diurnally varying quantities of hydrogen in the regolith with maximum concentration on the day side of the dawn terminator. This flux suppression has been observed using the Lunar Exploration Neutron Detector (LEND) on the polar-orbiting Lunar Reconnaissance Orbiter (LRO). The chemical form of hydrogen is not determined, but other remote sensing methods and elemental availability suggest water. The observed variability is interpreted as frost collecting in or on the cold nightside surface, thermally desorbing in sunlight during the lunar morning,and migrating away from the warm subsolar region across the nearby terminator to return to the lunar surface. The maximum concentration, averaged over the upper ~1m of regolith to which neutron detection is sensitive,is estimated to be 0.0125±0.0022 weight-percent water-equivalent hydrogen (wt% WEH), yielding an accumulation of 190±30 ml recoverable water per square meter of regolith at each dawn. The source of hydrogen (water) must be in equilibrium with losses due to solar photolysis and escape. A chemical recycling process or self-shielding from solar UV must be assumed in order to bring the loss rate down to compatibility with possible sources, including solar wind or micrometeoroid delivery of hydrogen, which require near-complete retention of hydrogen,or outgassing of primordial volatiles, for which a plausible supply rate requires significantly less retention efficiency.

Influence of gaseous hydrogen on the mechanical properties of incoloy 903. [gas-metal interactions/iron alloys

NASA Technical Reports Server (NTRS)

1975-01-01

Solid specimens of the alloy Inconel 903 (iron based alloy) were exposed to four gaseous environments and high temperatures. Air, pure helium, pure hydrogen, and hydrogen and water vapor combined were the gaseous environments employed, and the temperature was 1400 F. Various mechanical property tests (low cycle fatigue, creep-rupture, tensile properties) were performed on the alloy. Results indicate that the hydrogen and water vapor environment cause a sharp reduction in the mechanical properties of the alloy. Photographs of the test equipment used and the microstructure of the tested alloy are included.

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, Frederick T.

1981-01-01

Intermetallic compounds with the CaCu.sub.5 type of crystal structure, particularly LaNiCo.sub.4 and CaNi.sub.5, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation colum. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale mutli-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen can produce large quantities of heavy water at an effective cost for use in heavy water reactors.

Distillation Kinetics of Solid Mixtures of Hydrogen Peroxide and Water and the Isolation of Pure Hydrogen Peroxide in Ultrahigh Vacuum

NASA Technical Reports Server (NTRS)

Teolis, B. D.; Baragiola, R. A.

2006-01-01

We present results of the growth of thin films of crystalline H2O2 and H2O2.2H2O (dihydrate) in ultrahigh vacuum by distilling an aqueous solution of hydrogen peroxide. We traced the process using infrared reflectance spectroscopy, mass loss on a quartz crystal microbalance, and in a few cases ultraviolet-visible reflectance. We find that the different crystalline phases-water, dihydrate, and hydrogen peroxide-have very different sublimation rates, making distillation efficient to isolate the less volatile component, crystalline H2O2.

Method and system for producing hydrogen using sodium ion separation membranes

DOEpatents

Bingham, Dennis N; Klingler, Kerry M; Turner, Terry D; Wilding, Bruce M; Frost, Lyman

2013-05-21

A method of producing hydrogen from sodium hydroxide and water is disclosed. The method comprises separating sodium from a first aqueous sodium hydroxide stream in a sodium ion separator, feeding the sodium produced in the sodium ion separator to a sodium reactor, reacting the sodium in the sodium reactor with water, and producing a second aqueous sodium hydroxide stream and hydrogen. The method may also comprise reusing the second aqueous sodium hydroxide stream by combining the second aqueous sodium hydroxide stream with the first aqueous sodium hydroxide stream. A system of producing hydrogen is also disclosed.

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, F.T.

Intermetallic compounds with the CaCu/sub 5/ type of crystal structure, particularly LaNiCo/sub 4/ and CaNi/sub 5/, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation column. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale multi-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen cn produce large quantities of heavy water at an effective cost for use in heavy water reactors.

Method and apparatus for separation of heavy and tritiated water

DOEpatents

Lee, Myung W.

2001-01-01

The present invention is a bi-thermal membrane process for separating and recovering hydrogen isotopes from a fluid containing hydrogen isotopes, such as water and hydrogen gas. The process in accordance with the present invention provides counter-current cold and hot streams of the fluid separated with a thermally insulating and chemically transparent proton exchange membrane (PEM). The two streams exchange hydrogen isotopes through the membrane: the heavier isotopes migrate into the cold stream, while the lighter isotopes migrate into the hot stream. The heavy and light isotopes are continuously withdrawn from the cold and hot streams respectively.

Hydrogen Production by a Hyperthermophilic Membrane-Bound Hydrogenase in Soluble Nanolipoprotein Particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, S E; Hopkins, R C; Blanchette, C

Hydrogenases constitute a promising class of enzymes for ex vivo hydrogen production. Implementation of such applications is currently hindered by oxygen sensitivity and, in the case of membrane-bound hydrogenases (MBH), poor water solubility. Nanolipoprotein particles (NLPs), formed from apolipoproteins and phospholipids, offer a novel means to incorporate MBH into in a well-defined water-soluble matrix that maintains the enzymatic activity and is amenable to incorporation into more complex architectures. We report the synthesis, hydrogen-evolving activity and physical characterization of the first MBH-NLP assembly. This may ultimately lead to the development of biomimetic hydrogen production devices.

Hydrogen-bond dynamics at the bio-water interface in hydrated proteins: a molecular-dynamics study.

PubMed

Nandi, Prithwish K; English, Niall J; Futera, Zdenek; Benedetto, Antonio

2016-12-21

Water is fundamental to the biochemistry of enzymes. It is well known that without a minimum amount of water, enzymes are not biologically active. Bare minimal solvation for biological function corresponds to about a single layer of water covering enzymes' surfaces. Many contradictory studies on protein-hydration-water-coupled dynamics have been published in recent decades. Following prevailing wisdom, a dynamical crossover in hydration water (at around 220 K for hydrated lysozymes) can trigger larger-amplitude motions of the protein, activating, in turn, biological functions. Here, we present a molecular-dynamics-simulation study on a solvated model protein (hen egg-white lysozyme), in which we determine, inter alia, the relaxation dynamics of the hydrogen-bond network between the protein and its hydration water molecules on a residue-per-residue basis. Hydrogen-bond breakage/formation kinetics is rather heterogeneous in temperature dependence (due to the heterogeneity of the free-energy surface), and is driven by the magnitude of thermal motions of various different protein residues which provide enough thermal energy to overcome energy barriers to rupture their respective hydrogen bonds with water. In particular, arginine residues exhibit the highest number of such hydrogen bonds at low temperatures, losing almost completely such bonding above 230 K. This suggests that hydration water's dynamical crossover, observed experimentally for hydrated lysozymes at ∼220 K, lies not at the origin of the protein residues' larger-amplitude motions, but rather arises as a consequence thereof. This highlights the need for new experimental investigations, and new interpretations to link protein dynamics to functions, in the context of key interrelationships with the solvation layer.

Effects of oxygenated or hydrogenated water on growth performance, blood parameters, and antioxidant enzyme activity of broiler chickens.

PubMed

Shin, D; Cho, E S R; Bang, H-T; Shim, K S

2016-11-01

This study was conducted to investigate the effects of providing oxygenated and hydrogenated water on the growth performance, blood biochemical parameters, and immunoglobulin concentrations and antioxidant enzyme activity of broiler chickens. In our investigation, 144 Ross × Ross broiler chicks were randomly allotted to three different treatment groups with four replicates (treatment × replicate × bird = 3 × 4 × 12). All chicks were given one of the following types of water for five weeks: tap water (CON), hydrogenated water (HNW), and oxygenated water (ONW). ONW supplementation increased the final body weight and weight gain and also improved both feed intake and feed conversion of broiler chickens as compared to those of CON broiler chickens (P < 0.05). The abdominal fat and its ratio to the final body weight showed that fat accumulation in the broiler chicken abdomen was reduced when broiler chickens drank only ONW for five weeks (P < 0.05). ONW supplementation improved blood parameters, including triacylglyceride, total cholesterol, and low-density lipoprotein-cholesterol. Additionally, in accordance with a globulin increase in broiler chickens, both IgG and IgM generation were significantly enhanced when ONW was supplied to broiler chickens (P < 0.05) but only a numerical advance was observed in the HNW group (P > 0.05). Both oxygenated and hydrogenated water supplementation significantly improved the antioxidant effects (P < 0.05), and it seems that superoxide dismutase refinement was completed due to oxygen and/or hydrogen enhancement of drinking water. These results indicate that oxygen enhancement of drinking water may be recommended to improve growth performance by increasing immunoglobulins mainly IgG and IgM. © Crown copyright 2016.

Method of recycling lithium borate to lithium borohydride through diborane

DOEpatents

Filby, Evan E.

1976-01-01

This invention provides a method for the recycling of lithium borate to lithium borohydride which can be reacted with water to generate hydrogen for utilization as a fuel. The lithium borate by-product of the hydrogen generation reaction is reacted with hydrogen chloride and water to produce boric acid and lithium chloride. The boric acid and lithium chloride are converted to lithium borohydride through a diborane intermediate to complete the recycle scheme.

Measuring Hydrogen Concentrations in Metals

NASA Technical Reports Server (NTRS)

Danford, M. D.

1985-01-01

Commercial corrosion-measurement system adapted to electrochemical determination of hydrogen concentrations in metals. New technique based on diffusion of hydrogen through foil specimen of metal. In sample holder, hydrogen produced on one side of foil, either by corrosion reaction or by cathodic current. Hydrogen diffused through foil removed on other side by constant anode potential, which leads to oxidation of hydrogen to water. Anode current is measure of concentration of hydrogen diffusing through foil. System used to study hydrogen uptake, hydrogen elimination by baking, effect of heat treatment, and effect of electroplating on high-strength steels.

The effect of pressure on the hydration structure around hydrophobic solute: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Sarma, Rahul; Paul, Sandip

2012-03-01

Molecular dynamics simulations are performed to study the effects of pressure on the hydrophobic interactions between neopentane molecules immersed in water. Simulations are carried out for five different pressure values ranging from 1 atm to 8000 atm. From potential of mean force calculations, we find that with enhancement of pressure, there is decrease in the well depth of contact minimum (CM) and the relative stability of solvent separated minimum over CM increases. Lower clustering of neopentane at high pressure is also observed in association constant and cluster-structure analysis. Selected site-site radial distribution functions suggest efficient packing of water molecules around neopentane molecules at elevated pressure. The orientational profile calculations of water molecules show that the orientation of water molecules in the vicinity of solute molecule is anisotropic and this distribution becomes flatter as we move away from the solute. Increasing pressure slightly changes the water distribution. Our hydrogen bond properties and dynamics calculations reveal pressure-induced formation of more and more number of water molecules with five and four hydrogen bond at the expense of breaking of two and three hydrogen bonded water molecules. We also find lowering of water-water continuous hydrogen bond lifetime on application of pressure. Implication of these results for relative dispersion of hydrophobic molecules at high pressure are discussed.

Water-driven micromotors.

PubMed

Gao, Wei; Pei, Allen; Wang, Joseph

2012-09-25

We demonstrate the first example of a water-driven bubble-propelled micromotor that eliminates the requirement for the common hydrogen peroxide fuel. The new water-driven Janus micromotor is composed of a partially coated Al-Ga binary alloy microsphere prepared via microcontact mixing of aluminum microparticles and liquid gallium. The ejection of hydrogen bubbles from the exposed Al-Ga alloy hemisphere side, upon its contact with water, provides a powerful directional propulsion thrust. Such spontaneous generation of hydrogen bubbles reflects the rapid reaction between the aluminum alloy and water. The resulting water-driven spherical motors can move at remarkable speeds of 3 mm s(-1) (i.e., 150 body length s(-1)), while exerting large forces exceeding 500 pN. Factors influencing the efficiency of the aluminum-water reaction and the resulting propulsion behavior and motor lifetime, including the ionic strength and environmental pH, are investigated. The resulting water-propelled Al-Ga/Ti motors move efficiently in different biological media (e.g., human serum) and hold considerable promise for diverse biomedical or industrial applications.

Bibliography of Soviet Laser Developments, March-April 1988

DTIC Science & Technology

1988-08-01

f. Iodine g. Hydrogen h. Ammonia --- i. Carbon Tetrafluoride --- j. Nitrous Oxide k. Water Vapor I. Heavy-Water Vapor --- m. Submillimeter --- n...1988, 25-26. 36. Porskiy, Yu.Ye.; Sitenkov, Yu.L.; Khokhlov, Yu.M. (-0-). Influence of the discharge circuit inductance on the value of specific...Hydrogen h. Ammonia i. Carbon Tetrafluoride j. Nitrous Oxide k. Water Vapor 1. Heavy-Water Vapor m. Submillimeter 9 n. Metal Vapor 59. Astadzhov, D.N

Analytical model for three-dimensional Mercedes-Benz water molecules.

PubMed

Urbic, T

2012-06-01

We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature.

Analytical model for three-dimensional Mercedes-Benz water molecules

NASA Astrophysics Data System (ADS)

Urbic, T.

2012-06-01

We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature.

Analytical model for three-dimensional Mercedes-Benz water molecules

PubMed Central

Urbic, T.

2013-01-01

We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature. PMID:23005100

Structure of Aqueous Trehalose Solution by Neutron Diffraction and Structural Modeling.

PubMed

Olsson, Christoffer; Jansson, Helén; Youngs, Tristan; Swenson, Jan

2016-12-15

The molecular structure of an aqueous solution of the disaccharide trehalose (C 12 H 22 O 11 ) has been studied by neutron diffraction and empirical potential structure refinement modeling. Six different isotope compositions with 33 wt % trehalose (corresponding to 38 water molecules per trehalose molecule) were measured to ensure that water-water, trehalose-water, and trehalose-trehalose correlations were accurately determined. In fact, this is the first neutron diffraction study of an aqueous trehalose solution in which also the nonexchangeable hydrogen atoms in trehalose are deuterated. With this approach, it was possible to determine that (1) there is a substantial hydrogen bonding between trehalose and water (∼11 hydrogen bonds per trehalose molecule), which is in contrast to previous neutron diffraction studies, and (2) there is no tendency of clustering of trehalose, in contrast to what is generally observed by molecular dynamics simulations and experimentally found for other disaccharides. Thus, the results give the structural picture that trehalose prefers to interact with water and participate in a hydrogen-bonded network. This strong network character of the solution might be one of the key reasons for its extraordinary stabilization effect on biological materials.

Polarization response of clathrate hydrates capsulated with guest molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Qun; Li, Jinshan, E-mail: ljs915@263.net, E-mail: myang@scu.edu.cn; Huang, Hui

2016-05-28

Clathrate hydrates are characterized by their water cages encapsulating various guest atoms or molecules. The polarization effect of these guest-cage complexes was studied with combined density functional theory and finite-field calculations. An addition rule was noted for these systems whose total polarizability is approximately equal to the polarizability sum of the guest and the cage. However, their distributional polarizability computed with Hirshfeld partitioning scheme indicates that the guest–cage interaction has considerable influence on their polarization response. The polarization of encapsulated guest is reduced while the polarization of water cage is enhanced. The counteraction of these two opposite effects leads tomore » the almost unchanged total polarizability. Further analysis reveals that the reduced polarizability of encapsulated guest results from the shielding effect of water cage against the external field and the enhanced polarizability of water cage from the enhanced bonding of hydrogen bonds among water molecules. Although the charge transfer through the hydrogen bonds is rather small in the water cage, the polarization response of clathrate hydrates is sensitive to the changes of hydrogen bonding strength. The guest encapsulation strengthens the hydrogen bonding network and leads to enhanced polarizability.« less

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

PubMed Central

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-01-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ∼3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries. PMID:28585527

Process for producing methane from gas streams containing carbon monoxide and hydrogen

DOEpatents

Frost, Albert C.

1980-01-01

Carbon monoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbon monoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO.sub.2, from which a relatively pure methane product may be obtained. While carbon monoxide-containing gas streams having hydrogen or water present therein can be used only the carbon monoxide available after reaction with said hydrogen or water is decomposed to form said active surface carbon. Although hydrogen or water will be converted, partially or completely, to methane that can be utilized in a combustion zone to generate heat for steam production or other energy recovery purposes, said hydrogen is selectively removed from a CO--H.sub.2 -containing feed stream by partial oxidation thereof prior to disproportionation of the CO content of said stream.

Method of generating hydrogen by catalytic decomposition of water

DOEpatents

Balachandran, Uthamalingam; Dorris, Stephen E.; Bose, Arun C.; Stiegel, Gary J.; Lee, Tae-Hyun

2002-01-01

A method for producing hydrogen includes providing a feed stream comprising water; contacting at least one proton conducting membrane adapted to interact with the feed stream; splitting the water into hydrogen and oxygen at a predetermined temperature; and separating the hydrogen from the oxygen. Preferably the proton conducting membrane comprises a proton conductor and a second phase material. Preferable proton conductors suitable for use in a proton conducting membrane include a lanthanide element, a Group VIA element and a Group IA or Group IIA element such as barium, strontium, or combinations of these elements. More preferred proton conductors include yttrium. Preferable second phase materials include platinum, palladium, nickel, cobalt, chromium, manganese, vanadium, silver, gold, copper, rhodium, ruthenium, niobium, zirconium, tantalum, and combinations of these. More preferably second phase materials suitable for use in a proton conducting membrane include nickel, palladium, and combinations of these. The method for generating hydrogen is preferably preformed in the range between about 600.degree. C. and 1,700.degree. C.

Interstellar hydrogen bonding

NASA Astrophysics Data System (ADS)

Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

2018-06-01

This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

NASA Astrophysics Data System (ADS)

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-06-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ~3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries.

NASA’s MAVEN Mission Observes Ups and Downs of Water Escape from Mars

NASA Image and Video Library

2017-12-08

After investigating the upper atmosphere of the Red Planet for a full Martian year, NASA’s MAVEN mission has determined that the escaping water does not always go gently into space. Sophisticated measurements made by a suite of instruments on the Mars Atmosphere and Volatile Evolution, or MAVEN, spacecraft revealed the ups and downs of hydrogen escape – and therefore water loss. The escape rate peaked when Mars was at its closest point to the sun and dropped off when the planet was farthest from the sun. The rate of loss varied dramatically overall, with 10 times more hydrogen escaping at the maximum. “MAVEN is giving us unprecedented detail about hydrogen escape from the upper atmosphere of Mars, and this is crucial for helping us figure out the total amount of water lost over billions of years,” said Ali Rahmati, a MAVEN team member at the University of California at Berkeley who analyzed data from two of the spacecraft’s instruments. Hydrogen in Mars’ upper atmosphere comes from water vapor in the lower atmosphere. An atmospheric water molecule can be broken apart by sunlight, releasing the two hydrogen atoms from the oxygen atom that they had been bound to. Several processes at work in Mars’ upper atmosphere may then act on the hydrogen, leading to its escape. Read more: go.nasa.gov/2dAgAV4 NASA image use policy. NASA Goddard Space Flight Center enables NASA’s mission through four scientific endeavors: Earth Science, Heliophysics, Solar System Exploration, and Astrophysics. Goddard plays a leading role in NASA’s accomplishments by contributing compelling scientific knowledge to advance the Agency’s mission. Follow us on Twitter Like us on Facebook Find us on Instagram

Isothermal Decomposition of Hydrogen Peroxide Dihydrate

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Baragiola, R. A.

2011-01-01

We present a new method of growing pure solid hydrogen peroxide in an ultra high vacuum environment and apply it to determine thermal stability of the dihydrate compound that forms when water and hydrogen peroxide are mixed at low temperatures. Using infrared spectroscopy and thermogravimetric analysis, we quantified the isothermal decomposition of the metastable dihydrate at 151.6 K. This decomposition occurs by fractional distillation through the preferential sublimation of water, which leads to the formation of pure hydrogen peroxide. The results imply that in an astronomical environment where condensed mixtures of H2O2 and H2O are shielded from radiolytic decomposition and warmed to temperatures where sublimation is significant, highly concentrated or even pure hydrogen peroxide may form.

Theoretical vibrational sum-frequency generation spectroscopy of water near lipid and surfactant monolayer interfaces. II. Two-dimensional spectra.

PubMed

Roy, S; Gruenbaum, S M; Skinner, J L

2014-12-14

The structural stability and function of biomolecules is strongly influenced by the dynamics and hydrogen bonding of interfacial water. Understanding and characterizing the dynamics of these water molecules require a surface-sensitive technique such as two-dimensional vibrational sum-frequency generation (2DSFG) spectroscopy. We have combined theoretical 2DSFG calculations with molecular dynamics simulations in order to investigate the dynamics of water near different lipid and surfactant monolayer surfaces. We show that 2DSFG can distinguish the dynamics of interfacial water as a function of the lipid charge and headgroup chemistry. The dynamics of water is slow compared to the bulk near water-zwitterionic and water-anionic interfaces due to conformational constraints on interfacial water imposed by strong phosphate-water hydrogen bonding. The dynamics of water is somewhat faster near water-cationic lipid interfaces as no such constraint is present. Using hydrogen bonding and rotational correlation functions, we characterize the dynamics of water as a function of the distance from the interface between water and zwitterionic lipids. We find that there is a transition from bulk-like to interface-like dynamics approximately 7 Å away from a zwitterionic phosphatidylcholine monolayer surface.

Water cooling system for an air-breathing hypersonic test vehicle

NASA Technical Reports Server (NTRS)

Petley, Dennis H.; Dziedzic, William M.

1993-01-01

This study provides concepts for hypersonic experimental scramjet test vehicles which have low cost and low risk. Cryogenic hydrogen is used as the fuel and coolant. Secondary water cooling systems were designed. Three concepts are shown: an all hydrogen cooling system, a secondary open loop water cooled system, and a secondary closed loop water cooled system. The open loop concept uses high pressure helium (15,000 psi) to drive water through the cooling system while maintaining the pressure in the water tank. The water flows through the turbine side of the turbopump to pump hydrogen fuel. The water is then allowed to vent. In the closed loop concept high pressure, room temperature, compressed liquid water is circulated. In flight water pressure is limited to 6000 psi by venting some of the water. Water is circulated through cooling channels via an ejector which uses high pressure gas to drive a water jet. The cooling systems are presented along with finite difference steady-state and transient analysis results. The results from this study indicate that water used as a secondary coolant can be designed to increase experimental test time, produce minimum venting of fluid and reduce overall development cost.

Influence of hydronium, sulfate, chloride and other non-carbonate ions on hydrogen generation by anaerobic corrosion of granular cast iron.

PubMed

Ruhl, Aki S; Jekel, Martin

2013-10-15

Permeable reactive barriers are successfully applied for the removal of various contaminants. The concomitant reduction of hydrogen ions and the subsequent formation of hydrogen gas by anaerobic corrosion lead to decreased pore volume filled with water and thus residence times, so called gas clogging. Long term column experiments were conducted to elucidate the impact of ubiquitous water constituents on the formation of hydrogen gas and potential passivation due to corrosion products. The collected gas volumes revealed a relation to the hydronium concentration (pH) but were only slightly increased in the presence of chloride and sulfate and not significantly influenced in the presence of phosphate, silicate, humic acid and ammonium compared to deionized water. Significant gas volumes within the reactive filling were verified by gravimetry. The presence of nitrate completely eliminated hydrogen formation by competition for electrons. Solid phase analyses revealed that neither chloride nor sulfate was incorporated in corrosion products in concentrations above 0.1 weight percent, and they did not alter the formation of mainly magnetite in comparison to deionized water. Copyright © 2013 Elsevier Ltd. All rights reserved.

Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

USGS Publications Warehouse

Coplen, T.B.; Qi, H.

2010-01-01

An anomalous stable hydrogen isotopic fractionation of 4 ??? in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) ??2H reproducibility (1?? standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ??? to 0.58 ???. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen. ?? This article not subject to U.S. Copyright. Published 2010 by the American Chemical Society.

Theoretical study of the changes in the vibrational characteristics arising from the hydrogen bonding between Vitamin C ( L-ascorbic acid) and H 2O

NASA Astrophysics Data System (ADS)

Dimitrova, Yordanka

2006-02-01

The vibrational characteristics (vibrational frequencies, infrared intensities and Raman activities) for the hydrogen-bonded system of Vitamin C ( L-ascorbic acid) with five water molecules have been predicted using ab initio SCF/6-31G(d, p) calculations and DFT (BLYP) calculations with 6-31G(d, p) and 6-31++G(d, p) basis sets. The changes in the vibrational characteristics from free monomers to a complex have been calculated. The ab initio and BLYP calculations show that the complexation between Vitamin C and five water molecules leads to large red shifts of the stretching vibrations for the monomer bonds involved in the hydrogen bonding and very strong increase in their IR intensity. The predicted frequency shifts for the stretching vibrations from Vitamin C taking part in the hydrogen bonding are up to -508 cm -1. The magnitude of the wavenumber shifts is indicative of relatively strong OH···H hydrogen-bonded interactions. In the same time the IR intensity and Raman activity of these vibrations increase upon complexation. The IR intensity increases dramatically (up to 12 times) and Raman activity increases up to three times. The ab initio and BLYP calculations show, that the symmetric OH vibrations of water molecules are more sensitive to the complexation. The hydrogen bonding leads to very large red shifts of these vibrations and very strong increase in their IR intensity. The asymmetric OH stretching vibrations of water, free from hydrogen bonding are less sensitive to the complexation than the hydrogen-bonded symmetric O sbnd H stretching vibrations. The increases of the IR intensities for these vibrations are lower and red shifts are negligible.

Corrosion behavior of surface films on boron-implanted high purity iron and stainless steels

NASA Technical Reports Server (NTRS)

Kim, H. J.; Carter, W. B.; Hochman, R. F.; Meletis, E. I.

1985-01-01

Boron (dose, 2 x 10 to the 17th ions/sq cm) was implanted into high purity iron, AISI 316 austenitic stainless steel, and AISI 440C martensitic stainless steel, at 40 keV. The film structure of implanted samples was examined and characterized by contrast and diffraction analyses utilizing transmission electron microscopy. The effect of B(+) ion implantation on the corrosion behavior was studied using the potentiodynamic polarization technique. Tests were performed in deaerated 1 N H2SO4 and 0.1 M NaCl solutions. Scanning electron microscopy was used to examine the morphology of the corroded surfaces after testing.

Structural properties of hydration shell around various conformations of simple polypeptides.

PubMed

Czapiewski, Dariusz; Zielkiewicz, Jan

2010-04-08

In this paper we investigate structural properties of water within the solvation shell around the peptide core created by a well-defined conformation of polypeptide chain. The following secondary structures are investigated: linear (straight chain), and three helices PII (polyproline-like), 3(10), and alpha. We propose using the two-particle contribution to entropy as a rational measure of the water structural ordering within the solvation layer. This contribution divides into two terms, depending on the peptide-water and water-water interactions, respectively, and in this paper both terms are investigated. The structure of "solvation" water is described by the second term, and therefore it mainly attracts our attention. Determination of this term, however, is not an easy task, requiring some controversial approximations. Therefore, we have transformed this term to the form of some rational parameter which measures the local structural ordering of water within the solvation shell. Moreover, the results of several independent investigations are reported: we adopt the harmonic approximation for an independent estimation of the water entropy within the solvation shell, and we also study structure of the water-water hydrogen bond network, mean geometry of a single hydrogen bond, the self-diffusion coefficients (both translational and rotational) of water, and the mean lifetimes of water-water and water-peptide hydrogen bonds. All the obtained results lead to the conclusion that the local structure of water within the solvation shell changes only slightly in comparison to the bulk one. If so, the measure of local water ordering proposed by us is exploited with the aim to gain the deeper insight on the structural properties of "solvation" water. It has been shown that this parameter can be factored into three terms, which measure translational, configurational, and orientational ordering, respectively. Using this factoring, the ordering map for a precise description of the water local ordering has been built. An interesting correlation is observed: the points on this map lie approximately on the straight line, while the linear conformations clearly deviate from the general tendency. Further analysis of the obtained results allows us to express the supposition that an increasing local ordering of water around given secondary structure corresponds to an increasing relative stability of this structure in aqueous solution. Analyzing the geometry of the water-water hydrogen bond network within the solvation layer, we find some systematic deviations of this geometry from the bulk water properties. We also observe that the alanine peptides (excluding the linear form) disturb the hydrogen bond network in the less range, and in another way than the various conformations of polyglycine, while the linear form of polyalanine behaves very similarly to the glycine ones. Next, investigating the dynamic properties, we also conclude that water near the peptide surface creates a pseudorigid structure, a "halo" around the peptide core. This "halo" is stabilized by slightly higher energy of the hydrogen bonds network: we have found that within this region the hydrogen bonds network is slightly less distorted, the water-water hydrogen bonds are a little more stable and their mean lifetime is clearly longer that that of bulk water. Significant differences between the alanine- and glycine-based polypeptides are also visible. It has also been found that this solvation layer interacts with the polyalanine in another way than with polyglycine. Although in the case of the glycine-based polypeptide this layer slides relatively freely over the peptide surface, for the alanine-based polypeptide this sliding is strongly hindered by the presence of the methyl groups, and this effect is additionally enhanced by a rise in the solvation layer rigidity. Thus, the survey of various dynamic properties allows us to perceive and to explain distinct differences in behavior of water within the solvation shell around both glycine and alanine peptides.

Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensley, Alyssa J. R.; Wang, Yong; Mei, Donghai

A mechanistic understanding of the roles of water is essential for developing highly active and selective catalysts for hydrodeoxygenation (HDO) reactions since water is ubiquitous in such reaction systems. Here, we present a study for phenol HDO on Fe catalysts using density functional theory which examines the effect of water on three elementary pathways for phenol HDO using an explicit solvation model. The presence of water is found to significantly decrease activation barriers required by hydrogenation reactions via two pathways. First, the proton transfer in the hydrogen bonding network of the liquid water phase is nearly barrierless, which significantly promotesmore » the direct through space tautomerization of phenol. Second, due to the high degree of oxophilicity on Fe, liquid water molecules are found to be easily dissociated into surface hydroxyl groups that can act as Brønsted acid sites. These sites dramatically promote hydrogenation reactions on the Fe surface. As a result, the hydrogen assisted dehydroxylation becomes the dominant phenol HDO pathway. This work provides new fundamental insights into aqueous phase HDO of biomass-derived oxygenates over Fe-based catalysts; e.g., the activity of Fe-based catalysts can be optimized by tuning the surface coverage of Brønsted acid sites via surface doping.« less

Chemical milling solution reveals stress corrosion cracks in titanium alloy

NASA Technical Reports Server (NTRS)

Braski, D. N.

1967-01-01

Solution of hydrogen flouride, hydrogen peroxide, and water reveals hot salt stress corrosion cracks in various titanium alloys. After the surface is rinsed in water, dried, and swabbed with the solution, it can be observed by the naked eye or at low magnification.

Possible Role of Hydrogen in the Earth Core

NASA Astrophysics Data System (ADS)

Takahashi, E.; Imai, T.

2011-12-01

Possible role of hydrogen in the Earth core has been discussed by Stevenson (1977) and demonstrated experimentally by Fukai (1984), Okuchi (1997) and others. Planetary theory proposes a possibility of hydrogen incorporation in Earth's magma ocean from ambient solar nebula gas (Ikoma & Genda 2005, Genda & Ikoma 2008). More recently, migration of snow line during planet formation was examined (Min et al., 2010; Oka et al, 2011) and it was proposed that the Earth building material originally contained abundant water as ice and hydrous minerals. Therefore, it is very important to investigate the fate of water in the planet building process and clarify the role of hydrogen in the planetary core. Using SPring-8 synchrotron (NaCl capsule, LiAlH4 as hydrogen source), we determined the melting curve of FeH up to 20 GPa under hydrogen saturated conditions (Sakamaki, Takahashi et al, 2009). Observed melting point is below 1300C and has a very small dT/dP slope. By extrapolating the melting curve using Lindeman's law, we proposed that hydrogen could lower the melting temperature of the Earth core by more than 1500K than current estimate. Here we report our new experiments using SPring-8 synchrotron (single crystal diamond capsule, water as hydrogen source). Hydrogen concentration and melting temperature of FeHx that coexists with hydrous mantle minerals were determined at 15-20GPa and 1000-1600C. We show that 1) hydrogen concentration in FeHx at 1000C, coexisting with hydrous-B and ringwoodite is approximately X=0.6. 2) Upon heating, hydrous-B decomposes and hydrogen strongly partitions into FeHx (X=0.8~1.0) than ringwoodite. 3) FeHx that coexists with ringwoodite melts between ~1300C (solidus) and ~1600C (liquidus). Combined our new experiments with those by Sakamaki et al (2009) and Shibazaki et al (2009), partitioning of hydrogen between proto-core and primitive mantle is discussed. We propose that >90% of water in the source material may have entered the Earth core. Given large hydrogen concentration in the Earth core, temperature of the outermost core could be as low as that of lower mantle adiabat. Presence of the light element-rich layer at the top 300km layer of the outer core (Helffrich & Kaneshima, 2010) may be easily understood if there is no temperature gap between the core and the lower mantle.

6-[(Dimethyl­amino)methyl­ene­amino]-1,3-dimethyl­pyrimidine-2,4(1H,3H)-dione dihydrate

PubMed Central

Das, Subrata; Saikia, Binoy K.; Sridhar, B.; Thakur, Ashim J.

2008-01-01

Uracil, the pyrimidine nucleobase, which combined with adenine forms one of the major motifs present in the biopolymer RNA, is also involved in the self-assembly of RNA. In the title compound, C9H14N4O2·2H2O, the asymmetric unit contains one dimethyl­amino­uracil group and two water mol­ecules. The plane of the N=C—NMe2 side chain is inclined at 27.6 (5)° to the plane of the uracil ring. Both water mol­ecules form O—H⋯O hydrogen bonds with the carbonyl O atoms of the uracil group. Additional water–water hydrogen-bond inter­actions are also observed in the crystal structure. The O—H⋯O hydrogen bonds lead to the formation of a two-dimensional hydrogen-bonded network cage consisting of two dimethyl­amino­uracil groups and six water mol­ecules. PMID:21201655

Tritiated Water on Molecular Sieve without Hydrogen Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walters, R.T.

2001-09-10

Several molecular sieve beds loaded with tritiated water failed to generate hydrogen gas from tritium self-radiolysis at the expected rate. Preliminary gamma-ray irradiation experiments of 4A molecular sieve with varying amounts of oxygen in the over-gas evoke a quenching mechanism. The data suggest that the gas phase rate constant for the production of hydrogen gas is several orders of magnitude smaller than the third order rate constant for scavenging of radical fragments by oxygen.

Method of recycling lithium borate to lithium borohydride through methyl borate

DOEpatents

Filby, Evan E.

1977-01-01

This invention provides a method for the recycling of lithium borate to lithium borohydride which can be reacted with water to generate hydrogen for utilization as a fuel. The lithium borate by-product of the hydrogen generation reaction is reacted with hydrogen chloride and water to produce boric acid and lithium chloride. The boric acid and lithium chloride are converted to lithium borohydride through a methyl borate intermediate to complete the recycle scheme.

Geometrical behavior of hydrogen bonding patterns in the alpha-dodecyl-omega-hydroxy-tris(oxyethylene)-water system monitored by near infrared spectroscopy.

PubMed

Ohno, Keiichi; Takao, Hiroshi; Katsumoto, Yukiteru

2006-03-01

Changes in the geometry of hydrogen bonding patterns in the alpha-dodecyl-omega-hydroxy-tris(oxyethylene) (C(12)E(3))-water system have been investigated by near infrared (NIR) spectroscopy. In the 5,300-4,600 cm(-1) region, the characteristic bands for C(12)E(3) and water can be separately investigated, since the combination bands of the OH stretching and its COH bending of alcohols are observed at 5,000-4,650 cm(-1), whereas the combination bands of the OH stretching and its HOH bending of water, at 5,300-5,000 cm(-1). The NIR result has revealed that the addition of water to C(12)E(3) promotes the formation of the OHcdots, three dots, centeredOHcdots, three dots, centeredO hydrogen bonds.

The antitumour drug 7-ethyl-10-hydroxycamptothecin monohydrate and its solid-state hydrolysis mechanism on heating.

PubMed

Ali, Md Ashraf; Noguchi, Shuji; Watanabe, Miteki; Iwao, Yasunori; Itai, Shigeru

2016-10-01

7-Ethyl-10-hydroxycamptothecin [systematic name: (4S)-4,11-diethyl-4,9-dihydroxy-1H-pyrano[3',4':6,7]indolizino[1,2-b]quinoline-3,14(4H,12H)-dione, SN-38] is an antitumour drug which exerts activity through the inhibition of topoisomerase I. The crystal structure of SN-38 as the monohydrate, C 22 H 20 N 2 O 5 ·H 2 O, reveals that it is a monoclinic crystal, with one SN-38 molecule and one water molecule in the asymmetric unit. When the crystal is heated to 473 K, approximately 30% of SN-38 is hydrolyzed at its lactone ring, resulting in the formation of the inactive carboxylate form. The molecular arrangement around the water molecule and the lactone ring of SN-38 in the crystal structure suggests that SN-38 is hydrolyzed by the water molecule at (x, y, z) nucleophilically attacking the carbonyl C atom of the lactone ring at (x - 1, y, z - 1). Hydrogen bonding around the water molecules and the lactone ring appears to promote this hydrolysis reaction: two carbonyl O atoms, which are hydrogen bonded as hydrogen-bond acceptors to the water molecule at (x, y, z), might enhance the nucleophilicity of this water molecule, while the water molecule at (-x, y + 1/2, -z), which is hydrogen bonded as a hydrogen-bond donor to the carbonyl O atom at (x - 1, y, z - 1), might enhance the electrophilicity of the carbonyl C atom.

111 oriented gold nanoplatelets on multilayer graphene as visible light photocatalyst for overall water splitting

PubMed Central

Mateo, Diego; Esteve-Adell, Iván; Albero, Josep; Royo, Juan F. Sánchez; Primo, Ana; Garcia, Hermenegildo

2016-01-01

Development of renewable fuels from solar light appears as one of the main current challenges in energy science. A plethora of photocatalysts have been investigated to obtain hydrogen and oxygen from water and solar light in the last decades. However, the photon-to-hydrogen molecule conversion is still far from allowing real implementation of solar fuels. Here we show that 111 facet-oriented gold nanoplatelets on multilayer graphene films deposited on quartz is a highly active photocatalyst for simulated sunlight overall water splitting into hydrogen and oxygen in the absence of sacrificial electron donors, achieving hydrogen production rate of 1.2 molH2 per gcomposite per h. This photocatalytic activity arises from the gold preferential orientation and the strong gold–graphene interaction occurring in the composite system. PMID:27264495

111 oriented gold nanoplatelets on multilayer graphene as visible light photocatalyst for overall water splitting.

PubMed

Mateo, Diego; Esteve-Adell, Iván; Albero, Josep; Royo, Juan F Sánchez; Primo, Ana; Garcia, Hermenegildo

2016-06-06

Development of renewable fuels from solar light appears as one of the main current challenges in energy science. A plethora of photocatalysts have been investigated to obtain hydrogen and oxygen from water and solar light in the last decades. However, the photon-to-hydrogen molecule conversion is still far from allowing real implementation of solar fuels. Here we show that 111 facet-oriented gold nanoplatelets on multilayer graphene films deposited on quartz is a highly active photocatalyst for simulated sunlight overall water splitting into hydrogen and oxygen in the absence of sacrificial electron donors, achieving hydrogen production rate of 1.2 molH2 per gcomposite per h. This photocatalytic activity arises from the gold preferential orientation and the strong gold-graphene interaction occurring in the composite system.

On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions.

PubMed

Ahmed, Mohammed; Namboodiri, V; Singh, Ajay K; Mondal, Jahur A

2014-10-28

The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) < bulk water < Cl(-) < I(-). It is believed that these structural perturbations influence the dynamics of coherent energy transfer and librational reorientation of water in the hydration shell of anions.

[Impacts of dominated landscape types on hydrogen and oxygen isotope effects of spring water in the Hani Rice Terraces].

PubMed

Jiao, Yuan Mei; Liu, Cheng Jing; Liu, Xin; Liu, Zhi Lin; Ding, Yin Ping

2017-07-18

Analysis of hydrogen and oxygen stable isotopes is an effective method to track the water cycle in watershed. Impact of landscape pattern on the isotope effects of spring water is a new interdisciplinary topic between landscape ecology and isotope hydrology. Taking the Quanfuzhuang River basin located in the core area of UNESCO World Cultural Heritage of Honghe Hani Rice Terrace as the object, collecting the monthly samples of 78 points of spring water and 39 precipitation at altitude of 1500 m (terraces), 1700 m (terraces) and 1900 m (forest) from March 2015 to March 2016, we analyzed the hydrogen and oxygen stable isotopes of water samples under the different landscape types. The results indicated that the dominated landscape types were forests and rice terraces, being 66.6% and 22.1% of the whole landscape area respectively, and they had a spatial vertical pattern of forest located at the mountain top and rice terraces at the down-slope. The correlation analysis showed that the spring water not only came from the precipitation, but also from other water sources which had a more positive δ 18 O and δD values, the spring water in up-slope forests mainly came from precipitation, while that in down-slope rice terraces came from precipitation, ri-ver water, rice terrace water and under ground water. Therefore, the mixing effects of spring water δ 18 O and δD were more significant in rice terraces. The overall altitude effect of the hydrogen and oxygen stable isotopes in spring water was obvious. The linear decreasing rates of δ 18 O and δD values were -0.125‰·(100 m) -1 and -0.688‰·(100 m) -1 , respectively. The deuterium surplus value increased with the altitude because of the impacts of landscape pattern and the local cycle of water isotopes. In summary, the dominant landscape types had a significant impact on the hydrogen and oxygen isotopes of spring water, which could be used as response indicator to reveal the impacts of landscape pattern on hydrological process.

Research Update: Photoelectrochemical water splitting and photocatalytic hydrogen production using ferrites (MFe2O4) under visible light irradiation

NASA Astrophysics Data System (ADS)

Dillert, Ralf; Taffa, Dereje H.; Wark, Michael; Bredow, Thomas; Bahnemann, Detlef W.

2015-10-01

The utilization of solar light for the photoelectrochemical and photocatalytic production of molecular hydrogen from water is a scientific and technical challenge. Semiconductors with suitable properties to promote solar-driven water splitting are a desideratum. A hitherto rarely investigated group of semiconductors are ferrites with the empirical formula MFe2O4 and related compounds. This contribution summarizes the published results of the experimental investigations on the photoelectrochemical and photocatalytic properties of these compounds. It will be shown that the potential of this group of compounds in regard to the production of solar hydrogen has not been fully explored yet.

Enceladus Hydrothermal Activity

NASA Image and Video Library

2017-04-13

This graphic illustrates how scientists on NASA's Cassini mission think water interacts with rock at the bottom of the ocean of Saturn's icy moon Enceladus, producing hydrogen gas (H2). The Cassini spacecraft detected the hydrogen in the plume of gas and icy material spraying from Enceladus during its deepest and last dive through the plume on Oct. 28, 2015. Cassini also sampled the plume's composition during previous flybys, earlier in the mission. From these observations scientists have determined that nearly 98 percent of the gas in the plume is water vapor, about 1 percent is hydrogen, and the rest is a mixture of other molecules including carbon dioxide, methane and ammonia. The graphic shows water from the ocean circulating through the seafloor, where it is heated and interacts chemically with the rock. This warm water, laden with minerals and dissolved gases (including hydrogen and possibly methane) then pours into the ocean creating chimney-like vents. The hydrogen measurements were made using Cassini's Ion and Neutral Mass Spectrometer, or INMS, instrument, which sniffs gases to determine their composition. The finding is an independent line of evidence that hydrothermal activity is taking place in the Enceladus ocean. Previous results from Cassini's Cosmic Dust Analyzer instrument, published in March 2015, suggested hot water is interacting with rock beneath the ocean; the new findings support that conclusion and indicate that the rock is reduced in its geochemistry. With the discovery of hydrogen gas, scientists can now conclude that there is a source of chemical free energy in Enceladus' ocean. https://photojournal.jpl.nasa.gov/catalog/PIA21442

Studies of Hydrogen Production by the Water Gas Shift Reaction and Related Chemistry

DTIC Science & Technology

1983-04-15

STUDIES OF HYDROGEN PRODUCTION BY THE WATER GAS SHIFT REACTION AND RELATED CHEMISTRY Institution: The University of Rochester Department of Chemistry...been app-’.iv -7 for public release and sale; it di.,tribution is unlimited. Abstract Many systems have been investigated for the catalysis of the water ...temperatures (80 - 100’C). In addition aqueous acidic conditions for these systems have been pursued with particular interest in adopting water gas shift

Tuning the mechanical properties of graphene oxide paper and its associated polymer nanocomposites by controlling cooperative intersheet hydrogen bonding.

PubMed

Compton, Owen C; Cranford, Steven W; Putz, Karl W; An, Zhi; Brinson, L Catherine; Buehler, Markus J; Nguyen, SonBinh T

2012-03-27

The mechanical properties of pristine graphene oxide paper and paper-like films of polyvinyl alcohol (PVA)-graphene oxide nanocomposite are investigated in a joint experimental-theoretical and computational study. In combination, these studies reveal a delicate relationship between the stiffness of these papers and the water content in their lamellar structures. ReaxFF-based molecular dynamics (MD) simulations elucidate the role of water molecules in modifying the mechanical properties of both pristine and nanocomposite graphene oxide papers, as bridge-forming water molecules between adjacent layers in the paper structure enhance stress transfer by means of a cooperative hydrogen-bonding network. For graphene oxide paper at an optimal concentration of ~5 wt % water, the degree of cooperative hydrogen bonding within the network comprising adjacent nanosheets and water molecules was found to optimally enhance the modulus of the paper without saturating the gallery space. Introducing PVA chains into the gallery space further enhances the cooperativity of this hydrogen-bonding network, in a manner similar to that found in natural biomaterials, resulting in increased stiffness of the composite. No optimal water concentration could be found for the PVA-graphene oxide nanocomposite papers, as dehydration of these structures continually enhances stiffness until a final water content of ~7 wt % (additional water cannot be removed from the system even after 12 h of annealing). © 2011 American Chemical Society

Hydrogen escape from Mars enhanced by deep convection in dust storms

NASA Astrophysics Data System (ADS)

Heavens, Nicholas G.; Kleinböhl, Armin; Chaffin, Michael S.; Halekas, Jasper S.; Kass, David M.; Hayne, Paul O.; McCleese, Daniel J.; Piqueux, Sylvain; Shirley, James H.; Schofield, John T.

2018-02-01

Present-day water loss from Mars provides insight into Mars's past habitability1-3. Its main mechanism is thought to be Jeans escape of a steady hydrogen reservoir sourced from odd-oxygen reactions with near-surface water vapour2, 4,5. The observed escape rate, however, is strongly variable and correlates poorly with solar extreme-ultraviolet radiation flux6-8, which was predicted to modulate escape9. This variability has recently been attributed to hydrogen sourced from photolysed middle atmospheric water vapour10, whose vertical and seasonal distribution is only partly characterized and understood11-13. Here, we report multi-annual observational estimates of water content and dust and water transport to the middle atmosphere from Mars Climate Sounder data. We provide strong evidence that the transport of water vapour and ice to the middle atmosphere by deep convection in Martian dust storms can enhance hydrogen escape. Planet-encircling dust storms can raise the effective hygropause (where water content rapidly decreases to effectively zero) from 50 to 80 km above the areoid (the reference equipotential surface). Smaller dust storms contribute to an annual mode in water content at 40-50 km that may explain seasonal variability in escape. Our results imply that Martian atmospheric chemistry and evolution can be strongly affected by the meteorology of the lower and middle atmosphere of Mars.

Sulfur mass-independent fractionation in subsurface fracture waters indicates a long-standing sulfur cycle in Precambrian rocks.

PubMed

Li, L; Wing, B A; Bui, T H; McDermott, J M; Slater, G F; Wei, S; Lacrampe-Couloume, G; Lollar, B Sherwood

2016-10-27

The discovery of hydrogen-rich waters preserved below the Earth's surface in Precambrian rocks worldwide expands our understanding of the habitability of the terrestrial subsurface. Many deep microbial ecosystems in these waters survive by coupling hydrogen oxidation to sulfate reduction. Hydrogen originates from water-rock reactions including serpentinization and radiolytic decomposition of water induced by decay of radioactive elements in the host rocks. The origin of dissolved sulfate, however, remains unknown. Here we report, from anoxic saline fracture waters ∼2.4 km below surface in the Canadian Shield, a sulfur mass-independent fractionation signal in dissolved sulfate. We demonstrate that this sulfate most likely originates from oxidation of sulfide minerals in the Archaean host rocks through the action of dissolved oxidants (for example, HO · and H 2 O 2 ) themselves derived from radiolysis of water, thereby providing a coherent long-term mechanism capable of supplying both an essential electron donor (H 2 ) and a complementary acceptor (sulfate) for the deep biosphere.

Chloride concentrations and stable isotopes of hydrogen and oxygen in surface water and groundwater in and near Fish Creek, Teton County, Wyoming, 2005-06

USGS Publications Warehouse

Eddy-Miller, Cheryl A.; Wheeler, Jerrod D.

2010-01-01

Fish Creek, an approximately 25-kilometer long tributary to the Snake River, is located in Teton County in western Wyoming near the town of Wilson. The U.S. Geological Survey, in cooperation with the Teton Conservation District, conducted a study to determine the interaction of local surface water and groundwater in and near Fish Creek. In conjunction with the surface water and groundwater interaction study, samples were collected for analysis of chloride and stable isotopes of hydrogen and oxygen in water. Chloride concentrations ranged from 2.9 to 26.4 milligrams per liter (mg/L) near Teton Village, 1.2 to 4.9 mg/L near Resor's Bridge, and 1.8 to 5.0 mg/L near Wilson. Stable isotope data for hydrogen and oxygen in water samples collected in and near the three cross sections on Fish Creek are shown in relation to the Global Meteoric Water Line and the Local Meteoric Water Line.

Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

NASA Astrophysics Data System (ADS)

Patki, Gauri Dilip

Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from <100 nm to ˜10 nm particles, the hydrogen production rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

Efficient and Safe Chemical Gas Generators with Nanocomposite Reactive Materials

DTIC Science & Technology

2015-11-30

ammonia borane has been developed that involves the reaction of mechanically alloyed Al·Mg powder with water as a source of heat for ammonia borane...Edward L. Dreizin, Evgeny Shafirovich. Hydrogen generation from ammonia borane and water through combustion reactions with mechanically alloyed...on combustion of hydrogen-generating mixtures It is known that ammonia borane (AB) forms combustible mixtures with gelled water and nanoscale

A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water—USGS50 Lake Kyoga Water

USGS Publications Warehouse

Coplen, Tyler B.; Wassenaar, Leonard I; Mukwaya, Christine; Qi, Haiping; Lorenz, Jennifer M.

2015-01-01

This isotopic reference material, designated as USGS50, is intended as one of two reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer, of use especially for isotope-hydrology laboratories analyzing freshwater samples from equatorial and tropical regions.

Photogeneration of active formate decomposition catalysts to produce hydrogen from formate and water

DOEpatents

King, Jr., Allen D.; King, Robert B.; Sailers, III, Earl L.

1983-02-08

A process for producing hydrogen from formate and water by photogenerating an active formate decomposition catalyst from transition metal carbonyl precursor catalysts at relatively low temperatures and otherwise mild conditions is disclosed. Additionally, this process may be expanded to include the generation of formate from carbon monoxide and hydroxide such that the result is the water gas shift reaction.

Tested Demonstrations.

ERIC Educational Resources Information Center

Sands, Robert; And Others

1982-01-01

Procedures for two demonstrations are provided. The solubility of ammonia gas in water is demonstrated by introducing water into a closed can filled with the gas, collapsing the can. The second demonstration relates scale of standard reduction potentials to observed behavior of metals in reactions with hydrogen to produce hydrogen gas. (Author/JN)

Water in the active site of ketosteroid isomerase.

PubMed

Hanoian, Philip; Hammes-Schiffer, Sharon

2011-08-09

Classical molecular dynamics simulations were utilized to investigate the structural and dynamical properties of water in the active site of ketosteroid isomerase (KSI) to provide insight into the role of these water molecules in the enzyme-catalyzed reaction. This reaction is thought to proceed via a dienolate intermediate that is stabilized by hydrogen bonding with residues Tyr16 and Asp103. A comparative study was performed for the wild-type (WT) KSI and the Y16F, Y16S, and Y16F/Y32F/Y57F (FFF) mutants. These systems were studied with three different bound ligands: equilenin, which is an intermediate analog, and the intermediate states of two steroid substrates. Several distinct water occupation sites were identified in the active site of KSI for the WT and mutant systems. Three additional sites were identified in the Y16S mutant that were not occupied in WT KSI or the other mutants studied. The number of water molecules directly hydrogen bonded to the ligand oxygen was approximately two in the Y16S mutant and one in the Y16F and FFF mutants, with intermittent hydrogen bonding of one water molecule in WT KSI. The molecular dynamics trajectories of the Y16F and FFF mutants reproduced the small conformational changes of residue 16 observed in the crystal structures of these two mutants. Quantum mechanical/molecular mechanical calculations of (1)H NMR chemical shifts of the protons in the active site hydrogen-bonding network suggest that the presence of water in the active site does not prevent the formation of short hydrogen bonds with far-downfield chemical shifts. The molecular dynamics simulations indicate that the active site water molecules exchange much more frequently for WT KSI and the FFF mutant than for the Y16F and Y16S mutants. This difference is most likely due to the hydrogen-bonding interaction between Tyr57 and an active site water molecule that is persistent in the Y16F and Y16S mutants but absent in the FFF mutant and significantly less probable in WT KSI. © 2011 American Chemical Society

Light water detritiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fedorchenko, O.A.; Aleksee, I.A.; Bondarenko, S.D.

2015-03-15

Hundreds of thousands of tons of tritiated light water have been accumulating from the enterprises of nuclear fuel cycles around the world. The Dual-Temperature Water-Hydrogen (DTWH) process looks like the only practical alternative to Combined Electrolysis and Catalytic Exchange (CECE). In DTWH power-consuming lower reflux device (electrolytic cell) is replaced by a so-called 'hot tower' (LPCE column operating at conditions which ensure relatively small value of elementary separation factor α(hot)). In the upper, cold tower, the tritium transfers from hydrogen to water while in the lower, hot tower - in the opposite direction - from water to hydrogen. The DTWHmore » process is much more complicated compared to CECE; it must be thoroughly computed and strictly controlled by an automatic control system. The use of a simulation code for DTWH is absolutely important. The simulation code EVIO-5 deals with 3 flows inside a column (hydrogen gas, water vapour and liquid water) and 2 simultaneous isotope exchange sub-processes (counter-current phase exchange and co-current catalytic exchange). EVIO-5 takes into account the strong dependence of process performance on given conditions (temperature and pressure). It calculates steady-state isotope concentration profiles considering a full set of reversible exchange reactions between different isotope modifications of water and hydrogen (12 molecular species). So the code can be used for simulation of LPCE column operation for detritiation of hydrogen and water feed, which contains H and D not only at low concentrations but above 10 at.% also. EVIO-5 code is used to model a Tritium Removal Facility with a throughput capacity of about 400 m{sup 3}/day. Simulation results show that a huge amount of wet-proofed catalyst is required (about 6000 m{sup 3}), mainly (90%) in the first stage. One reason for these large expenses (apart from a big scale of the problem itself) is the relatively high tritium separation factor in the hot tower. The introduction of some quantity of deuterium into the gaseous flow before the hot tower lowers the tritium separation factor in that column. One possible variant of deuterium introduction to the hot tower of the first stage was modelled. The decontamination capacity increases by a 2.5 factor.« less

Catalytic homogeneous hydrogenation of compounds containing X --> O semipolar bonds (X = N, S, P) with para-hydrogen as a promising route for preparation of para-water.

PubMed

Ustynyuk, Yuri A; Gavrikov, Alexei V; Sergeyev, Nikolay M

2006-11-28

The quantum-chemical simulation (DFT, PBE, TZ2p basis set) of the mechanism of catalytic hydrogenation of compounds containing R(n)X --> O semipolar bonds (R(n)X = N(2), Me(2)S, C(5)H(5)N, Ph(3)P) on the Wilkinson catalyst (Ph(3)P)(3)RhCl with para-hydrogen showed that this process proceeds with retention of proton nuclear spin correlation, which enables a principal possibility to synthesize para-H(2)O, i.e. the nuclear spin isomer of water with antiparallel proton spins, using this route.

Hydrogen Hotspots on Vesta

NASA Image and Video Library

2012-09-20

This image shows that NASA Dawn mission detected abundances of hydrogen in a wide swath around the equator of the giant asteroid Vesta. The hydrogen probably exists in the form of hydroxyl or water bound to minerals in Vesta surface.

An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911

Effect of high-temperature water and hydrogen on the fracture behavior of a low-alloy reactor pressure vessel steel

NASA Astrophysics Data System (ADS)

Roychowdhury, S.; Seifert, H.-P.; Spätig, P.; Que, Z.

2016-09-01

Structural integrity of reactor pressure vessels (RPV) is critical for safety and lifetime. Possible degradation of fracture resistance of RPV steel due to exposure to coolant and hydrogen is a concern. In this study tensile and elastic-plastic fracture mechanics (EPFM) tests in air (hydrogen pre-charged) and EFPM tests in hydrogenated/oxygenated high-temperature water (HTW) was done, using a low-alloy RPV steel. 2-5 wppm hydrogen caused embrittlement in air tensile tests at room temperature (25 °C) and at 288 °C, effects being more significant at 25 °C and in simulated weld coarse grain heat affected zone material. Embrittlement at 288 °C is strain rate dependent and is due to localized plastic deformation. Hydrogen pre-charging/HTW exposure did not deteriorate the fracture resistance at 288 °C in base metal, for investigated loading rate range. Clear change in fracture morphology and deformation structures was observed, similar to that after air tests with hydrogen.

Simulation of Water Gas Shift Zeolite Membrane Reactor

NASA Astrophysics Data System (ADS)

Makertiharta, I. G. B. N.; Rizki, Z.; Zunita, Megawati; Dharmawijaya, P. T.

2017-07-01

The search of alternative energy sources keeps growing from time to time. Various alternatives have been introduced to reduce the use of fossil fuel, including hydrogen. Many pathways can be used to produce hydrogen. Among all of those, the Water Gas Shift (WGS) reaction is the most common pathway to produce high purity hydrogen. The WGS technique faces a downstream processing challenge due to the removal hydrogen from the product stream itself since it contains a mixture of hydrogen, carbon dioxide and also the excess reactants. An integrated process using zeolite membrane reactor has been introduced to improve the performance of the process by selectively separate the hydrogen whilst boosting the conversion. Furthermore, the zeolite membrane reactor can be further improved via optimizing the process condition. This paper discusses the simulation of Zeolite Membrane Water Gas Shift Reactor (ZMWGSR) with variation of process condition to achieve an optimum performance. The simulation can be simulated into two consecutive mechanisms, the reaction prior to the permeation of gases through the zeolite membrane. This paper is focused on the optimization of the process parameters (e.g. temperature, initial concentration) and also membrane properties (e.g. pore size) to achieve an optimum product specification (concentration, purity).

The role of the reactor wall in hydrothermal biomass conversions.

PubMed

Fábos, Viktória; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

2012-11-01

The processing of renewable feedstocks to platform chemicals and, to a lesser degree, fuels is a key part of sustainable development. In particular, the combination of lignocellulosic biomass with hydrothermal upgrading (HTU), using high temperature and pressure water (HTPW), is experiencing a renaissance. One of the many steps in this complicated process is the in-situ hydrogenation of intermediate compounds. As formic acid and related low-molecular-weight oxygenates are among the species generated, it is conceivable that they act as a hydrogen source. Such hydrogenations have been suggested to be catalyzed by water, by bases like NaOH, and/or to involve "reactive/nascent hydrogen". To achieve the temperatures and pressures required for HTU, it is necessary to conduct the reactions in high-pressure vessels. Metals are typical components of their walls and/or internal fittings. Here, using cyclohexanone as a model compound for more complex biomass-derived molecules, iron in the wall of high-pressure stainless steel reactors is shown to be responsible for the hydrogenation of ketones with low-molecular-weight oxygenates acting as a hydrogen source in combination with water. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aluminum and Other Coatings for the Passivation of Tritium Storage Vessels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spencer, W.; Korinko, P.

Using a highly sensitive residual gas analyzer, the off-gassing of hydrogen, water, and hydrocarbons from surface-treated storage vessels containing deuterium was measured. The experimental storage vessels were compared to a low-off-gassing, electro-polished 304L canister. Alternative vessels were made out of aluminum, or were coatings on 304L steel. Coatings included powder pack aluminide, electro-plated aluminum, powder pack chromide, dense electro-plated chromium, copper plated, and copper plated with 25 and 50 percent nano-diamond. Vessels were loaded with low pressure deuterium to observe exchange with protium or hydrogen as observed with formation of HD and HDO. Off gas of D 2O or possiblemore » CD 4 was observed at mass 20. The main off-gas in all of the studies was H 2. The studies indicated that coatings required significant post-coating treatment to reduce off-gas and enhance the permeation barrier from gases likely added during the coating process. Dense packed aluminum coatings needed heating to drive off water. Electro-plated aluminum, chromium and copper coatings appeared to trap hydrogen from the plating process. Nano-diamond appeared to enhance the exchange rate with hydrogen off gas, and its coating process trapped significant amounts of hydrogen. Aluminum caused more protium exchange than chromium-treated surfaces. Aluminum coatings released more water, but pure aluminum vessels released small amounts of hydrogen, little water, and generally performed well. Chromium coating had residual hydrogen that was difficult to totally outgas but otherwise gave low residuals for water and hydrocarbons. Our studies indicated that simple coating of as received 304L metal will not adequately block hydrogen. The base vessel needs to be carefully out-gassed before applying a coating, and the coating process will likely add additional hydrogen that must be removed. Initial simple bake-out and leak checks up to 350° C for a few hours was found to be inadequate. All of the studies indicated that vessels needed several days of vacuum baking at 350-450° C to fully outgas the residual gases, which were mostly hydrogen. The current standard practice of out-gassing from ultra-clean, electro-polished 304L vessels with both vacuum bake-out and followed by an oxidative bake out to enhance the chromium surface performed the best in these studies.« less

Coupling Glucose Dehydrogenation with CO2 Hydrogenation by Hydrogen Transfer in Aqueous Media at Room Temperature.

PubMed

Ding, Guodong; Su, Ji; Zhang, Cheng; Tang, Kan; Yang, Lisha; Lin, Hongfei

2018-05-08

Conversion of carbon dioxide into value-added chemicals and fuels provides a direct solution to reduce excessive CO2 in the atmosphere. Herein, a novel catalytic reaction system is presented by coupling the dehydrogenation of glucose with the hydrogenation of a CO2 derived salt, ammonium carbonate, in the ethanol-water mixture. For the first time, the hydrogenation of CO2 into formate by glucose has been achieved under ambient conditions. Under the optimal reaction conditions, the highest yield of formate reached ~ 46 %. We find that the apparent pH value in the ethanol-water mixture plays a central role in determining the performance of the hydrogen transfer reaction. Based on the 13C NMR and ESI-MS results, a possible pathway of the coupled glucose dehydrogenation and CO2 hydrogenation reactions was proposed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interplay between translational diffusion and large-amplitude angular jumps of water molecules

NASA Astrophysics Data System (ADS)

Liu, Chao; Zhang, Yangyang; Zhang, Jian; Wang, Jun; Li, Wenfei; Wang, Wei

2018-05-01

Understanding the microscopic mechanism of water molecular translational diffusion is a challenging topic in both physics and chemistry. Here, we report an investigation on the interplay between the translational diffusion and the large-amplitude angular jumps of water molecules in bulk water using molecular dynamics simulations. We found that large-amplitude angular jumps are tightly coupled to the translational diffusions. Particularly, we revealed that concurrent rotational jumps of spatially neighboring water molecules induce inter-basin translational jumps, which contributes to the fast component of the water translational diffusion. Consequently, the translational diffusion shows positional heterogeneity; i.e., the neighbors of the water molecules with inter-basin translational jumps have larger probability to diffuse by inter-basin translational jumps. Our control simulations showed that a model water molecule with moderate hydrogen bond strength can diffuse much faster than a simple Lennard-Jones particle in bulk water due to the capability of disturbing the hydrogen bond network of the surrounding water molecules. Our results added to the understanding of the microscopic picture of the water translational diffusion and demonstrated the unique features of water diffusion arising from their hydrogen bond network structure compared with those of the simple liquids.

Hydrogen production from water-glucose solution over NiO/La-NaTaO3 photocatalyst

NASA Astrophysics Data System (ADS)

Mardian, R.; Husin, H.; Pontas, K.; Zaki, M.; Asnawi, T. M.; Ahmadi

2018-03-01

This paper reports the evaluation of La-NaTaO3 photocatalyst performance in producing hydrogen from water-glucose solution. The main goal of the studies is to investigate the influence of glucose as a sacrificial reagent on the photocatalytic efficiency in water splitting reactions under ultraviolet (UV) irradiation. Photocatalyst has been fabricated via sol-gel method and being confirmed using x-ray diffraction (XRD) and scanning electron microscopy (SEM). Nickel loaded La-NaTaO3 photocatalyst are prepared by impregnation method. It was observed that the prepared photocatalysts displayed particle sizes in the 30-250 nm range with orthorhombic structure. Their photocatalytic activity for hydrogen production via water splitting was conducted in a Pyrex glass reactor under UV light irradiation. The aqueous solution contained glucose employed as a renewable organic scavenger. A significant improvement in hydrogen production was observed in glucose-water mixtures and NiO loaded photocatalyst. The prepared La-NaTaO3 showed that the highest activity for hydrogen generation of 35.1 mmol h-1.g-1 was obtained at 0.10 mol.L-1 glucose and 0.3 wt.% NiO. This suggests the important role played by the glucose as electron donor and loading nickel on La-NaTaO3 as a cocatalyst increasing electron storage and suppressing electron-hole recombination.

The hydrolysis of epoxides catalyzed by inorganic ammonium salts in water: kinetic evidence for hydrogen bond catalysis.

PubMed

Nozière, B; Fache, F; Maxut, A; Fenet, B; Baudouin, A; Fine, L; Ferronato, C

2018-01-17

Naturally-occurring inorganic ammonium ions have been recently reported as efficient catalysts for some organic reactions in water, which contributes to the understanding of the chemistry in some natural environments (soils, seawater, atmospheric aerosols, …) and biological systems, and is also potentially interesting for green chemistry as many of their salts are cheap and non-toxic. In this work, the effect of NH 4 + ions on the hydrolysis of small epoxides in water was studied kinetically. The presence of NH 4 + increased the hydrolysis rate by a factor of 6 to 25 compared to pure water and these catalytic effects were shown not to result from other ions, counter-ions or from acid or base catalysis, general or specific. The small amounts of amino alcohols produced in the reactions were identified as the actual catalysts by obtaining a strong acceleration of the reactions when adding these compounds directly to the epoxides in water. Replacing the amino alcohols by other strong hydrogen-bond donors, such as trifluoroethanol (TFE) or hexafluoroisopropanol (HFIP) gave the same results, demonstrating that the kinetics of these reactions was driven by hydrogen-bond catalysis. Because of the presence of many hydrogen-bond donors in natural environments (for instance amines and hydroxy-containing compounds), hydrogen-bond catalysis is likely to contribute to many reaction rates in these environments.

Hydrogen-water vapor mixtures: Control of hydrothermal atmospheres by hydrogen osmosis

USGS Publications Warehouse

Shaw, H.R.

1963-01-01

Experiments at 700??C and 800 bars total pressure demonstrate positive deviations from ideality for mixtures of hydrogen and H2O gases. The deviations are greater than predicted with Stockmayer's method. The composition of the mixture and the fugacity of hydrogen are controlled by diffusing hydrogen through metallic membranes. The results give the fugacities of both H 2O and oxygen.

Local structure of dilute aqueous DMSO solutions, as seen from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Idrissi, Abdenacer; Marekha, Bogdan A.; Barj, Mohammed; Miannay, François Alexandre; Takamuku, Toshiyuki; Raptis, Vasilios; Samios, Jannis; Jedlovszky, Pál

2017-06-01

The information about the structure of dimethyl sulfoxide (DMSO)-water mixtures at relatively low DMSO mole fractions is an important step in order to understand their cryoprotective properties as well as the solvation process of proteins and amino acids. Classical MD simulations, using the potential model combination that best reproduces the free energy of mixing of these compounds, are used to analyze the local structure of DMSO-water mixtures at DMSO mole fractions below 0.2. Significant changes in the local structure of DMSO are observed around the DMSO mole fraction of 0.1. The array of evidence, based on the cluster and the metric and topological parameters of the Voronoi polyhedra distributions, indicates that these changes are associated with the simultaneous increase of the number of DMSO-water and decrease of water-water hydrogen bonds with increasing DMSO concentration. The inversion between the dominance of these two types of H-bonds occurs around XDMSO = 0.1, above which the DMSO-DMSO interactions also start playing an important role. In other words, below the DMSO mole fraction of 0.1, DMSO molecules are mainly solvated by water molecules, while above it, their solvation shell consists of a mixture of water and DMSO. The trigonal, tetrahedral, and trigonal bipyramidal distributions of water shift to lower corresponding order parameter values indicating the loosening of these orientations. Adding DMSO does not affect the hydrogen bonding between a reference water molecule and its first neighbor hydrogen bonded water molecules, while it increases the bent hydrogen bond geometry involving the second ones. The close-packed local structure of the third, fourth, and fifth water neighbors also is reinforced. In accordance with previous theoretical and experimental data, the hydrogen bonding between water and the first, the second, and the third DMSO neighbors is stronger than that with its corresponding water neighbors. At a given DMSO mole fraction, the behavior of the intensity of the high orientational order parameter values indicates that water molecules are more ordered in the vicinity of the hydrophilic group while their structure is close-packed near the hydrophobic group of DMSO.

A hydrogen gas-water equilibration method produces accurate and precise stable hydrogen isotope ratio measurements in nutrition studies

USDA-ARS?s Scientific Manuscript database

Stable hydrogen isotope methodology is used in nutrition studies to measure growth, breast milk intake, and energy requirement. Isotope ratio MS is the best instrumentation to measure the stable hydrogen isotope ratios in physiological fluids. Conventional methods to convert physiological fluids to ...

Round-the-clock power supply and a sustainable economy via synergistic integration of solar thermal power and hydrogen processes

PubMed Central

Gençer, Emre; Mallapragada, Dharik S.; Maréchal, François; Tawarmalani, Mohit; Agrawal, Rakesh

2015-01-01

We introduce a paradigm—“hydricity”—that involves the coproduction of hydrogen and electricity from solar thermal energy and their judicious use to enable a sustainable economy. We identify and implement synergistic integrations while improving each of the two individual processes. When the proposed integrated process is operated in a standalone, solely power production mode, the resulting solar water power cycle can generate electricity with unprecedented efficiencies of 40–46%. Similarly, in standalone hydrogen mode, pressurized hydrogen is produced at efficiencies approaching ∼50%. In the coproduction mode, the coproduced hydrogen is stored for uninterrupted solar power production. When sunlight is unavailable, we envision that the stored hydrogen is used in a “turbine”-based hydrogen water power (H2WP) cycle with the calculated hydrogen-to-electricity efficiency of 65–70%, which is comparable to the fuel cell efficiencies. The H2WP cycle uses much of the same equipment as the solar water power cycle, reducing capital outlays. The overall sun-to-electricity efficiency of the hydricity process, averaged over a 24-h cycle, is shown to approach ∼35%, which is nearly the efficiency attained by using the best multijunction photovoltaic cells along with batteries. In comparison, our proposed process has the following advantages: (i) It stores energy thermochemically with a two- to threefold higher density, (ii) coproduced hydrogen has alternate uses in transportation/chemical/petrochemical industries, and (iii) unlike batteries, the stored energy does not discharge over time and the storage medium does not degrade with repeated uses. PMID:26668380

Round-the-clock power supply and a sustainable economy via synergistic integration of solar thermal power and hydrogen processes.

PubMed

Gençer, Emre; Mallapragada, Dharik S; Maréchal, François; Tawarmalani, Mohit; Agrawal, Rakesh

2015-12-29

We introduce a paradigm-"hydricity"-that involves the coproduction of hydrogen and electricity from solar thermal energy and their judicious use to enable a sustainable economy. We identify and implement synergistic integrations while improving each of the two individual processes. When the proposed integrated process is operated in a standalone, solely power production mode, the resulting solar water power cycle can generate electricity with unprecedented efficiencies of 40-46%. Similarly, in standalone hydrogen mode, pressurized hydrogen is produced at efficiencies approaching ∼50%. In the coproduction mode, the coproduced hydrogen is stored for uninterrupted solar power production. When sunlight is unavailable, we envision that the stored hydrogen is used in a "turbine"-based hydrogen water power (H2WP) cycle with the calculated hydrogen-to-electricity efficiency of 65-70%, which is comparable to the fuel cell efficiencies. The H2WP cycle uses much of the same equipment as the solar water power cycle, reducing capital outlays. The overall sun-to-electricity efficiency of the hydricity process, averaged over a 24-h cycle, is shown to approach ∼35%, which is nearly the efficiency attained by using the best multijunction photovoltaic cells along with batteries. In comparison, our proposed process has the following advantages: (i) It stores energy thermochemically with a two- to threefold higher density, (ii) coproduced hydrogen has alternate uses in transportation/chemical/petrochemical industries, and (iii) unlike batteries, the stored energy does not discharge over time and the storage medium does not degrade with repeated uses.

H.sub.2O doped WO.sub.3, ultra-fast, high-sensitivity hydrogen sensors

DOEpatents

Liu, Ping [Denver, CO; Tracy, C Edwin [Golden, CO; Pitts, J Roland [Lakewood, CO; Lee, Se-Hee [Lakewood, CO

2011-03-22

An ultra-fast response, high sensitivity structure for optical detection of low concentrations of hydrogen gas, comprising: a substrate; a water-doped WO.sub.3 layer coated on the substrate; and a palladium layer coated on the water-doped WO.sub.3 layer.

Lunar Water Resource Demonstration

NASA Technical Reports Server (NTRS)

Muscatello, Anthony C.

2008-01-01

In cooperation with the Canadian Space Agency, the Northern Centre for Advanced Technology, Inc., the Carnegie-Mellon University, JPL, and NEPTEC, NASA has undertaken the In-Situ Resource Utilization (ISRU) project called RESOLVE. This project is a ground demonstration of a system that would be sent to explore permanently shadowed polar lunar craters, drill into the regolith, determine what volatiles are present, and quantify them in addition to recovering oxygen by hydrogen reduction. The Lunar Prospector has determined these craters contain enhanced hydrogen concentrations averaging about 0.1%. If the hydrogen is in the form of water, the water concentration would be around 1%, which would translate into billions of tons of water on the Moon, a tremendous resource. The Lunar Water Resource Demonstration (LWRD) is a part of RESOLVE designed to capture lunar water and hydrogen and quantify them as a backup to gas chromatography analysis. This presentation will briefly review the design of LWRD and some of the results of testing the subsystem. RESOLVE is to be integrated with the Scarab rover from CMIJ and the whole system demonstrated on Mauna Kea on Hawaii in November 2008. The implications of lunar water for Mars exploration are two-fold: 1) RESOLVE and LWRD could be used in a similar fashion on Mars to locate and quantify water resources, and 2) electrolysis of lunar water could provide large amounts of liquid oxygen in LEO, leading to lower costs for travel to Mars, in addition to being very useful at lunar outposts.

Effect Of Substrates On The Fractionation Of Hydrogen Isotopes During Lipid-Biosynthesis By Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, S. S.; Pagani, M.

2010-12-01

Lipids form an important class of proxies for paleoclimatological research, and hydrogen isotope ratios of lipids are being increasingly used for understanding changes in the hydrological system. Proper understanding of hydrogen isotope fractionation during lipid biosynthesis is therefore important and attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis in various organisms. Hydrogen isotope ratios of lipids depend on the hydrogen isotopic composition of the ambient water, hydrogen isotopic composition of NADPH used during biosynthesis, growth conditions, pathways of lipid biosynthesis, and substrates in the case of heterotrophic organisms. Recently it has been observed that NADPH contributes a significant part of the hydrogen in fatty acids synthesized by bacteria during heterotrophic growth (Zhang et al, 2009). As NADPH is formed by reduction of NADP+ during metabolism of substrates, different metabolic pathways form NADPH with different D/H ratios, which in turn results in variation in D/H ratios of lipids (Zhang et al, 2009). Therefore, substrates play a significant role in hydrogen isotopic compositions of lipids. For this study, we are investigating the effects of substrates on hydrogen isotope fractionation during biosynthesis of isoprenoidal lipids by heterotrophically growing halophilic archaea. Haloarcula marismortui is a halophilic archaea which synthesizes Archaeol (a diether lipid) and other isoprenoidal lipids. We have grown Haloarcula marismortui in pure cultures on three different substrates and are in the process of evaluating isotopic variability of Archaeol and other lipids associated with substrate and the D/H composition of ambient water. Our results will be helpful for a better understanding of hydrogen isotope fractionations during lipid synthesis by archaea. Also, halophilic archaea are the only source of archaeol in hypersaline environments. Therefore, our results will also indicate whether archaeol can be used as a proxy of ambient water hydrogen isotopic compositions in hypersaline environments.

Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer

NASA Astrophysics Data System (ADS)

Pan, Hui

2016-02-01

Water electrolysis is an efficient way for hydrogen production. Finding efficient, cheap, and eco-friendly electrocatalysts is essential to the development of this technology. In the work, we present a first-principles study on the effects of tension on the hydrogen evolution reaction of a novel electrocatalyst, vanadium disulfide (VS2) monolayer. Two electrocatalytic processes, individual and collective processes, are investigated. We show that the catalytic ability of VS2 monolayer at higher hydrogen coverage can be efficiently improved by escalating tension. We find that the individual process is easier to occur in a wide range of hydrogen coverage and the collective process is possible at a certain hydrogen coverage under the same tension. The best hydrogen evolution reaction with near-zero Gibbs free energy can be achieved by tuning tension. We further show that the change of catalytic activity with tension and hydrogen coverage is induced by the change of free carrier density around the Fermi level, that is, higher carrier density, better catalytic performance. It is expected that tension can be a simple way to improve the catalytic activity, leading to the design of novel electrocatalysts for efficient hydrogen production from water electrolysis.

The Imprint of Atmospheric Evolution in the D/H of Hesperian Clay Minerals on Mars

NASA Technical Reports Server (NTRS)

Mahaffy, P. R.; Webster, C. R.; Stern, J. C.; Brunner, A. E.; Atreya, S. K.; Conrad, P. G.; Domagal-Goldman, S.; Eigenbrode, J. L.; Flesch, G. J.; Christensen, L. E.;

Glacial melt water in Greenland - A renewable resource for the future

NASA Astrophysics Data System (ADS)

Alther, G. R.; Ruedisili, L. C.; Stauber, H.; Kollbrunner, C. F.

1981-06-01

Glacial melt water in Greenland can be used as a renewable resource for generating electricity (a yearly estimate of 60-115 GW), and it can serve as a supplementary source for drinking and irrigation, metallurgical processing, and the manufacturing of liquid hydrogen as fuel. Southern Greenland is particularly suited for this melt water hydropower project, having high precipitation and summer temperatures, large quantities of melt water, natural 'nunatak' dams, and coastal ranges with steep gradients. Transportation of the generated energy is proposed in the form of sea cables and overland transmission lines, hydrogen gas pipelines, and tankers for liquid hydrogen transport. A hypothetical glacial power station is schematically illustrated, and production costs are calculated. The glacial melt project would serve as an economical source of energy with minimal damage to the environment.

Molecular Hydrogen Attenuates Neuropathic Pain in Mice

PubMed Central

Kawaguchi, Masanori; Satoh, Yasushi; Otsubo, Yukiko; Kazama, Tomiei

2014-01-01

Neuropathic pain remains intractable and the development of new therapeutic strategies are urgently required. Accumulating evidence indicates that overproduction of oxidative stress is a key event in the pathogenesis of neuropathic pain. However, repeated intra-peritoneal or intrathecal injections of antioxidants are unsuitable for continuous use in therapy. Here we show a novel therapeutic method against neuropathic pain: drinking water containing molecular hydrogen (H2) as antioxidant. The effect of hydrogen on neuropathic pain was investigated using a partial sciatic nerve ligation model in mice. As indicators of neuropathic pain, temporal aspects of mechanical allodynia and thermal hyperalgesia were analysed for 3 weeks after ligation. Mechanical allodynia and thermal hyperalgesia were measured using the von Frey test and the plantar test, respectively. When mice were allowed to drink water containing hydrogen at a saturated level ad libitum after ligation, both allodynia and hyperalgesia were alleviated. These symptoms were also alleviated when hydrogen was administered only for the induction phase (from day 0 to 4 after ligation). When hydrogen was administered only for the maintenance phase (from day 4 to 21 after ligation), hyperalgesia but not allodynia was alleviated. Immunohistochemical staining for the oxidative stress marker, 4-hydroxy-2-nonenal and 8-hydroxydeoxyguanosine, showed that hydrogen administration suppressed oxidative stress induced by ligation in the spinal cord and the dorsal root ganglion. In conclusion, oral administration of hydrogen water may be useful for alleviating neuropathic pain in a clinical setting. PMID:24941001

Studies of Hydrogen Production by the Water Gas Shift Reaction and Related Chemistry

DTIC Science & Technology

1983-04-15

HYDROGEN PRODUCTION BY THE WATER GAS SHIFT REACTION AND RELATED CHEMISTRY Institution: The University of Rochester Department of Chemistry -. Rochester...been in siated for the catalysis of the water gas shift reaction, W20 + CO H𔃼 + C02, and for electrocatalytic oxidation of CO, CO + H󈧘 C02 + 2H...particular interest in adopting water gas shift catalysts to act as electrocatalysts for the anode reaction of CO fuel cells. Under these conditions the best

The water dimer II: Theoretical investigations

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Anamika; Xantheas, Sotiris S.; Saykally, Richard J.

2018-05-01

As the archetype of aqueous hydrogen bonding, the water dimer has been extensively studied by both theory and experiment for nearly seven decades. In this article, we present a detailed chronological review of the theoretical advances made using electronic structure methods to address the structure, hydrogen bonding and vibrational spectroscopy of the water dimer, as well as the role of its potential energy surface in the development of classical force fields to describe intermolecular interactions in clusters and the condensed phases of water.

The Water Dimer II: Theoretical Investigations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukhopadhyay, Anamika; Xantheas, Sotiris S.; Saykally, Richard J.

As the archetype of aqueous hydrogen bonding, the water dimer has been extensively studied by both theory and experiment for nearly seven decades. Here in this article, we present a detailed chronological review of the theoretical advances made using electronic structure methods to address the structure, hydrogen bonding and vibrational spectroscopy of the water dimer, as well as the role of its potential energy surface in the development of classical force fields to describe intermolecular interaction in clusters and the condensed phases of water.

Hydrogen Isotopes Record the History of the Martian Hydrosphere and Atmosphere

NASA Technical Reports Server (NTRS)

Usui, T.; Simon, J. I.; Jones, J. H.; Kurokawa, H.; Sato, M.; Alexander, C. M. O'D; Wang, J.

2015-01-01

The surface geology and geomorphology of Mars indicates that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. This study presents insights from hydrogen isotopes for the origin and evolution of Martian water reservoirs.

The Water Dimer II: Theoretical Investigations

DOE PAGES

Mukhopadhyay, Anamika; Xantheas, Sotiris S.; Saykally, Richard J.

2018-03-29

As the archetype of aqueous hydrogen bonding, the water dimer has been extensively studied by both theory and experiment for nearly seven decades. Here in this article, we present a detailed chronological review of the theoretical advances made using electronic structure methods to address the structure, hydrogen bonding and vibrational spectroscopy of the water dimer, as well as the role of its potential energy surface in the development of classical force fields to describe intermolecular interaction in clusters and the condensed phases of water.

The role of molecular hydrogen and methane oxidation in the water vapour budget of the stratosphere

NASA Technical Reports Server (NTRS)

Le Texier, H.; Solomon, S.; Garcia, R. R.

1988-01-01

The detailed photochemistry of methane oxidation has been studied in a coupled chemical/dynamical model of the middle atmosphere. The photochemistry of formaldehyde plays an important role in determining the production of water vapor from methane oxidation. At high latitudes, the production and transport of molecular hydrogen is particularly important in determining the water vapor distribution. It is shown that the ratio of the methane vertical gradient to the water vapor vertical gradient at any particular latitude should not be expected to be precisely 2, due both to photochemical and dynamical effects. Modeled H2O profiles are compared with measurements from the Limb Infrared Monitor of the Stratosphere (LIMS) experiment at various latitudes. Molecular hydrogen is shown to be responsible for the formation of a secondary maximum displayed by the model water vapor profiles in high latitude summer, a feature also found in the LIMS data.

Method of generating hydrogen gas from sodium borohydride

DOEpatents

Kravitz, Stanley H.; Hecht, Andrew M.; Sylwester, Alan P.; Bell, Nelson S.

2007-12-11

A compact solid source of hydrogen gas, where the gas is generated by contacting water with micro-disperse particles of sodium borohydride in the presence of a catalyst, such as cobalt or ruthenium. The micro-disperse particles can have a substantially uniform diameter of 1-10 microns, and preferably about 3-5 microns. Ruthenium or cobalt catalytic nanoparticles can be incorporated in the micro-disperse particles of sodium borohydride, which allows a rapid and complete reaction to occur without the problems associated with caking and scaling of the surface by the reactant product sodium metaborate. A closed loop water management system can be used to recycle wastewater from a PEM fuel cell to supply water for reacting with the micro-disperse particles of sodium borohydride in a compact hydrogen gas generator. Capillary forces can wick water from a water reservoir into a packed bed of micro-disperse fuel particles, eliminating the need for using an active pump.

Compact solid source of hydrogen gas

DOEpatents

Kravitz, Stanley H.; Hecht, Andrew M.; Sylwester, Alan P.; Bell, Nelson S.

2004-06-08

A compact solid source of hydrogen gas, where the gas is generated by contacting water with micro-disperse particles of sodium borohydride in the presence of a catalyst, such as cobalt or ruthenium. The micro-disperse particles can have a substantially uniform diameter of 1-10 microns, and preferably about 3-5 microns. Ruthenium or cobalt catalytic nanoparticles can be incorporated in the micro-disperse particles of sodium borohydride, which allows a rapid and complete reaction to occur without the problems associated with caking and scaling of the surface by the reactant product sodium metaborate. A closed loop water management system can be used to recycle wastewater from a PEM fuel cell to supply water for reacting with the micro-disperse particles of sodium borohydride in a compact hydrogen gas generator. Capillary forces can wick water from a water reservoir into a packed bed of micro-disperse fuel particles, eliminating the need for using an active pump.

Isotopy of the hydrosphere

NASA Astrophysics Data System (ADS)

Ferronskii, V. I.; Poliakov, V. A.

This book is concerned with the natural relations regarding the distribution of the stable isotopes of hydrogen and oxygen in the hydrosphere, taking into account the most important problems with respect to the dynamics and the origin of waters. The solution of these problems on an isotopic basis is considered. The physicochemical principles of isotope separation are discussed along with the isotopic composition of atmospheric moisture, the isotopic composition of surface continental waters, the hydrogen and oxygen isotopic composition of minerals of magmatic and metamorphic rocks and fluid inclusions, the isotopic composition of groundwaters of modern volcanic regions, and the origin of the earth's hydrosphere in the light of isotopic, cosmochemical, and theoretical studies. Attention is also given to the separation of hydrogen and oxygen isotopes of waters in the underground cycle, the isotopic composition of the deep-formation waters of sedimentary basins, the relationship between surface and ground waters, and the groundwater residence time in an aquifer.

Low hydrogen contents in the cores of terrestrial planets.

PubMed

Clesi, Vincent; Bouhifd, Mohamed Ali; Bolfan-Casanova, Nathalie; Manthilake, Geeth; Schiavi, Federica; Raepsaet, Caroline; Bureau, Hélène; Khodja, Hicham; Andrault, Denis

2018-03-01

Hydrogen has been thought to be an important light element in Earth's core due to possible siderophile behavior during core-mantle segregation. We reproduced planetary differentiation conditions using hydrogen contents of 450 to 1500 parts per million (ppm) in the silicate phase, pressures of 5 to 20 GPa, oxygen fugacity varying within IW-3.7 and IW-0.2 (0.2 to 3.7 log units lower than iron-wüstite buffer), and Fe alloys typical of planetary cores. We report hydrogen metal-silicate partition coefficients of ~2 × 10 -1 , up to two orders of magnitude lower than reported previously, and indicative of lithophile behavior. Our results imply H contents of ~60 ppm in the Earth and Martian cores. A simple water budget suggests that 90% of the water initially present in planetary building blocks was lost during planetary accretion. The retained water segregated preferentially into planetary mantles.

Molecular dynamics simulations of trihalomethanes removal from water using boron nitride nanosheets.

PubMed

Azamat, Jafar; Khataee, Alireza; Joo, Sang Woo

2016-04-01

Molecular dynamics simulations were performed to investigate the separation of trihalomethanes (THMs) from water using boron nitride nanosheets (BNNSs). The studied systems included THM molecules and a functionalized BNNS membrane immersed in an aqueous solution. An external pressure was applied to the z axis of the systems. Two functionalized BNNSs with large fluorinated-hydrogenated pore (F-H-pores) and small hydrogen-hydroxyl pore (H-OH-pores) were used. The pores of the BNNS membrane were obtained by passivating each nitrogen and boron atoms at the pore edges with fluorine and hydrogen atoms in the large pore or with hydroxyl and hydrogen atoms in the small pore. The results show that the BNNS with a small functionalized pore was impermeable to THM molecules, in contrast to the BNNS with a large functionalized pore. Using these membranes, water contaminants can be removed at lower cost.

Status of the DOE /STOR/-sponsored national program on hydrogen production from water via thermochemical cycles

NASA Technical Reports Server (NTRS)

Baker, C. E.

1977-01-01

A pure thermochemical cycle is a system of linked regenerative chemical reactions which accepts only water and heat and produces hydrogen. Thermochemical cycles are potentially a more efficient and cheaper means of producing hydrogen from water than is the generation of electricity followed by electrolysis. The Energy Storage Systems Division of the Department of Energy is currently funding a national program on thermochemical hydrogen production. The National Aeronautics and Space Administration is responsible for the technical management of this program. The goal is to develop a cycle which can potentially operate with an efficiency greater than 40% using a heat source providing a maximum available temperature of 1150 K. A closed bench-scale demonstration of such a cycle would follow. This cycle would be labeled a 'reference cycle' and would serve as a baseline against which future cycles would be compared.

Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems.

DTIC Science & Technology

1986-01-15

has been found in a O/W microemulsion containing sodium lauryl sulfate , cyclohexane, n-butanol and water. SHORT TERM PROJECTS New O/W and W/O...microemulsion containing lauryl acid sodium salt, cyclohexane, n-butanol and water towards hydrogen peroxide has been tested. Kinetic measurements...using hydrogen peroxide The system lauryl acid sodium salt, cyclohexane, n-butanol, water has been selected as one of those potentially compatible

Hydrogen generation through static-feed water electrolysis

NASA Technical Reports Server (NTRS)

Jensen, F. C.; Schubert, F. H.

1975-01-01

A static-feed water electrolysis system (SFWES), developed under NASA sponsorship, is presented for potential applicability to terrestrial hydrogen production. The SFWES concept uses (1) an alkaline electrolyte to minimize power requirements and materials-compatibility problems, (2) a method where the electrolyte is retained in a thin porous matrix eliminating bulk electrolyte, and (3) a static water-feed mechanism to prevent electrode and electrolyte contamination and to promote system simplicity.

An analysis of hydrogen production via closed-cycle schemes. [thermochemical processings from water

NASA Technical Reports Server (NTRS)

Chao, R. E.; Cox, K. E.

1975-01-01

A thermodynamic analysis and state-of-the-art review of three basic schemes for production of hydrogen from water: electrolysis, thermal water-splitting, and multi-step thermochemical closed cycles is presented. Criteria for work-saving thermochemical closed-cycle processes are established, and several schemes are reviewed in light of such criteria. An economic analysis is also presented in the context of energy costs.

Effects of protein conformational flexibilities and electrostatic interactions on the low-frequency vibrational spectrum of hydration water.

PubMed

Pal, Somedatta; Bandyopadhyay, Sanjoy

2013-05-16

The conformational flexibility of a protein and its ability to form hydrogen bonds with water are expected to influence the microscopic properties of water layer hydrating the protein. Detailed molecular dynamics simulations with an aqueous solution of the globular protein barstar have been carried out to explore such influence on the low-frequency vibrational spectrum of the hydration water molecules. The calculations reveal that enhanced degree of confinement at the protein surface on freezing its local motions leads to increasingly restricted oscillatory motions of the hydration water molecules as evident from larger blue shifts of the corresponding band. Interestingly, conformational fluctuations of the protein and electrostatic component of its interaction with the solvent have been found to affect the transverse and longitudinal oscillations of hydration water molecules in a nonuniform manner. It is further noticed that the distributions of the low-frequency modes for the water molecules hydrogen bonded to the residues of different segments of the protein are heterogeneously altered. The effect is more around the frozen protein matrix and agrees well with slower protein-water hydrogen bond relaxations.

Use of triphenyl phosphate as risk mitigant for metal amide hydrogen storage materials

DOEpatents

Cortes-Concepcion, Jose A.; Anton, Donald L.

2016-04-26

A process in a resulting product of the process in which a hydrogen storage metal amide is modified by a ball milling process using an additive of TPP. The resulting product provides for a hydrogen storage metal amide having a coating that renders the hydrogen storage metal amide resistant to air, ambient moisture, and liquid water while improving useful hydrogen storage and release kinetics.

A high stability Ni-La0.5Ce0.5O2-δ asymmetrical metal-ceramic membrane for hydrogen separation and generation

NASA Astrophysics Data System (ADS)

Zhu, Zhiwen; Sun, Wenping; Wang, Zhongtao; Cao, Jiafeng; Dong, Yingchao; Liu, Wei

2015-05-01

In this work, hydrogen permeation properties of Ni-La0.5Ce0.5O2-δ (LDC) asymmetrical cermet membrane are investigated, including hydrogen fluxes (JH2) under different hydrogen partial pressures, the influence of water vapor on JH2 and the long-term stability of the membrane operating under the containing-CO2 atmosphere. Ni-LDC asymmetrical membrane shows the best hydrogen permeability among LDC-based hydrogen separation membranes, inferior to Ni-BaZr0.1Ce0.7Y0.2O3-δ asymmetrical membrane. The water vapor in feed gas is beneficial to hydrogen transport process, which promote an increase of JH2 from 5.64 × 10-8 to 6.83 × 10-8 mol cm-2 s-1 at 900 °C. Stability testing of hydrogen permeation suggests that Ni-LDC membrane remains stable against CO2. A dual function of combining hydrogen separation and generation can be realized by humidifying the sweep gas and enhance the hydrogen output by 1.0-1.5 times. Ni-LDC membrane exhibits desirable performance and durability in dual-function mode. Morphologies and phase structures of the membrane after tests are also characterized by SEM and XRD.

Free energy of adhesion of lipid bilayers on silica surfaces

NASA Astrophysics Data System (ADS)

Schneemilch, M.; Quirke, N.

2018-05-01

The free energy of adhesion per unit area (hereafter referred to as the adhesion strength) of lipid arrays on surfaces is a key parameter that determines the nature of the interaction between materials and biological systems. Here we report classical molecular simulations of water and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers at model silica surfaces with a range of silanol densities and structures. We employ a novel technique that enables us to estimate the adhesion strength of supported lipid bilayers in the presence of water. We find that silanols on the silica surface form hydrogen bonds with water molecules and that the water immersion enthalpy for all surfaces varies linearly with the surface density of these hydrogen bonds. The adhesion strength of lipid bilayers is a linear function of the surface density of hydrogen bonds formed between silanols and the lipid molecules on crystalline surfaces. Approximately 20% of isolated silanols form such bonds but more than 99% of mutually interacting geminal silanols do not engage in hydrogen bonding with water. On amorphous silica, the bilayer displays much stronger adhesion than expected from the crystalline surface data. We discuss the implications of these results for nanoparticle toxicity.

Molecular metal-Oxo catalysts for generating hydrogen from water

DOEpatents

Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

2015-02-24

A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

Method for low temperature catalytic production of hydrogen

DOEpatents

Mahajan, Devinder

2003-07-22

The invention provides a process for the catalytic production of a hydrogen feed by exposing a hydrogen feed to a catalyst which promotes a base-catalyzed water-gas-shift reaction in a liquid phase. The hydrogen feed can be provided by any process known in the art of making hydrogen gas. It is preferably provided by a process that can produce a hydrogen feed for use in proton exchange membrane fuel cells. The step of exposing the hydrogen feed takes place preferably from about 80.degree. C. to about 150.degree. C.

Hydrogen Isotopes in Amino Acids and Soils Offer New Potential to Study Complex Processes

NASA Astrophysics Data System (ADS)

Fogel, M. L.; Newsome, S. D.; Williams, E. K.; Bradley, C. J.; Griffin, P.; Nakamoto, B. J.

2016-12-01

Hydrogen isotopes have been analyzed extensively in the earth and biogeosciences to trace water through various environmental systems. The majority of the measurements have been made on water in rocks and minerals (inorganic) or non-exchangeable H in lipids (organic), important biomarkers that represent a small fraction of the organic molecules synthesized by living organisms. Our lab has been investigating hydrogen isotopes in amino acids and complex soil organic matter, which have traditionally been thought to be too complex to interpret owing to complications from potentially exchangeable hydrogen. For the amino acids, we show how hydrogen in amino acids originates from two sources, food and water, and demonstrate that hydrogen isotopes can be routed directly between organisms. Amino acid hydrogen isotopes may unravel cycling in extremophiles in order to discover novel biochemical pathways central to the organism. For soil organic matter, recent approaches to understanding the origin of soil organic matter are pointing towards root exudates along with microbial biomass as the source, rather than aboveground leaf litter. Having an isotope tracer in very complex, potentially exchangeable organic matter can be handled with careful experimentation. Although no new instrumentation is being used per se, extension of classes of organic matter to isotope measurements has potential to open up new doors for understanding organic matter cycling on earth and in planetary materials.

Photocatalytic hydrogen production of the CdS/TiO2-WO3 ternary hybrid under visible light irradiation.

PubMed

Chen, Yi-Lin; Lo, Shang-Lien; Chang, Hsiang-Ling; Yeh, Hsiao-Mei; Sun, Liping; Oiu, Chunsheng

2016-01-01

An attractive and effective method for converting solar energy into clean and renewable hydrogen energy is photocatalytic water splitting over semiconductors. The study aimed at utilizing organic sacrificial agents in water, modeled by formic acid, in combination with visible light driven photocatalysts to produce hydrogen with high efficiencies. The photocatalytic hydrogen production of cadmium sulfide (CdS)/titanate nanotubes (TNTs) binary hybrid with specific CdS content was investigated. After visible light irradiation for 3 h, the hydrogen production rate of 25 wt% CdS/TNT achieved 179.35 μmol·h(-1). Thanks to the two-step process, CdS/TNTs-WO3 ternary hybrid can better promote the efficiency of water splitting compared with CdS/TNTs binary hybrid. The hydrogen production of 25 wt% CdS/TNTs-WO3 achieved 212.68 μmol·h(-1), under the same condition. Coating of platinum metal onto the WO3 could further promote the reaction. Results showed that 0.2 g 0.1 wt% Pt/WO3 + 0.2 g 25 wt% CdS/TNTs had the best hydrogen production rate of 428.43 μmol·h(-1). The resultant materials were well characterized by high-resolution transmission electron microscope, X-ray diffraction, scanning electron microscopy, and UV-Vis spectra.

Hydrogen incorporation by plasma treatment gives mesoporous black TiO 2 thin films with visible photoelectrochemical water oxidation activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Islam, Syed Z.; Reed, Allen; Nagpure, Suraj

In this work, we use neutron reflectometry (NR) to investigate the roles of hydrogen in plasma treated hydrogen doped mesoporous black titania thin films in their visible light absorption and enhanced photoactivity for water oxidation. The cubic ordered mesoporous TiO 2 thin films are prepared by a surfactant-templated sol-gel method and are treated with hydrogen plasma, an approach hypothesized to capitalize on the high degree of disorder in the material and the high energy of the plasma species to achieve efficient hydrogen doping. UV-vis absorbance spectra indicate that H 2 plasma treatment makes TiO 2 films black, with broad-spectrum enhancementmore » of visible light absorption, and XPS analysis shows peak for Ti 3+ state in treated films. The presence of hydrogen in black mesoporous titania (H-TiO 2) films is confirmed by the scattering length density (SLD) profiles obtained from neutron reflectometry measurements. The H-TiO 2 shows ca. 28 times and 8 times higher photocurrent for photoelectrochemical water oxidation compared to undoped TiO 2 films under UV (365 nm) and blue (455 nm) LED irradiation, respectively. These findings provide the first direct evidence that the dramatic change in visible light absorbance of H-treated black TiO 2 is accompanied by significant hydrogen uptake and not just Ti 3+ generation or surface disordering.« less

Hydrogen incorporation by plasma treatment gives mesoporous black TiO 2 thin films with visible photoelectrochemical water oxidation activity

DOE PAGES

Islam, Syed Z.; Reed, Allen; Nagpure, Suraj; ...

2017-10-26

In this work, we use neutron reflectometry (NR) to investigate the roles of hydrogen in plasma treated hydrogen doped mesoporous black titania thin films in their visible light absorption and enhanced photoactivity for water oxidation. The cubic ordered mesoporous TiO 2 thin films are prepared by a surfactant-templated sol-gel method and are treated with hydrogen plasma, an approach hypothesized to capitalize on the high degree of disorder in the material and the high energy of the plasma species to achieve efficient hydrogen doping. UV-vis absorbance spectra indicate that H 2 plasma treatment makes TiO 2 films black, with broad-spectrum enhancementmore » of visible light absorption, and XPS analysis shows peak for Ti 3+ state in treated films. The presence of hydrogen in black mesoporous titania (H-TiO 2) films is confirmed by the scattering length density (SLD) profiles obtained from neutron reflectometry measurements. The H-TiO 2 shows ca. 28 times and 8 times higher photocurrent for photoelectrochemical water oxidation compared to undoped TiO 2 films under UV (365 nm) and blue (455 nm) LED irradiation, respectively. These findings provide the first direct evidence that the dramatic change in visible light absorbance of H-treated black TiO 2 is accompanied by significant hydrogen uptake and not just Ti 3+ generation or surface disordering.« less

Hydrogen incorporation by plasma treatment gives mesoporous black TiO 2 thin films with visible photoelectrochemical water oxidation activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Islam, Syed Z.; Reed, Allen; Nagpure, Suraj

2018-05-01

In this work, we use neutron reflectometry (NR) to investigate the roles of hydrogen in plasma treated hydrogen doped mesoporous black titania thin films in their visible light absorption and enhanced photoactivity for water oxidation. The cubic ordered mesoporous TiO2 thin films are prepared by a surfactant-templated sol-gel method and are treated with hydrogen plasma, an approach hypothesized to capitalize on the high degree of disorder in the material and the high energy of the plasma species to achieve efficient hydrogen doping. UV-vis absorbance spectra indicate that H2 plasma treatment makes TiO2 films black, with broad-spectrum enhancement of visible lightmore » absorption, and XPS analysis shows peak for Ti3+ state in treated films. The presence of hydrogen in black mesoporous titania (H-TiO2) films is confirmed by the scattering length density (SLD) profiles obtained from neutron reflectometry measurements. The H-TiO2 shows ca. 28 times and 8 times higher photocurrent for photoelectrochemical water oxidation compared to undoped TiO2 films under UV (365 nm) and blue (455 nm) LED irradiation, respectively. These findings provide the first direct evidence that the dramatic change in visible light absorbance of H-treated black TiO2 is accompanied by significant hydrogen uptake and not just Ti3+ generation or surface disordering.« less

Particulate Photocatalyst Sheets Based on Carbon Conductor Layer for Efficient Z-Scheme Pure-Water Splitting at Ambient Pressure.

PubMed

Wang, Qian; Hisatomi, Takashi; Suzuki, Yohichi; Pan, Zhenhua; Seo, Jeongsuk; Katayama, Masao; Minegishi, Tsutomu; Nishiyama, Hiroshi; Takata, Tsuyoshi; Seki, Kazuhiko; Kudo, Akihiko; Yamada, Taro; Domen, Kazunari

2017-02-01

Development of sunlight-driven water splitting systems with high efficiency, scalability, and cost-competitiveness is a central issue for mass production of solar hydrogen as a renewable and storable energy carrier. Photocatalyst sheets comprising a particulate hydrogen evolution photocatalyst (HEP) and an oxygen evolution photocatalyst (OEP) embedded in a conductive thin film can realize efficient and scalable solar hydrogen production using Z-scheme water splitting. However, the use of expensive precious metal thin films that also promote reverse reactions is a major obstacle to developing a cost-effective process at ambient pressure. In this study, we present a standalone particulate photocatalyst sheet based on an earth-abundant, relatively inert, and conductive carbon film for efficient Z-scheme water splitting at ambient pressure. A SrTiO 3 :La,Rh/C/BiVO 4 :Mo sheet is shown to achieve unassisted pure-water (pH 6.8) splitting with a solar-to-hydrogen energy conversion efficiency (STH) of 1.2% at 331 K and 10 kPa, while retaining 80% of this efficiency at 91 kPa. The STH value of 1.0% is the highest among Z-scheme pure water splitting operating at ambient pressure. The working mechanism of the photocatalyst sheet is discussed on the basis of band diagram simulation. In addition, the photocatalyst sheet split pure water more efficiently than conventional powder suspension systems and photoelectrochemical parallel cells because H + and OH - concentration overpotentials and an IR drop between the HEP and OEP were effectively suppressed. The proposed carbon-based photocatalyst sheet, which can be used at ambient pressure, is an important alternative to (photo)electrochemical systems for practical solar hydrogen production.

Efficacy of Various Chemical Disinfectants on Biofilms Formed in Spacecraft Potable Water System Component

NASA Technical Reports Server (NTRS)

Wong, Willy; Garcia, Veronica; Castro, Victoria; Ott, Mark; Duane

2009-01-01

As the provision of potable water is critical for successful habitation of the International Space Station (ISS), life support systems were installed in December 2008 to recycle both humidity from the atmosphere and urine to conserve available water in the vehicle. Pre-consumption testing from the dispensing needle at the Potable Water Dispenser (PWD) indicated that bacterial concentrations exceeded the current ISS specifications of 50 colony forming units (CFU) per ml. Subsequent investigations revealed that a corrugated stainless steel flex hose upstream of the dispensing needle in the PWD was filled with non-sterile water and left at room temperature for over one month before launch. To simulate biofilm formation that was suspected in the flight system, sterile flex hoses were seeded with a consortium of bacterial isolates previously recovered from other ISS water systems, which included Ralstonia pickettii, Burkholderia multivorans, Caulobacter vibrioides., and Cupriavidus pauculus. After 5 days of incubation, these hoses were challenged with various chemical disinfectants including hydrogen peroxide, colloidal silver, and buffered pH solutions to determine the ability of the disinfectants to decrease and maintain bacterial concentrations below ISS specifications. Disinfection efficacy over time was measured by collecting daily heterotrophic plate counts following exposure to the disinfectants. A single flush with either 6% hydrogen peroxide solution or a mixture of 3% hydrogen peroxide and 400 ppb colloidal silver effectively reduced the bacterial concentrations to less than 1 CFU/ml for a period of up to 2 months. Testing results indicated that hydrogen peroxide and mixtures of hydrogen peroxide and colloidal silver have tremendous potential as alternative disinfectants for ISS water systems.

Determining the Energetics of the Hydrogen Bond through FTIR: A Hands-On Physical Chemistry Lab Experiment

ERIC Educational Resources Information Center

Guerin, Abby C.; Riley, Kristi; Rupnik, Kresimir; Kuroda, Daniel G.

2016-01-01

Hydrogen bonds are very important chemical structures that are responsible for many unique and important properties of solvents, such as the solvation power of water. These distinctive features are directly related to the stabilization energy conferred by hydrogen bonds to the solvent. Thus, the characterization of hydrogen bond energetics has…

Chemistry of neutral species in the effluent of the micro atmospheric pressure plasma jet in water-helium admixture

NASA Astrophysics Data System (ADS)

Willems, Gert; Benedikt, Jan; von Keudell, Achim

2016-09-01

A thorough understanding and good control of produced neutral and charged species by cold atmospheric plasmas is essential for potential environmental and/or bio-medical applications. In this study we use the COST reference micro plasma jet (µ-APPJ), which is a radio-frequency capacitive coupled plasma source with 1 mm electrode distance, which has been operated in helium-water vapour mixture and has been studied as a potential source of hydroxyl radicals and hydrogen peroxide molecules. The water vapour concentration was up to 1.2%. Molecular Beam mass spectrometry is used as diagnostic tool. An absolute calibration of hydrogen peroxide was conducted using a double bubbler concept, because the ionization cross section for hydrogen peroxide is not available. Additionally the effluent chemistry was investigated by use of a 0D and 2D model. Absolute densities of hydrogen peroxide and hydroxyl radicals from atmospheric plasma will be presented. Their dependency on water vapour concentration in the carrier gas as well as distance to target have been investigated. The measured density is between 5E-13 cm-3 (2.4ppm) and 1.5E-14 cm-3 (7.2ppm) for both hydrogen peroxide molecules and hydroxyl radicals. The achieved results are in good agreement with other experiments.

Structure of hydrated calcium carbonates: A first-principles study

NASA Astrophysics Data System (ADS)

Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D.

2014-09-01

The structures of both ikaite (CaCO3 · 6H2 O) and monohydrocalcite (CaCO3 ·H2 O) were computed at the PBE0 level of theory, using all electron Gaussian type basis sets. Correction for the long-range dispersion contribution was included for the oxygen-oxygen interactions by using an additive pairwise term with the atomic coefficients fitted against the calcite vs aragonite enthalpy difference. The potential chirality of monohydrocalcite is discussed, as well as the helical motifs created by the three-fold rototranslational axes parallel to the [001] direction. These elements represent a significant link between monohydrocalcite and vaterite, both appearing as intermediate species during CaCO3 crystallization from amorphous calcium carbonate. The hydrogen bond pattern, never fully discussed for monohydrocalcite, is here described and compared to the available experimental data. Both phases are characterized by the presence of hydrogen bonds of moderate to high strength. Water molecules in monohydrocalcite interact quite strongly with 2 CO32- units through such hydrogen bonds, whereas their interaction with each other is minor. On the contrary, water molecules in ikaite create a complex network of hydrogen bonds, where each water molecule is strongly hydrogen bonded to one CO32- anion and to one or two other water molecules.

Gas phase reaction of nitric acid with hydroxyl radical without and with water. A theoretical investigation.

PubMed

Gonzalez, Javier; Anglada, Josep M

2010-09-02

The gas phase reaction between nitric acid and hydroxyl radical, without and with a single water molecule, has been investigated theoretically using the DFT-B3LYP, MP2, QCISD, and CCSD(T) theoretical approaches with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction without water begins with the formation of a prereactive hydrogen-bonded complex and has several elementary reactions processes. They include proton coupled electron transfer, hydrogen atom transfer, and proton transfer mechanisms, and our kinetic study shows a quite good agreement of the behavior of the rate constant with respect to the temperature and to the pressure with the experimental results from the literature. The addition of a single water molecule results in a much more complex potential energy surface although the different elementary reactions found have the same electronic features that the naked reaction. Two transition states are stabilized by the effect of a hydrogen bond interaction originated by the water molecule, and in the prereactive hydrogen bond region there is a geometrical rearrangement necessary to prepare the HO and HNO(3) moieties to react to each other. This step contributes the reaction to be slower than the reaction without water and explains the experimental finding, pointing out that there is no dependence for the HNO(3) + HO reaction on water vapor.

Infrared signature of micro-hydration in the organophosphate sarin: An ab initio study

DOE PAGES

Alam, Todd M.; Pearce, Charles Joseph

2015-06-28

The infrared (IR) spectra of micro-hydrated Sarin•(H 2O) n clusters containing between one and four explicit waters have been studied using ab initio density functional theory (DFT) methods. The phosphate group P=O bond vibration region (~1270 to 1290 cm –1) revealed the largest frequency variation with hydration, with a frequency red shift reflecting the direct hydrogen bond formation between the P=O of Sarin and water. Small variations to the P-F stretch (~810 to 815 cm –1) and the C-O-P vibrational modes (~995 to 1004 cm –1) showed that the water interactions with these functional groups were minor, and that themore » structures of Sarin were not extensively perturbed in the hydrated complexes. Increasing the number of explicit hydration waters produced only small vibrational changes in the lowest free energy complexes. These minor changes were consistent with a single water-phosphate hydrogen bond being the dominant structure, though a second water-phosphate hydrogen bond was observed in some complexes and was identified by an additional red shift of the P=O bond vibration. As a result, the H 2O•H 2O vibrational modes (~3450 to 3660 cm –1) increased in complexity with higher hydration levels and reflect the extended hydrogen bonding networks formed between the explicit waters in the hydrated Sarin clusters.« less

Hydrogen-bond symmetrization breakdown and dehydrogenation mechanism in FeO2H at high pressure

NASA Astrophysics Data System (ADS)

Hu, Q.; Zhu, S.; Mao, H. K.; Mao, W. L.; Sheng, H.

2017-12-01

The cycling of hydrogen plays an important role in the geochemical evolution of our planet. In Earth's interiors, hydrogen cycling is mainly carried out by hydrous minerals. Under high-pressure conditions, asymmetric hydroxyl bonds in hydrous minerals tend to form a symmetric O-H-O configuration that improves their thermal stability. Therefore it is possible to transport water into the deeper part of the Earth's lower mantle. Here, we employ first-principles free-energy landscape sampling methods based on a recently developed stochastic surface walking algorithm to reveal the transition mechanism of a water-bearing mineral, FeO2H, at deep mantle conditions. By resolving the lowest-energy transition pathway from ɛ-FeO2H to the high-pressure Py-phase, we demonstrate that half of the O-H bonds in the mineral rupture during the structural transition, leading toward the breakdown of symmetrized hydrogen bonds and eventual dehydrogenation. Our study sheds new light on the stability of symmetric hydrogen bonds in hydrous minerals during structural transitions and suggests a dehydrogenation mechanism from water in the deep mantle.

Hydrogen fuel - Universal energy

NASA Astrophysics Data System (ADS)

Prince, A. G.; Burg, J. A.

The technology for the production, storage, transmission, and consumption of hydrogen as a fuel is surveyed, with the physical and chemical properties of hydrogen examined as they affect its use as a fuel. Sources of hydrogen production are described including synthesis from coal or natural gas, biomass conversion, thermochemical decomposition of water, and electrolysis of water, of these only electrolysis is considered economicially and technologically feasible in the near future. Methods of production of the large quantities of electricity required for the electrolysis of sea water are explored: fossil fuels, hydroelectric plants, nuclear fission, solar energy, wind power, geothermal energy, tidal power, wave motion, electrochemical concentration cells, and finally ocean thermal energy conversion (OTEC). The wind power and OTEC are considered in detail as the most feasible approaches. Techniques for transmission (by railcar or pipeline), storage (as liquid in underwater or underground tanks, as granular metal hydride, or as cryogenic liquid), and consumption (in fuel cells in conventional power plants, for home usage, for industrial furnaces, and for cars and aircraft) are analyzed. The safety problems of hydrogen as a universal fuel are discussed, noting that they are no greater than those for conventional fuels.

Hydrogen generation from deliquescence of ammonia borane using Ni-Co/r-GO catalyst

NASA Astrophysics Data System (ADS)

Chou, Chang-Chen; Chen, Bing-Hung

2015-10-01

Hydrogen generation from the catalyzed deliquescence/hydrolysis of ammonia borane (AB) using the Ni-Co catalyst supported on the graphene oxide (Ni-Co/r-GO catalyst) under the conditions of limited water supply was studied with the molar feed ratio of water to ammonia borane (denoted as H2O/AB) at 2.02, 3.97 and 5.93, respectively. The conversion efficiency of ammonia borane to hydrogen was estimated both from the cumulative volume of the hydrogen gas generated and the conversion of boron chemistry in the hydrolysates analyzed by the solid-state 11B NMR. The conversion efficiency of ammonia borane could reach nearly 100% under excess water dosage, that is, H2O/AB = 3.97 and 5.93. Notably, the hydrogen storage capacity could reach as high as 6.5 wt.% in the case with H2O/AB = 2.02. The hydrolysates of ammonia borane in the presence of Ni-Co/r-GO catalyst were mainly the mixture of boric acid and metaborate according to XRD, FT-IR and solid-state 11B NMR analyses.

Feasibility of the Hydrogen Sulfide Test for the Assessment of Drinking Water Quality in Post-Earthquake Haiti

PubMed Central

Weppelmann, Thomas A.; Alam, Meer T.; Widmer, Jocelyn; Morrissey, David; Rashid, Mohammed H.; Beau De Rochars, Valery M.; Morris, J. Glenn; Ali, Afsar; Johnson, Judith A.

2014-01-01

In 2010 a magnitude 7.0 earthquake struck Haiti, severely damaging the drinking and waste water infrastructure and leaving millions homeless. Compounding this problem, the introduction of Vibrio cholera resulted in a massive cholera outbreak that infected over 700,000 people and threatened the safety of Haiti’s drinking water. To mitigate this public health crisis, non-government organizations installed thousands of wells to provide communities with safe drinking water. However, despite increased access, Haiti currently lacks the monitoring capacity to assure the microbial safety of any of its water resources. For these reasons, this study was designed to assess the feasibility of using a simple, low cost method to detect indicators of fecal contamination of drinking water that could be implemented at the community level. Water samples from 358 sources of drinking water in the Léogâne flood basin were screened with a commercially available hydrogen sulfide test and a standard membrane method for the enumeration of thermotolerant coliforms. When compared with the gold standard method, the hydrogen sulfide test had a sensitivity of 65% and a specificity of 93%. While the sensitivity of the assay increased at higher fecal coliform concentrations, it never exceeded 88%, even with fecal coliform concentrations greater than 100 colony forming units per 100 milliliters. While its simplicity makes the hydrogen sulfide test attractive for assessing water quality in low resource settings, the low sensitivity raises concerns about its use as the sole indicator of the presence or absence of fecal coliforms in individual or community water sources. PMID:25182685

An advanced carbon reactor subsystem for carbon dioxide reduction

NASA Technical Reports Server (NTRS)

Noyes, Gary P.; Cusick, Robert J.

1986-01-01

An evaluation is presented of the development status of an advanced carbon-reactor subsystem (ACRS) for the production of water and dense, solid carbon from CO2 and hydrogen, as required in physiochemical air revitalization systems for long-duration manned space missions. The ACRS consists of a Sabatier Methanation Reactor (SMR) that reduces CO2 with hydrogen to form methane and water, a gas-liquid separator to remove product water from the methane, and a Carbon Formation Reactor (CFR) to pyrolize methane to carbon and hydrogen; the carbon is recycled to the SMR, while the produce carbon is periodically removed from the CFR. A preprototype ACRS under development for the NASA Space Station is described.

Ambient pressure fuel cell system

DOEpatents

Wilson, Mahlon S.

2000-01-01

An ambient pressure fuel cell system is provided with a fuel cell stack formed from a plurality of fuel cells having membrane/electrode assemblies (MEAs) that are hydrated with liquid water and bipolar plates with anode and cathode sides for distributing hydrogen fuel gas and water to a first side of each one of the MEAs and air with reactant oxygen gas to a second side of each one of the MEAs. A pump supplies liquid water to the fuel cells. A recirculating system may be used to return unused hydrogen fuel gas to the stack. A near-ambient pressure blower blows air through the fuel cell stack in excess of reaction stoichiometric amounts to react with the hydrogen fuel gas.

Research Update: Photoelectrochemical water splitting and photocatalytic hydrogen production using ferrites (MFe{sub 2}O{sub 4}) under visible light irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dillert, Ralf; Laboratorium für Nano- und Quantenengineering, Gottfried Wilhelm Leibniz Universität Hannover, Schneiderberg 39, 30167 Hannover; Taffa, Dereje H.

2015-10-01

The utilization of solar light for the photoelectrochemical and photocatalytic production of molecular hydrogen from water is a scientific and technical challenge. Semiconductors with suitable properties to promote solar-driven water splitting are a desideratum. A hitherto rarely investigated group of semiconductors are ferrites with the empirical formula MFe{sub 2}O{sub 4} and related compounds. This contribution summarizes the published results of the experimental investigations on the photoelectrochemical and photocatalytic properties of these compounds. It will be shown that the potential of this group of compounds in regard to the production of solar hydrogen has not been fully explored yet.

Energy and Water Management

NASA Technical Reports Server (NTRS)

Valek, Susan E.

2008-01-01

Energy efficiency isn't just a good idea; it's a necessity, both for cost reasons and to meet federal regulatory requirements. First, rising energy unit costs continue to erode NASA's mission budget. NASA spent roughly $156M on facility energy in FY 2007. Although that represents less than one per cent of NASA's overall annual budget, the upward trend in energy costs concerns the agency. While NASA reduced consumption 13%, energy unit costs have risen 63%. Energy cost increases counteract the effects of energy conservation, which results in NASA buying less yet spending more. The second factor is federal energy legislation. The National Energy Conservation Policy Act, as amended by the Energy Policy Act of 2005, Executive Order (EO) 13423 (January, 2007), and the Energy Independence and Security Act (December, 2007), mandates energy/water conservation goals for all federal agencies, including NASA. There are also reporting requirements associated with this legislation. The Energy/Water Management Task was created to support NASA Headquarters Environmental Management Division (HO EMD) in meeting these requirements. With assistance from TEERM, HQ EMD compiled and submitted the NASA Annual Report to the Department of Energy FY 2007. The report contains information on how NASA is meeting federally mandated energy and water management goals. TEERM monitored input for timeliness, errors, and conformity to the new energy/water reporting guidelines and helped compile the information into the final report. TEERM also assists NASA Energy/Water Management with proposal and award calls, updates to the energy/water management database, and facilitating communication within the energy/water management community. TEERM is also supporting NASA and the Interagency Working Group (IWG) on Hydrogen and Fuel Cells. Established shortly after the President announced the Hydrogen Fuel Initiative in 2003, this IWG serves as the mechanism for collaboration among the Federal agencies involved in hydrogen-related research, development, and demonstration. TEERM developed a matrix showing all Hydrogen and Fuel Cell activities from the various NASA centers to be included in the Group's extensive hydrogen research taxonomy of past, present, and future hydrogen activities of the Federal government.

Conformational stability of the propylene oxide-water adduct: direct spectroscopic detection of O-H...O hydrogen bonded conformers.

PubMed

Su, Zheng; Wen, Qing; Xu, Yunjie

2006-05-24

The 1:1 molecular adduct of propylene oxide and water (PO-H(2)O) was studied using Fourier transform microwave spectroscopy and high level ab initio methods. Two distinct structural conformers with the water molecule acting as a proton donor were detected experimentally: one with the water on the same side as the methyl group with respect to the ether ring, i.e., syn-PO-H(2)O, the other with the water molecule binding to the O-atom from the opposite side of the methyl group, i.e., anti-PO-H(2)O. The nonbonded hydrogen is entgegen to the ether ring in both conformers. Rotational spectra of four isotopic species, namely PO-H(2)O, PO-DOH, PO-HOD, and PO-D(2)O, were recorded for the two conformers. The hydrogen bond parameters: r(O(epoxy)...H), angle(ring-O(epoxy)...H), and angle(O(epoxy)...H-O) are 1.908 A, 112 degrees, and 177 degrees for syn-PO-H(2)O, and 1.885 A, 104.3 degrees, and 161.7 degrees for anti-PO-H(2)O, respectively. The experimental results suggest that the hydrogen bond in syn-PO-H(2)O is stronger and the monomer subunits are more rigidly locked in their positions than in the ethylene oxide-water adduct. The stabilizing effect of the methyl group to the intermolecular hydrogen bond is discussed in terms of the experimentally estimated binding energies, the structural parameters, and the ab initio calculations.

Vapor-fed microfluidic hydrogen generator.

PubMed

Modestino, M A; Dumortier, M; Hosseini Hashemi, S M; Haussener, S; Moser, C; Psaltis, D

2015-05-21

Water-splitting devices that operate with humid air feeds are an attractive alternative for hydrogen production as the required water input can be obtained directly from ambient air. This article presents a novel proof-of-concept microfluidic platform that makes use of polymeric ion conductor (Nafion®) thin films to absorb water from air and performs the electrochemical water-splitting process. Modelling and experimental tools are used to demonstrate that these microstructured devices can achieve the delicate balance between water, gas, and ionic transport processes required for vapor-fed devices to operate continuously and at steady state, at current densities above 3 mA cm(-2). The results presented here show that factors such as the thickness of the Nafion films covering the electrodes, convection of air streams, and water content of the ionomer can significantly affect the device performance. The insights presented in this work provide important guidelines for the material requirements and device designs that can be used to create practical electrochemical hydrogen generators that work directly under ambient air.

Decoupling Hydrogen and Oxygen Production in Acidic Water Electrolysis Using a Polytriphenylamine-Based Battery Electrode.

PubMed

Ma, Yuanyuan; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

2018-03-05

Hydrogen production through water splitting is considered a promising approach for solar energy harvesting. However, the variable and intermittent nature of solar energy and the co-production of H 2 and O 2 significantly reduce the flexibility of this approach, increasing the costs of its use in practical applications. Herein, using the reversible n-type doping/de-doping reaction of the solid-state polytriphenylamine-based battery electrode, we decouple the H 2 and O 2 production in acid water electrolysis. In this architecture, the H 2 and O 2 production occur at different times, which eliminates the issue of gas mixing and adapts to the variable and intermittent nature of solar energy, facilitating the conversion of solar energy to hydrogen (STH). Furthermore, for the first time, we demonstrate a membrane-free solar water splitting through commercial photovoltaics and the decoupled acid water electrolysis, which potentially paves the way for a new approach for solar water splitting. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical, electrochemical and photochemical molecular water oxidation catalysts.

PubMed

Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Sala, Xavier

2015-11-01

Hydrogen release from the splitting of water by simply using sunlight as the only energy source is an old human dream that could finally become a reality. This process involves both the reduction and oxidation of water into hydrogen and oxygen, respectively. While the first process has been fairly overcome, the conversion of water into oxygen has been traditionally the bottleneck process hampering the development of a sustainable hydrogen production based on water splitting. Fortunately, a revolution in this field has occurred during the past decade, since many research groups have been conducting an intense research in this area. Thus, while molecular, well-characterized catalysts able to oxidize water were scarce just five years ago, now a wide range of transition metal based compounds has been reported as active catalysts for this transformation. This review reports the most prominent key advances in the field, covering either examples where the catalysis is triggered chemically, electrochemically or photochemically. Copyright © 2014 Elsevier B.V. All rights reserved.

Sulfur mass-independent fractionation in subsurface fracture waters indicates a long-standing sulfur cycle in Precambrian rocks

PubMed Central

Li, L.; Wing, B. A.; Bui, T. H.; McDermott, J. M.; Slater, G. F.; Wei, S.; Lacrampe-Couloume, G.; Lollar, B. Sherwood

2016-01-01

The discovery of hydrogen-rich waters preserved below the Earth's surface in Precambrian rocks worldwide expands our understanding of the habitability of the terrestrial subsurface. Many deep microbial ecosystems in these waters survive by coupling hydrogen oxidation to sulfate reduction. Hydrogen originates from water–rock reactions including serpentinization and radiolytic decomposition of water induced by decay of radioactive elements in the host rocks. The origin of dissolved sulfate, however, remains unknown. Here we report, from anoxic saline fracture waters ∼2.4 km below surface in the Canadian Shield, a sulfur mass-independent fractionation signal in dissolved sulfate. We demonstrate that this sulfate most likely originates from oxidation of sulfide minerals in the Archaean host rocks through the action of dissolved oxidants (for example, HO· and H2O2) themselves derived from radiolysis of water, thereby providing a coherent long-term mechanism capable of supplying both an essential electron donor (H2) and a complementary acceptor (sulfate) for the deep biosphere. PMID:27807346

Water Splitting via Decoupled Photocatalytic Water Oxidation and Electrochemical Proton Reduction Mediated by Electron-Coupled-Proton Buffer.

PubMed

Li, Fei; Yu, Fengshou; Du, Jian; Wang, Yong; Zhu, Yong; Li, Xiaona; Sun, Licheng

2017-10-18

Water splitting mediated by electron-coupled-proton buffer (ECPB) provides an efficient way to avoid gas mixing by separating oxygen evolution from hydrogen evolution in space and time. Though electrochemical and photoelectrochemcial water oxidation have been incorporated in such a two-step water splitting system, alternative ways to reduce the cost and energy input for decoupling two half-reactions are desired. Herein, we show the feasibility of photocatalytic oxygen evolution in a powder system with BiVO 4 as a photocatalyst and polyoxometalate H 3 PMo 12 O 40 as an electron and proton acceptor. The resulting reaction mixture was allowed to be directly used for the subsequent hydrogen evolution with the reduced H 3 PMo 12 O 40 as electron and proton donors. Our system exhibits excellent stability in repeated oxygen and hydrogen evolution, which brings considerable convenience to decoupled water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen

PubMed Central

Bockris, John O’M.

2011-01-01

The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan). Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs) by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech. PMID:28824125

A heterogeneous lunar interior for hydrogen isotopes as revealed by the lunar highlands samples

NASA Astrophysics Data System (ADS)

Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Flemming, Roberta L.; Rossman, George R.; Eiler, John M.; Neal, Clive R.; Osinski, Gordon R.

2017-09-01

Knowing the amount and timing of water incorporation into the Moon has fundamental implications for our understanding of how the Earth-Moon system formed. Water has been detected in lunar samples but its abundance, distribution and origin are debated. To address these issues, we report water concentrations and hydrogen isotope ratios obtained by secondary ion mass spectrometry (SIMS) of plagioclase from ferroan anorthosites (FANs), the only available lithology thought to have crystallized directly from the lunar magma ocean (LMO). The measured water contents are consistent with previous results by Fourier transform infrared spectroscopy (FTIR). Combined with literature data, δD values of lunar igneous materials least-degassed at the time of their crystallization range from -280 to + 310 ‰, the latter value being that of FAN 60015 corrected for cosmic ray exposure. We interpret these results as hydrogen isotopes being fractionated during degassing of molecular hydrogen (H2) in the LMO, starting with the magmatic δD value of primordial water at the beginning of LMO being about - 280 ‰, evolving to about + 310 ‰ at the time of anorthite crystallization, i.e. during the formation of the primary lunar crust. The degassing of hydrogen in the LMO is consistent with those of other volatile elements. The wide range of δD values observed in lunar igneous rocks could be due to either various degrees of mixing of the different mantle end members, or from a range of mantle sources that were degassed to different degrees during magma evolution. Degassing of the LMO is a viable mechanism that resulted in a heterogeneous lunar interior for hydrogen isotopes.

J-2X Fuel Turbopump Point of Departure: The Performance of the J-2s Fuel Turbopump Inducer

NASA Technical Reports Server (NTRS)

Sargent, S. R.; Becht, D. G.; Mulder, A. D.

2008-01-01

To aid the J-2X program design effort with detailed performance and environment information, the J-2S fuel turbopump (FTP) inducer has undergone a thorough test series in both water and hydrogen. The test series utilizes both inducer only and a complete pump configuration to assess the inducer interaction to the overall turbopump system. The test goals include verification of suction performance against heritage J-2S data, head production, effects of thermodynamic suppression head (TSH), and evaluation of the inducer dynamic pressure caused by cavitation instabilities. Test facilities at both Pratt & Whitney Rocketdyne (PWR) and NASA s Stennis Space Center (SSC) are employed for the testing. The inducer only water test effort conducted at PWR established performance curves for suction performance, head production, and efficiency over a wide operating range. Because the heritage J-2S suction performance data set is in hydrogen, it is desired to obtain current suction performance data in hydrogen as well, thus avoiding the reliance on a theoretical TSH correlation for direct comparison. This data then provides an empirically based TSH correlation allowing for the comparison of water test suction data to system suction requirements. The FTP testing performed at SSC provides these suction performance relationships as well as inlet duct dynamic pressures during liquid hydrogen operation. The test effort successfully confirms the heritage J-2S suction performance and establishes the amount of TSH between water and hydrogen operation at the design flow coefficient. Correlating data is also obtained for cavitating instability frequency content, illustrating the validity of using the wide flow range water test data to predict hydrogen performance.

Hydrogen from renewable energy - Photovoltaic/water electrolysis as an exemplary approach

NASA Technical Reports Server (NTRS)

Sprafka, R. J.; Tison, R. R.; Escher, W. J. D.

1984-01-01

A feasibility study has been conducted for a NASA Kennedy Space Center liquid hydrogen/liquid oxygen production facility using solar cell arrays as the power source for electrolysis. The 100 MW output of the facility would be split into 67.6 and 32 MW portions for electrolysis and liquefaction, respectively. The solar cell array would cover 1.65 sq miles, and would be made up of 249 modular 400-kW arrays. Hydrogen and oxygen are generated at either dispersed or centralized water electrolyzers. The yearly hydrogen output is projected to be 5.76 million lbs, with 8 times that much oxygen; these fuel volumes can support approximately 18 Space Shuttle launches/year.