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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

A covalent modification for graphene by adamantane groups through two-step chlorination-Grignard reactions

Chemical modification of graphene is a promising approach to manipulate its properties for its end applications. Herein we designed a two-step route through chlorination-Grignard reactions to covalently decorate the surface of graphene with adamantane groups. The chemically modified graphene was characterized by Raman spectroscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Chlorination of graphene occurred rapidly, and the substitution of chlorine atoms on chlorinated graphene by adamantane Grignard reagent afforded adamantane graphene in almost quantitative yield. Adamantane groups were found to be covalently bonded to the graphene carbons. The present two-step procedure may provide an effective and facile route for graphene modification with varieties of organic functional groups. - Graphical abstract: Adamantane groups covalently functionalized graphene is obtained by direct substitution of chlorinated graphene with bromoadamantane Grignard reagent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Synthesis of magnesium aluminate spinel by periclase and alumina chlorination

Highlights: • Use of chlorination for the synthesis of magnesium aluminate spinel. • The reagents used were alumina, periclase and chlorine. • Isothermal and non-isothermal assays were performed in air and Cl{sub 2}–N{sub 2} flows. • The chlorination produced magnesium aluminate spinel at 700 °C. • Selectivity of the chlorination reaction to obtain spinel is very high. - Abstract: A pyrometallurgical route for the synthesis of magnesium aluminate spinel by thermal treatment of a mechanical mixture containing 29 wt% MgO (periclase) and 71 wt% Al{sub 2}O{sub 3} (alumina) in chlorine atmosphere was developed and the results were compared with those obtained by calcining the same mixture of oxides in air atmosphere. Isothermal and non-isothermal assays were performed in an experimental piece of equipment adapted to work in corrosive atmospheres. Both reagents and products were analyzed by differential thermal analysis (DTA), X-ray diffraction (XRD) and X-ray fluorescence (XRF). Thermal treatment in Cl{sub 2} atmosphere of the MgO–Al{sub 2}O{sub 3} mixture produces magnesium aluminate spinel at 700 °C, while in air, magnesium spinel is generated at 930 °C. The synthesis reaction of magnesium aluminate spinel was complete at 800 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Synthesis of Hangman Chlorins

Two complementary rational synthetic routes have been developed in order to synthesize hangman chlorins, which differ with regard to the order of the installation (pre- and post-formation of the chlorin macrocycle) and position of the xanthene backbone about the chlorin periphery. The versatility of the synthetic method is demonstrated with the preparation of ten new hangman chlorins bearing a xanthene backbone and a pendant carboxylic acid. Cyclic voltammograms of hangman chlorins exhibit a hangman effect derived from intermolecular proton transfer. In conclusion, this hangman effect is manifested in catalytic hydrogen evolution production.

08 HYDROGEN↗
DOE OSTI2018

Chlorinated Wide-Bandgap Donor Polymer Enabling Annealing Free Nonfullerene Solar Cells with the Efficiency of 11.5%

Substituting the hydrogen atoms on the conjugated side chain of a wide-bandgap polymer J52 with chlorine atoms can simultaneously increase the J sc , V oc , and FF of nonfullerene OSCs, leading to an efficiency boost from 3.78 to 11.53%, which is among the highest efficiencies for as-cast OSCs reported to date. To illustrate the impressive 3-fold PCE enhancement, the chlorination effect on the optical properties and energy levels of polymers, film morphology, and underlying charge dynamics is systematically investigated. Grazing incidence wide-angle X-ray scattering studies show that chlorinated J52-2Cl exhibits strong molecule aggregation, the preferred face-on orientation, and enhanced intermolecular pi-pi interactions, hence increasing the charge carrier mobility by 1 order of magnitude. Moreover, chlorination modifies the miscibility between the donor and acceptor and consequently optimizes the phase separation morphology of J52-2Cl:ITIC blend films. Finallyhese results highlight chlorination as a promising approach to achieve highly efficient as-cast OSCs without any extra treatment.

14 SOLAR ENERGY↗
DOE OSTI2011

Silicon structuring by etching with liquid chlorine and fluorine precursors using femtosecond laser pulses

The aim of this study is to investigate the micrometer and submicrometer scale structuring of silicon by liquid chlorine and fluorine precursors with 200 fs laser pulses working at both fundamental (775 nm) and frequency doubled (387 nm) wavelengths. The silicon surface was irradiated at normal incidence by immersing the Si (111) substrates in a glass container filled with liquid chlorine (CCl{sub 4}) and fluorine (C{sub 2}Cl{sub 3}F{sub 3}) precursors. We report that silicon surfaces develop an array of spikes with single step irradiation processes at 775 nm and equally at 387 nm. When irradiating the Si surface with 400 pulses at 330 mJ/cm{sup 2} laser fluence and a 775 nm wavelength, the average height of the formed Si spikes in the case of fluorine precursors is 4.2 {mu}m, with a full width at half maximum of 890 nm. At the same irradiation wavelength chlorine precursors develop Si spikes 4 {mu}m in height and with a full width at half maximum of 2.3 {mu}m with irradiation of 700 pulses at 560 mJ/cm{sup 2} laser fluence. Well ordered areas of submicrometer spikes with an average height of about 500 nm and a width of 300 nm have been created by irradiation at 387 nm by chlorine precursors, whereas the fluorine precursors fabricate spikes with an average height of 700 nm and a width of about 200 nm. Atomic force microscopy and scanning electron microscopy of the surface show that the formation of the micrometer and sub-micrometer spikes involves a combination of capillary waves on the molten silicon surface and laser-induced etching of silicon, at both 775 nm and 387 nm wavelength irradiation. The energy-dispersive x-ray measurements indicate the presence of chlorine and fluorine precursors on the structured surface. The fluorine precursors create a more ordered area of Si spikes at both micrometer and sub-micrometer scales. The potential use of patterned Si substrates with gradient topography as model scaffolds for the systematic exploration of the role of 3D micro/nano morphology on cell adhesion and growth is envisaged.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Conjugated-linker dependence of the photophysical properties and electronic structure of chlorin dyads

The synthesis, photophysical properties and electronic structure of seven new chlorin dyads and associated benchmark monomers are described. Each dyad contains two identical chlorins linked at the macrocycle β-pyrrole 13-position. The extent of electronic communication between chlorin constituents depends on the nature of the conjugated linker. The communication is assessed by modification of prominent ground-state absorption and redox properties, rate constants and yields of excited-state decay processes, and molecular-orbital characteristics. Relative to the benchmark monomers, the chlorin dyads in toluene exhibit a substantial bathochromic shift of the long-wavelength absorption band (30 nm average), two-fold increased radiative rate constant [average (10 ns) -1 vs. (22 ns) -1 ], reduced singlet excited-state lifetimes (average 5.0 ns vs. 8.2 ns), and increased fluorescence quantum yields (average 0.56 vs. 0.42). The excited-state lifetime and fluorescence yield for the chlorin dyad with a benzothiadiazole linker are reduced substantially in benzonitrile vs. toluene due largely to ~25-fold accelerated internal conversion. The results aid design strategies for molecular architectures that may find utility in solar-energy conversion and photomedicine.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation

Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

organohalide respiration↗
NASA NTRS2006

Temporal Decrease in Upper Atmospheric Chlorine

We report a steady decrease in the upper stratospheric and lower mesospheric abundances of hydrogen chloride (HCl) from August 2004 through January 2006, as measured by the Microwave Limb Sounder (MLS) aboard the Aura satellite. For 60(deg)S to 60(deg)N zonal means, the average yearly change in the 0.7 to 0.1 hPa (approx.50 to 65 km) region is -27 +/- 3 pptv/year, or -0.78 +/- 0.08 percent/year. This is consistent with surface abundance decrease rates (about 6 to 7 years earlier) in chlorine source gases. The MLS data confirm that international agreements to reduce global emissions of ozone-depleting industrial gases are leading to global decreases in the total gaseous chlorine burden. Tracking stratospheric HCl variations on a seasonal basis is now possible with MLS data. Inferred stratospheric total chlorine (CITOT) has a value of 3.60 ppbv at the beginning of 2006, with a (2-sigma) accuracy estimate of 7%; the stratospheric chlorine loading has decreased by about 43 pptv in the 18-month period studied here. We discuss the MLS HCl measurements in the context of other satellite-based HCl data, as well as expectations from surface chlorine data. A mean age of air of approx. 5.5 years and an age spectrum width of 2 years or less provide a fairly good fit to the ensemble of measurements.

chlorine↗
DOE OSTI2011

Organochlorine Turnover in Forest Ecosystems: The Missing Link in the Terrestrial Chlorine Cycle

Research in the last 20 years has shown that chlorine undergoes transformations between inorganic and organic forms as part of a complex biogeochemical cycle in terrestrial systems. Natural organochlorine production appears to be associated with the decomposition of plant material on the soil surface, though the chlorine cycle budget implies that a proportion of natural organochlorine enters soil through plant litter and atmospheric deposition as well. Organochlorine compounds may form through biotic and abiotic pathways, but the rates and magnitude of production in the field remain undefined. We have performed a time-dependent trace of chlorine concentration through forest ecosystems, revealing distinct fractions of naturally produced organochlorine in plant biomass. Aliphatic organochlorine constitutes an intrinsic component of healthy leaves that persists through senescence and humification of the plant material, making a substantial contribution to the pool of soil organochlorine. Plant leaves also contain soluble aromatic organochlorine compounds that leach from leaf litter during early decay stages. As decay progresses, high concentrations of insoluble aromatic organochlorine accrue in the humus, through de novo production as well as adsorption. The rates of aromatic organochlorine production and degradation vary seasonally and conversely. This study presents the first unambiguous evidence that there exist multiple pools of chlorinated organic matter in the soil environment and that leaf litter deposition makes a significant and refractory contribution to the soil organochlorine pool, providing key insights into the biogeochemical chlorine cycle.

09 BIOMASS FUELS↗
DOE OSTI2017

Fine Tuning of Open-Circuit Voltage by Chlorination in Thieno[3,4- b ]thiophene–Benzodithiophene Terpolymers toward Enhanced Solar Energy Conversion

A new family of thieno[3,4-b]thiophene benzodithiophene terpolymers (PBTClx) have been designed and synthesized, in which the chlorine/fluorine content has been adjusted and optimized. As the content of chlorine is increased in polymers, the twist angle between the donor and acceptor is increased, which leads to a diminishment in the planarity and conjugation. As a result, the UV vis absorption is continuous blue-shifted, and the band gap increases from 1.57 to 2.04 eV when the chlorinated moieties increased from 0 to 100%. The highest occupied molecular orbital (HOMO) levels of those polymers are decreased by increasing the content of chlorinated moiety, which opens a window to constantly modify the V-oc values and eventually meets a balance point for optimized solar energy conversion. The highest power conversion efficiency of 8.31% is obtained by using PBTCl25 as the donor and PC71BM as the acceptor in polymer solar cells (PSCs), in which the Voc increased from 0.79 to 0.82 V after 25% chlorinated monomer involved in copolymerization. Herein, the chlorine replacement could be a good method to further pump the solar conversion by increasing the open circuit voltage without reducing other factors of the polymer solar cells.

Qu, Shiwei↗
DOE OSTI2018

Electron-Withdrawing Effects in the Photodissociation of CH 2 ICl To Form CH 2 Cl Radical, Simultaneously Viewed Through the Carbon K and Chlorine L 2,3 X-ray Edges

A fundamental chlorine-containing radical, CH 2 Cl, is generated by the ultrafast photodissociation of CH 2 ICl at 266 nm and studied at both the carbon K edge (~284 eV) and chlorine L 2,3 edge (~200 eV) by femtosecond X-ray transient absorption spectroscopy. The electronic structure of CH 2 Cl radical is characterized by a prominent new carbon 1s X-ray absorption feature at lower energy, resulting from a transition to the half-filled frontier carbon 2p orbital (singly occupied molecular orbital of the radical; SOMO). Shifts of other core-to-valence absorption features upon photodissociation of CH 2 ICl to yield ·CH 2 Cl indicate changes in the energies of core-level transitions of carbon and chlorine to the σ*(C-Cl) valence orbital. When the C-I bond breaks, loss of the electron-withdrawing iodine atom donates electron density back to carbon and shields the carbon 1s core level, resulting in a ~0.8 eV red shift of the carbon 1s to σ*(C-Cl) transition. Meanwhile, the 2p inner shell of the chlorine atom in the radical is less impacted by the iodine atom removal, as demonstrated by the observation of a ~0.6 eV blue shift of the transitions at the chlorine L 2,3 edges, mainly due to the stronger C-Cl bond and the increased energy of the σ* (C-Cl) orbital. The results suggest that the shift in the carbon 1s orbital is greater than the shift in the σ* (C-Cl) orbital upon going from the closed-shell molecule to the radical. Ab initio calculations using the equation of motion coupled-cluster theory establish rigorous assignment and positions of the X-ray spectral features in the parent molecule and the location of the SOMO in the CH 2 Cl radical.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Octupole moment driven free charge generation in partially chlorinated subphthalocyanine for planar heterojunction organic photodetectors

In this study, high-performance organic photodetectors are presented which utilize a pristine chlorinated subphthalocyanine photoactive layer. Optical and optoelectronic analyses indicate that the device photocurrent is primarily generated through direct charge generation within the chlorinated subphthalocyanine layer, rather than exciton separation at layer interfaces. Molecular modelling suggests that this direct charge generation is facilitated by chlorinated subphthalocyanine high octupole moment (-80 DÅ 2 ), which generates a 200 meV shift in molecular energetics. Increasing the thickness of chlorinated subphthalocyanine leads to faster response time, correlated with a decrease in trap density. Notably, photodetectors with a 50 nm thick chlorinated subphthalocyanine photoactive layer exhibit detectivities approaching 10 13 Jones, with a dark current below 10 -7 A cm -2 up to -5 V. Based on these findings, we conclude that high octupole moment molecular semiconductors are promising materials for high-performance organic photodetectors employing single-component photoactive layer.

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

Effect of chlorine and chromium on sulfur solubility in low-activity waste glass

According to an empirical sulfur solubility model developed from over 200 simulated low-activity waste (LAW) glasses, chlorine and chromium show strong effects on lowering sulfur solubility in glass. This work was aimed at understanding the mechanism behind the negative effect of chlorine and chromium on sulfur solubility. A simplified LAW glass was prepared and saturated by sodium sulfate, sodium chloride, and sodium chromate salts as single components and as mixtures with different ratios at 25 mol%, 50 mol%, and 75 mol% of sulfate mixed with chloride or chromate. A crucible-scale salt-saturation was performed by mixing the crushed glass powder with an excess amount of salts, melting at 1150 °C for one hour, and quenching. Three mixing-melting-quenching cycles were applied to determine saturation concentrations of sulfur, chromium, and chlorine incorporated into the simplified LAW glass. The glass compositions were analyzed by inductively coupled plasma–atomic emission spectroscopy, ion chromatography, and X-ray emission spectroscopy. It is proposed that the negative effect of chlorine and chromium on sulfur solubility can be explained based on the simple hypothesis that sulfur, chlorine, and chromium are present in the glass as anions competing for the voids or interstitial sites of the glass matrix, and that their solubility strongly depends on the effective size of corresponding anions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1978

Summary of airborne chlorine and hydrogen chloride gas measurements for August 20 and September 5, 1977 Voyager launches at Air Force Eastern Test Range, Florida

Airborne chlorine and hydrogen chloride measurements were made in the tropospheric ground cloud following the Voyager launches of August 20 and September 5, 1977. The maximum observed hydrogen chloride concentration for both launches was about 25 to 30 parts per million (ppm) occurring typically 2 to 6 minutes after launch. By completion of the sampling mission (1-1/2 hours for August, 4-1/2 hours for September), the maximum in-cloud concentration decayed to about 1 to 2 ppm. Maximum observed chlorine concentrations were about 40 to 55 parts per billion (ppb) about 2 to 8 minutes after launch; by about 15 minutes after launch, chlorine concentrations were less than 10 ppb (detection limit). In-cloud chlorine concentrations were well below 1 percent of hydrogen chloride concentrations. The appendix of the report discusses the chlorine instrument and the laboratory evaluation of the detector.

Gregory, G. L.↗
NASA NTRS1978

The reaction Cl + H2CO yields HCl + HCO: Decreased sensitivity of stratospheric ozone to chlorine perturbations

The absolute rate constant for the reaction Cl + H2CO yields HCl + HCO was determined by the flash-photolysis resonance fluorescence method to be 7.5 plus or minus 0.9 (2 sigma) times 10 to the minus 11th power cu cm/molecule sec at 298 K and to have a negligible temperature dependence. This rate which is more than 2000 times faster than the rate of Cl + CH4 indicates that formaldehyde (H2CO) will compete significantly with methane (CH4) for the conversion of active chlorine in the stratosphere to the inactive reservoir HCl. Chlorine will thus be a less efficient destroyer of stratosphere ozone than previously believed. Ambient stratospheric ozone will depend less on the ambient chlorine amount and the predicted response to chlorine perturbations will be lessened. One-dimensional eddy-diffusion photochemical model calculations indicate a factor of 1.1 less sensitivity to chlorine than recently reported. For a steady-state CFM release at 1975 rates (750,000 tons/year) the eventual ozone depletion is now calculated to be 14%.

Stief, L. J.↗
NASA NTRS1990

High temperature reactions of ceramics and metals with chlorine and oxygen

The reactions of chlorine and oxygen with solids are complex and quite dependent on material and reaction conditions. However, there are four reaction schemes that describe many of these reactions. These are direct reaction of chlorine with the oxide layer, penetration of the oxide layer by chlorine, paralinear behavior where oxidation and chlorination are of comparable rates, and finally, gas phase reactions where the volatile chlorides react with oxygen. Examples of chlorine and oxygen reactions with cobalt, nickel, chromium, molybdenum, and silicon carbide illustrate each of these four reaction schemes.

Jacobson, N. S.↗
NASA NTRS1993

Stratospheric chlorine injection by volcanic eruptions - HCl scavenging and implications for ozone

Because the output of volatile chlorine during a major volcanic event can greatly exceed the annual anthropogenic emissions of chlorine to the atmosphere, the fate of volcanic chlorine must be known. Although numerous observations have shown that volcanoes do not significantly contribute to the stratospheric chlorine burden, no quantitative explanation has been published. Hydrogen chloride (HCl) scavenging processes during the early phases of a volcanic eruption are discussed. A plume dynamics and thermodynamics model is used to show that HCl removal in condensed supercooled water can reduce HCl vapor concentrations by up to four orders of magnitude, preventing substantial stratospheric chlorine injection.

Tabazadeh, A.↗
NASA NTRS1994

Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

Pan, Chenyu↗