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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Surface-modified, dye-sensitized niobate nanosheets enabling an efficient solar-driven Z-scheme for overall water splitting

While dye-sensitized metal oxides are good candidates as H 2 evolution photocatalysts for solar-driven Z-scheme water splitting, their solar-to-hydrogen (STH) energy conversion efficiencies remain low because of uncontrolled charge recombination reactions. Here, we show that modification of Ru dye–sensitized, Pt-intercalated HCa 2 Nb 3 O 10 nanosheets ( Ru /Pt/HCa 2 Nb 3 O 10 ) with both amorphous Al 2 O 3 and poly(styrenesulfonate) (PSS) improves the STH efficiency of Z-scheme overall water splitting by a factor of ~100, when the nanosheets are used in combination with a WO 3 -based O 2 evolution photocatalyst and an I 3 - /I - redox mediator, relative to an analogous system that uses unmodified Ru /Pt/HCa 2 Nb 3 O 10 . By using the optimized photocatalyst, PSS/ Ru /Al 2 O 3 /Pt/HCa 2 Nb 3 O 10 , a maximum STH of 0.12% and an apparent quantum yield of 4.1% at 420 nm were obtained, by far the highest among dye-sensitized water splitting systems and comparable to conventional semiconductor-based suspended particulate photocatalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Recombination of Hydrogen in the Iodine Reactors

The H-Canyon facility is currently dissolving spent nuclear fuel, including Material Test Reactor (MTR) and High Flux Isotope Reactor (HFIR) fuel. Dissolution of aluminum spent nuclear fuel produces hydrogen and other NOx gases. A theory long held by H-Canyon Engineering and Facility Technical Advisors that the silver nitrate-coated berl saddles, present in the iodine reactor, used for off-gas treatment were acting as a catalytic hydrogen recombiner was captured during an external review of the Accelerated Basin Deinventory program. Results from a separate SRNL project using a Raman Spectrometer to monitor the offgas from the dissolution process indicated a lack of the expected hydrogen in the off-gas stream. To test this hypothesis, a laboratory scale iodine reactor was assembled and filled with silver nitrate-coated berl saddles. Testing with this laboratory scale reactor confirmed the recombination of hydrogen when a simulated dissolver off-gas was passed through the reactor containing silver nitrate-coated berl saddles at 173-188 °C. Control experiments performed with uncoated berl saddles resulted in no change to the hydrogen concentration after passing through the reactor. The residence time of the gas in the reactor was varied to determine if residence time had an impact on the amount of hydrogen recombination occurring. Results from these experiments indicated that at the shortest residence times tested (~5 seconds) recombination of the hydrogen still exceeded 90%; however, the percent recombination did increase at longer residence times, reaching 97.9% or greater for residence times over 10 seconds. Finally, testing performed with a simplified off-gas composition containing only hydrogen and air gave similar results, indicating that the presence of NO and N 2 O gases in the stream do not play a role in the recombination reaction.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1972

Laboratory CO2 photolysis studies related to planetary atmospheres

The CO(a 3II) state, the upper state of the Cameron bands, was characterized with respect to its average radiative lifetime and its quenching coefficients for a series of simple molecules. The CO2 recombination reaction (O(3P) + CO + M yields CO2 + M) was studied as a function of temperature. For M = CO, the rate constant can be expressed as k = 6.5 x 10/33 exp(-4340 plus or minus 550/RT) cm to the 6th power molec/2 sec/1, whereas the rate for M = CO2, the pertinent species in the planetary atmospheres, is 1.6 times greater. The quantum yield for CO2 photodissociation was measured in the 1200-1500 A region, using atomic line sources. The yield throughout this spectral region was much lower than that measured at 1470 A, the lowest value obtained being 8% at 1304 A.

Slanger, T. G.↗
NASA NTRS1971

The role of shock waves in the formation of organic compounds in the primeval atmosphere.

It is shown that shock waves from micrometeorites, meteors, meteorites, and thunder are of interest from the viewpoint of contributing significantly to the total accumulation of organic compounds in primeval times. The multitude of recombination reactions occurring in connection with shock waves could be an important factor in the formation of more complex compounds. Lower bound kinetic energies available to micrometeorites, cometary meteorites, stony and iron meteorites are calculated.

Hochstim, A. R.↗
NASA NTRS1973

Molecule formation. I - In normal H I clouds. II - In interstellar shock waves.

The formation of simple molecules and their role in the chemistry and physics of the interstellar medium is considered. The requirements for recombination reactions to occur on interstellar grains with the subsequent buildup of a molecular mantle are discussed. Together with a discussion of depletion and heating of the evolving gas, this forms the basis for a treatment of the precollision history of dust and gas. All the chemical reactions included in the calculations are given, as well as the results of calculations for two values of the intercloud pressure and for a range of cloud masses. Shock waves in clouds whose precollision history has been calculated are treated, followed by discussion of the shock structure and the dynamics of the grains. The process of sputtering is treated, and expressions are given for the cooling rates, including cooling due to the molecules formed behind the shock front. All the chemical reactions included in the calculations are given, as well as the results of calculations for a range of shock velocities and initial molecular hydrogen abundances.

Aannestad, P. A.↗
NASA NTRS1973

The photolytic stability of the Martian atmosphere.

Several recent suggestions for stabilizing the Martian atmosphere against photolysis have proved untenable. However, downward convective transport as well as a low altitude (0-35 km) aerosol, which catalyzes two-body molecular recombination reactions, can bring about such stability. The 'effective' convection velocity and 'average' two-body reaction rate coefficients required by observed abundances are evaluated. The computed profiles of CO and O at high altitude are shown to agree well with observations.

Whitten, R. C.↗
NASA NTRS1977

Low to high temperature energy conversion system

A method for converting heat energy from low temperature heat sources to higher temperature was developed. It consists of a decomposition chamber in which ammonia is decomposed into hydrogen and nitrogen by absorbing heat of decomposition from a low temperature energy source. A recombination reaction then takes place which increases the temperature of a fluid significantly. The system is of use for the efficient operation of compact or low capital investment turbine driven electrical generators, or in other applications, to enable chemical reactions that have a critical lower temperature to be used. The system also recovers heat energy from low temperature heat sources, such as solar collectors or geothermal sources, and converts it to high temperatures.

Miller, C. G.↗
NASA NTRS1978

Exact results on the temperature dependence of the specific equilibrium recombination rate coefficient

Two theorems based on Laplace transforms are used to relate threshold and high energy behavior to a temperature dependent variable. A recombination reaction involving electrically neutral species is presented to illustrate the dynamics of the activation energy and the associated rate coefficient. The distribution functions are shown to correspond with those predicted by Boltzmann's equations.

Mickens, R. E.↗
NASA NTRS1981

Excited ozone is a possible source of atmospheric N2O

Consideration is given to the possibility that internally excited ozone formed in the three-body recombination reaction between oxygen atoms and molecules may be a potential source of atmospheric N2O through a gas-phase reaction with nitrogen molecules. Determinations of the wavelength dependence of the quantum yield for N2O formation from the photolysis of dilute solutions of O3 in liquid N2 and of the O(1D) quantum yield in the gas-phase photolysis of O3 are interpreted as suggesting the possibility of the excited ozone reaction, and a new expression for N2O quantum yield is derived. An expression for the production rate of N2O through the proposed reaction is then obtained and used to calculate atmospheric concentrations and fluxes of N2O. The theoretical profile obtained is found to agree better with experimental data than that obtained without the excited ozone reaction taken into account and to demonstrate a wide variability in N2O mixing ratios. In addition, the existence of the new N2O source is noted to imply a significantly smaller flux of N2O from surface microbiological activities, and provide a possible physical basis for latitudinal and temporal N2O variations and an additional stability for the ozone layer.

Prasad, S. S.↗
NASA NTRS1981

The dissociative recombination of O2/+/ in the ionosphere

Aeronomical determinations of the dissociative recombination reaction rate coefficient for O2(+) and alpha depend directly on a knowledge of the rate coefficient for the charge exchange of O(+) with O2 and k. The aeronomical determination of alpha is reevaluated using Atmosphere Explorer satellite data in light of a subsequent laboratory measurement of k (Chen et al., 1978). The results are found to be in good agreement with laboratory determinations of the coefficient for night-time conditions. For data obtained under sunlit conditions, however, the results differed significantly with those of the laboratory measurements. These results imply that the state of the O2(+) molecule major thermospheric processes needs to be examined in greater detail.

Torr, M. R.↗
NASA NTRS1983

Phosphine photochemistry in Saturn's atmosphere

The phosphine photochemistry on Saturn is studied with a 1D photochemical model. The PH3 concentration is rapidly depleted with height (scale height 3.5 km) in the upper troposphere. Formation of P, a probable precursor of P4, (a potential red chromophore in the atmosphere), is highly improbable unless the rate constant for the recombination reaction PH + H2 + M yields PH3 + M is less than 10 to the -41st cm exp 6/molecule-squared sec. Coupling of PH3 and hydrocarbon photochemistry, specifically the C2H2 catalyzed photodissociation of CH, is important. Column production rates of the organophosphorus compounds CH3PH2 and HCP of 3 x 10 to the 8th/sq cm sec are predicted, with potentially observable column densities of greater than 1 x 10 to the 17th/sq cm.

Kaye, J. A.↗
NASA NTRS1984

Phosphine photochemistry in the atmosphere of Saturn

The photochemistry of PH3 in the atmosphere of Saturn is studied, including the effects of coupling with the photochemistries of NH3 and hydrocarbons. The vertical concentration of PH3 is found to be extremely sensitive to the eddy diffusion coefficient (K) profile used. If K is roughly 10,000 sq cm/sec in the upper troposphere, PH3 should be depleted there with a scale height of about 3.5 km. An upper limit of 100,000 sq cm/sec is estimated for K. If the gas phase concentration of P2H4 can be neglected, production of molecular phophorus is very unlikely unless the spin-forbidden recombination reaction PH+H2+M - PH3+M occurs with an exceptionally low rate. Coupling of PH3 and hydrocarbon photochemistries is very important. Possible observable amounts of the organophosphorus molecules CH3PH2 and HCP are tentatively predicted.

Kaye, J. A.↗
NASA NTRS1986

Solar flare ionization in the mesosphere observed by coherent-scatter radar

The coherent-scatter technique, as used with the Urbana radar, is able to measure relative changes in electron density at one altitude during the progress of a solar flare when that altitude contains a statistically steady turbulent layer. This work describes the analysis of Urbana coherent-scatter data from the times of 13 solar flares in the period from 1978 to 1983. Previous methods of measuring electron density changes in the D-region are summarized. Models of X-ray spectra, photoionization rates, and ion-recombination reaction schemes are reviewed. The coherent-scatter technique is briefly described, and a model is developed which relates changes in scattered power to changes in electron density. An analysis technique is developed using X-ray flux data from geostationary satellites and coherent scatter data from the Urbana radar which empirically distinguishes between proposed D-region ion-chemical schemes, and estimates the nonflare ion-pair production rate.

Parker, J. W.↗
NASA NTRS1987

Comment on 'Heavy ozone in the stratosphere'

It is suggested that the factor-of-two difference in ozone formation rate constants derived by Bates (1986) can also be explained by the omission of standard correction factors from the rate expression. Proper accounting for the fact that isotope exchange and recombination reactions share a common energized collision complex (which can decay by dissociation to products isotopically distinct from the original reactants) eliminates the anomalous dependence of the rate constant on the isotopic composition of the reactants and products through their symmetry numbers. In a reply, Bates argues that symmetry effects in association do not lead to enhancement of the total heavy ozone abundance.

Anderson, Stuart M.↗
NASA NTRS1988

The sensitivity of gas-phase models of dense interstellar clouds to changes in dissociative recombination branching ratios

The approach of Bates to the determination of neutral product branching ratios in ion-electron dissociative recombination reactions has been utilized in conjunction with quantum chemical techniques to redetermine branching ratios for a wide variety of important reactions of this class in dense interstellar clouds. The branching ratios have then been used in a pseudo time-dependent model calculation of the gas phase chemistry of a dark cloud resembling TMC-1 and the results compared with an analogous model containing previously used branching ratios. In general, the changes in branching ratios lead to stronger effects on calculated molecular abundances at steady state than at earlier times and often lead to reductions in the calculated abundances of complex molecules. However, at the so-called 'early time' when complex molecule synthesis is most efficient, the abundances of complex molecules are hardly affected by the newly used branching ratios.

Millar, T. J.↗
NASA NTRS1989

The evolution of organic mantles on interstellar grains

By laboratory simulation of the chemical processes on dust grains it was investigated how solid organic materials can be produced in the interstellar medium. The ice mantles that accrete on grains in molecular clouds, consisting primarily of H2O, CO, H2CO, NH3, and O2, are irradiated by the internal UV field, resulting in the storage of radicals upon photodissociation of the original molecules. Transient heating events lead to the production of oxygen-rich organic species by recombination reactions. The experiments indicated that in this way the observed amount of organic material can be produced if a grain passes a few times through a molecular cloud during its life. After the destruction of the cloud the grains enter a more diffuse medium. Here they are subjected to the interstellar UV field as well as to collisions with atomic hydrogen. Experiments show that the intense photoprocessing results in the removal of small species like H2O and NH3 as well as in carbonization of the organic molecules. Contrary to this, the atomic H flux will maintain a certain hydrogen level in the mantle. These processes likely convert the original, oxygen-rich organics into an unsaturated hydrocarbon type material such as that observed towards IRS 7 and in Comet Halley grains.

Schutte, Willem A.↗