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At least 55 records · Page 3

Lost and Found Opportunities Around the Chlorine Worth Study

Los Alamos National Laboratory performed a series of critical experiments in 2021 to examine the worth of chlorine in plutonium-fueled systems. This series of experiments has been dubbed the “Chlorine Worth Study,” and the evaluation of the experiments was presented to the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Technical Review Group in April, 2023. The primary purpose of these experiments was to enable validation of aqueous solutions crediting neutron absorption in 35 Cl. An external, independent view of the events leading up to the design and execution of these experiments indicates a missed opportunity to leverage sensitivity/uncertainty (S/U) analysis to assert validation without the experiments by taking an additional margin for the lack of direct validation of chlorine. On the other hand, the execution of these experiments also presents a rare opportunity to examine the efficacy of the S/U approach and extract useful information about the evaluated chlorine covariance data. TSUNAMI-1D models of representative application solutions were created and used to generate sensitivity data. Varying plutonium and chlorine concentrations were considered to examine the impact of these differences on the chlorine sensitivities and uncertainties. The data-induced uncertainty in k eff resulting from chlorine was calculated directly from uncertainty information calculated in the TSUNAMI-1D sequence. In all cases, this uncertainty was less than 0.1 %Δk. This result could potentially be used to justify a reactivity margin to account for the validation gap related to chlorine in the validation set. On the other hand, given that the experiments were performed, the community should endeavor to extract as much value from them and their results as possible. The results can be used to examine the actual bias associated with chlorine in these systems once the evaluations have been released. These data can be compared with the data-induced uncertainty margin discussed above to test the sufficiency of the validation gap penalty. This result will provide an indication of the performance of the chlorine covariance data specifically and the S/U validation approach generally. More advanced S/U techniques may also be employed to determine reactivity sensitivities associated with the chlorine in the experiments, potentially generating a more robust test of the chlorine covariance data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The Connection between Model Performance on the CCMVal Transport Diagnostics and Simulated Sensitivity of Ozone to Chlorine Change

The chemistry climate models that contributed simulations for past and future ozone evolution to the 2010 Scientific Assessment of Ozone Depletion were subject to extensive evaluation by the SPARC (Stratospheric Processes and their Role in Climate) CCMVal (Chemistry-Climate Model Validation) activity. The sensitivity of ozone to changes in composition and climate varies among the models, but the relationship between these variations and the model evaluations of CCMVal is not obvious. We have learned that the transport evaluation can be used to interpret the comparisons between observed and simulated columns of chlorine reservoirs, hydrochloric acid (HCl) and chlorine nitrate (ClONO2); these comparisons were part of the CCMVal evaluation of chemistry. The simulations with best performance on the transport diagnostics most faithfully reproduce the evolution and seasonal variation of the chlorine reservoirs as observed at NDACC (Network for Detection of Atmospheric Composition Change) stations (NyAlesund 78.9N, Kiruna 67.8N, Harestua 60.2N, Jungfraujoch 46.6N, Toronto 43.6N, Kitt Peak 31.9N, Izana 28.3N, Mauna Loa 19.5N, Lauder 45S and Arrival Heights 77.8S). In the simulations, the HCl in the lower stratosphere depends on total inorganic chlorine (Cly) and partitioning between HCl and ClON02. Total inorganic chlorine depends on the fractional release of chlorine from source gases, and ratio of ClON02 to HCl is inversely dependent on methane and varies quadratically with ozone. Simulated HCl from various models may agree with observations even though Cly is in error, partitioning is in error, or both. Simulated ozone sensitivity to chlorine is shown to be greater for models that produce larger values of chlorine nitrate for background chlorine levels, and vice versa. Comparisons with the NDACC data show why the models with 'best' transport have similar sensitivity to chlorine change. The realistic evolution of the simulated HCl and ClONO2 columns suggests realistic levels of Cly in the lower atmosphere. In addition, the wide range values for the sensitivity of ozone to chlorine obtained from the CCMVal simulations is explained by the wide range in lower atmospheric columns of ClONO2 and the concomitant wide range of levels for chlorine monoxide.

Douglass, Anne↗

Measurement of free chlorine levels in water using potentiometric responses of biofilms and applications for monitoring and managing the quality of potable water

We report residual free chlorine is not monitored continuously at scale in drinking water distribution systems because existing real-time sensor technologies require frequent maintenance, cleaning, and calibration, which makes these products too costly to be used throughout a distribution system. As a result, current measurement approaches require manual sampling, which is not feasible for the consistent monitoring of free chlorine because chlorine concentrations vary significantly throughout pipeline distribution and over time and space. This research presents an alternative and cost-effective method of predicting free chlorine levels in drinking water using graphite electrodes coated with naturally grown microbial biofilms. This Microbial Potentiometric Sensor (MPS) array was installed in a Continuously Mixed Batch Reactor (CMBR), and drinking water containing variable free chlorine concentrations. The chlorine concentrations were introduced in a controlled manner, and the MPS signals were monitored over time. MPS signals were measured from the change in Open Circuit Potential (OCP) across the MPS array in real-time. An empirically derived relationship between the normalized change in OCP and free chlorine was established by fitting individual and average MPS data to a decaying exponential growth function in order to predict free chlorine levels. The results show that free chlorine can be predicted with reasonable accuracy, with model validation showing an average absolute error of ±0.09 ppm below 1.1 ppm and ±0.30 ppm between 1.1 and 2.7 ppm. However, the accuracy of predictions was reduced at higher free chlorine levels. The researchers conclude that MPS systems may benefit drinking water distribution systems by measuring free chlorine. These advantages of the MPS are especially pronounced in the developing world because this system is inexpensive and does not require routine maintenance or cleaning. The system relies on a naturally forming and regenerating biofilm and an inexpensive potentiometric meter to produce stable measurements.

54 ENVIRONMENTAL SCIENCES↗

Kinetics of thermal de-chlorination of PVC under pyrolytic conditions

Highlights: Black-Right-Pointing-Pointer Several tests were performed in DTA/TGA for understanding the thermal behavior of pure PVC. Black-Right-Pointing-Pointer We did a kinetic model for the de-chlorination of PVC molecule. Black-Right-Pointing-Pointer A temperature of 340 Degree-Sign C was defined as the optimum temperature for breaking the bond of chlorine in the PVC molecule. Black-Right-Pointing-Pointer The experimental validation of this temperature, led to a removal rate of 99.9% chlorine. - Abstract: Although PVC-containing wastes are an important potential source of energy they are frequently disposed in landfill. In thermal treatment processes such as pyrolysis and gasification, the presence of poly(vinyl chloride) (PVC), a compound with 56.7% of chlorine, may cause problems concerned with environmental protection, as consequence of the formation of hydrochloric acid, chlorine gas and dioxins, as well as corrosion phenomena of the reactor/equipment materials. Thus, a possible solution may involve a previous removal of the chlorine from PVC containing waste through a pyrolysis process at low temperatures before the material being submitted to a subsequent thermal treatment, for energetic valorization. In this work, a kinetic model for the thermal decomposition of PVC has been developed, in view of its de-chlorination. DTA/TGA testing at different temperatures indicated a first order reaction and an activation energy of 133,800 J/mol. An almost completed de-chlorination reaction was obtained at 340 Degree-Sign C under an inert atmosphere. The resulted material is a C{sub n}H{sub n} type polymer with potential to be used in an energy recovery process. Validation test performed at laboratory scale indicate that the temperature of 340 Degree-Sign C enables the removal of {approx}99.9% of the chlorine present in PVC. The chloride can be fixed in the form of an aqueous solution of HCl or calcium chloride, driving to an alternative full process with environmental benefits and reduction of the costs associated to the PCV - containing materials/wastes management.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Variations in Stratospheric Inorganic Chlorine Between 1991 and 2006

So how quickly will the ozone hole recover? This depends on how quickly the chlorine content (Cl2) of the atmosphere will decline. The ozone hole forms over the Antarctic each southern spring (September and October). The extremely small ozone amounts in the ozone hole are there because of chemical reactions of ozone with chlorine. This chlorine originates largely from industrially produced chlorofluorocarbon (CFC) compounds. An international agreement, the Montreal Protocol, is drastically reducing the amount of chlorine-containing compounds that we are releasing into the atmosphere. To be able to attribute changes in stratospheric ozone to changes in chlorine we need to know the distribution of atmospheric chlorine. However, due to a lack of continuous observations of all the key chlorine gases, producing a continuous time series of stratospheric chlorine has not been achieved to date. We have for the first time devised a technique to make a 17-year time series for stratospheric chlorine that uses the long time series of HCl observations made from several space borne instruments and a neural network. The neural networks allow us to both inter-calibrate the various HCl instruments and to infer the total amount of atmospheric chlorine from HCl. These new estimates of Cl, provide a much needed critical test for current global models that currently predict significant differences in both Cl(sub y) and ozone recovery. These models exhibit differences in their projection of the recovery time and our chlorine content time series will help separate the good from the bad in these projections.

Lary, D. J.↗

Inhibition of chlorine-induced lung injury by the type 4 phosphodiesterase inhibitor rolipram

Chlorine is a highly toxic respiratory irritant that when inhaled causes epithelial cell injury, alveolar-capillary barrier disruption, airway hyperreactivity, inflammation, and pulmonary edema. Chlorine is considered a chemical threat agent, and its release through accidental or intentional means has the potential to result in mass casualties from acute lung injury. The type 4 phosphodiesterase inhibitor rolipram was investigated as a rescue treatment for chlorine-induced lung injury. Rolipram inhibits degradation of the intracellular signaling molecule cyclic AMP. Potential beneficial effects of increased cyclic AMP levels include inhibition of pulmonary edema, inflammation, and airway hyperreactivity. Mice were exposed to chlorine (whole body exposure, 228–270 ppm for 1 h) and were treated with rolipram by intraperitoneal, intranasal, or intramuscular (either aqueous or nanoemulsion formulation) delivery starting 1 h after exposure. Rolipram administered intraperitoneally or intranasally inhibited chlorine-induced pulmonary edema. Minor or no effects were observed on lavage fluid IgM (indicative of plasma protein leakage), KC (Cxcl1, neutrophil chemoattractant), and neutrophils. All routes of administration inhibited chlorine-induced airway hyperreactivity assessed 1 day after exposure. The results of the study suggest that rolipram may be an effective rescue treatment for chlorine-induced lung injury and that both systemic and targeted administration to the respiratory tract were effective routes of delivery. -- Highlights: ► Chlorine causes lung injury when inhaled and is considered a chemical threat agent. ► Rolipram inhibited chlorine-induced pulmonary edema and airway hyperreactivity. ► Post-exposure rolipram treatments by both systemic and local delivery were effective. ► Rolipram shows promise as a rescue treatment for chlorine-induced lung injury.

60 APPLIED LIFE SCIENCES↗

Inhibition of chlorine-induced pulmonary inflammation and edema by mometasone and budesonide

Chlorine gas is a widely used industrial compound that is highly toxic by inhalation and is considered a chemical threat agent. Inhalation of high levels of chlorine results in acute lung injury characterized by pneumonitis, pulmonary edema, and decrements in lung function. Because inflammatory processes can promote damage in the injured lung, anti-inflammatory therapy may be of potential benefit for treating chemical-induced acute lung injury. We previously developed a chlorine inhalation model in which mice develop epithelial injury, neutrophilic inflammation, pulmonary edema, and impaired pulmonary function. This model was used to evaluate nine corticosteroids for the ability to inhibit chlorine-induced neutrophilic inflammation. Two of the most potent corticosteroids in this assay, mometasone and budesonide, were investigated further. Mometasone or budesonide administered intraperitoneally 1 h after chlorine inhalation caused a dose-dependent inhibition of neutrophil influx in lung tissue sections and in the number of neutrophils in lung lavage fluid. Budesonide, but not mometasone, reduced the levels of the neutrophil attractant CXCL1 in lavage fluid 6 h after exposure. Mometasone or budesonide also significantly inhibited pulmonary edema assessed 1 day after chlorine exposure. Chlorine inhalation resulted in airway hyperreactivity to inhaled methacholine, but neither mometasone nor budesonide significantly affected this parameter. The results suggest that mometasone and budesonide may represent potential treatments for chemical-induced lung injury. - Highlights: • Chlorine causes lung injury when inhaled and is considered a chemical threat agent. • Corticosteroids may inhibit lung injury through their anti-inflammatory actions. • Corticosteroids inhibited chlorine-induced pneumonitis and pulmonary edema. • Mometasone and budesonide are potential rescue treatments for chlorine lung injury.

60 APPLIED LIFE SCIENCES↗

Development of a Chlorine Cathode and Anode Basket Assembly for Production of Uranium Chloride

A chlorine cathode has been developed for in situ chlorination of metals, oxides, and oxychlorides in molten chloride electrolytes that could be used to support synthesis of chloride fuel salts for molten salt reactors. The chlorine cathode is designed to electrochemically reduce chlorine gas to generate chloride ions that, when paired with a metal anode, chlorinate that metal as it is oxidized into the salt. The designed porous carbon electrode effectively distributes Cl 2 to the electrode surface and efficiently generates Clions in the molten chloride electrolyte. This report highlights recent improvements made to the electrode assembly, with a focus on operational control of the anode basket stability. Synthesis tests demonstrated the successful chlorination of uranium metal, resulting in 3.6 wt% uranium generated in the LiCl-KCl base salt in 45 minutes, performed in a bench-scale chlorination apparatus. Higher concentrations could be achieved by applying longer chlorination times or increasing the amount of uranium loaded in the anode basket. Overall, the chlorine cathode can be used with an appropriately designed anode to chlorinate uranium in situ for synthesis of molten salt reactor fuel salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Bromine-Chlorine Coupling in the Antarctic Ozone Hole

The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioninig in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5 - 25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70 deg. S, NO(sub y) = 2 ppbv, with Polar Stratospheric Clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC- perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO an Cl2O2 back to HCI. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (alpha-factor) ranges from 33 to 55, decreasing with increase of bromine.

Danilin, Michael Y.↗

Stable Chlorine Isotope Study: Application to Early Solar System Materials

A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the Cl-37/Cl-35 ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For example, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the 37Cl/35Cl ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For eample, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. In order to clarify the stable chlorine isotope features of early solar system materials, we have initiated development of the TIMS technique at NASA JSC applicable to analysis of small amounts of meteoritic and planetary materials. We report here the current status of chlorine isotope analysis at NASA JSC.

Mala,ira. M/↗

Influence of the chlorine concentration on the radiation efficiency of a XeCl exciplex lamp

The influence of the chlorine concentration on the radiation efficiency of coaxial exciplex lamps (excilamps) excited by a dielectric barrier discharge (DBD) in binary Xe-Cl{sub 2} mixtures at pressures of 240–250 Torr is investigated experimentally and theoretically. The experiments were carried out at Cl{sub 2} concentrations in the range of 0.01–1%. The DBD characteristics were calculated in the framework of a one-dimensional hydrodynamic model at Cl{sub 2} concentrations in the range of 0.1–5%. It is found that the radiation intensities of the emission bands of Xe*{sub 2}(172 nm) and XeCl* (308 nm) are comparable when the chlorine concentration in the mixture is in the range of 0.01–0.1%. In this case, in the mixture, the radiation intensity of the Xe*{sub 2} molecule rapidly decreases with increasing Cl{sub 2} concentration and, at a chlorine concentration of ≥0.2%, the radiation of the B → X band of XeCl* molecules with a peak at 308 nm dominates in the discharge radiation. The radiation efficiency of this band reaches its maximum value at chlorine concentrations in the range of 0.4–0.5%. The calculated efficiencies of DBD radiation exceed those obtained experimentally. This is due to limitations of the one-dimensional model, which assumes the discharge to be uniform in the transverse direction, whereas the actual excilamp discharge is highly inhomogeneous. The influence of the chlorine concentration on the properties of the DBD plasma in binary Xe-Cl{sub 2} mixtures is studied numerically. It is shown that an increase in the Cl{sub 2} concentration in the mixture leads to the attachment of electrons to chlorine atoms and a decrease in the electron density and discharge conductivity. As a result, the electric field and the voltage drop across the discharge gap increase, which, in turn, leads to an increase in the average electron energy and the probability of dissociation of Cl{sub 2} molecules and ionization of Xe atoms and Cl{sub 2} molecules. The total energy deposited in the discharge rises with increasing chlorine concentration due to an increase in the power spent on the heating of positive and negative ions. The power dissipated by electrons decreases with increasing chlorine concentration in the working mixture. Recommendations on the choice of the chlorine content in the mixture for reducing the intensity of VUV radiation of the second continuum of the Xe*{sub 2} excimer without a substantial decrease in the excilamp efficiency are formulated.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Design and synthesis of chlorinated benzothiadiazole-based polymers for efficient solar energy conversion

Here, chlorinated benzothiadiazide based polymers with multiple chlorine atoms has been designed and synthesized for polymer solar cells with enhanced open circuit voltage up to 0.85 V. The chlorine substitution is found to significantly adjust the band gap of the polymers, and change polymer’s orientation from random morphology of chlorine free PBT4T-2OD, to mixed face-on packing of one chlorine substituted PCBT4T-2OD, and finally to edge-on of two chlorine substituted PCCBT4T-2OD. The optimized chlorinated polymer, PCBT4T-2OD with only one chlorine atom substituted on BT moiety, has been founded to achieve the highest power conversion efficiency up to 8.20% with PC 71 BM, which is about 68% higher than that of its non-chlorine analogues.

14 SOLAR ENERGY↗

The chlorine budget of the troposphere

It has been hypothesized that chlorine compounds in the stratosphere could photodissociate and release atomic chlorine which catalytically destroys ozone. For an accurate assessment of the possibility of stratospheric ozone depletion, it will be necessary to know the chlorine budget of the entire atmosphere, including the troposphere and the stratosphere. Most chlorine species in the atmosphere are emitted at the surface and diffuse upward. Measurements involving chlorine are reviewed and photochemical calculations are discussed. It is found that between 0.1-1.0 ppbv of inorganic chlorine is present at the surface and about 0.02 ppbv (parts per billion by volume) at the tropopause. Most of the inorganic chlorine is believed to be in the form of HCl, and thus natural in origin. For organic chlorine the corresponding numbers are 1.9 ppbv and 1.7 ppbv, respectively. At the surface approximately 32% of the organic chlorine is natural and 68% anthropogenic.

Augustsson, T. R.↗

A study of the characteristics of indium tin oxide after chlorine electro-chemical treatment

Graphical abstract: The presence of Chlorine in the outer surface resulted in a highly electro-negative surface states and an increase in the vacuum energy level. - Highlights: • We investigated the influence of chlorine surface treatment on ITO properties. • Chlorination induced the change of the electro-static potential in the outer surface. • Chlorine electro-chemical treatment of ITO is a simple, fast and effective technique. - Abstract: In this work, we investigate the influence of a chlorine-based electro-chemical surface treatment on the characteristics of indium tin oxide (ITO) including the work function, chemical composition, and phase transition. The treated ITOs were characterized using X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), 4-point probe measurements, and grazing incidence X-ray diffraction (GI-XRD). We confirmed a change of the chemical composition in the near-surface region of the ITO and the formation of indium-chlorine (In-Cl) bonds and surface dipoles (via XPS). In particular, the change of the electro-static potential in the outer surface was caused by chlorination. Due to the vacuum-level shift after the electro-chemical treatment in a dilute hydrochloric acid, the ITO work function was increased by ∼0.43 eV (via UPS); furthermore, the electro-negativity of the chlorine anions attracted electrons to emit them from the hole transport layer (HTL) to the ITO anodes, resulting in an increase of the hole-injection efficiency.

36 MATERIALS SCIENCE↗

Research of sensing characteristic and dynamic measurement of graphene oxides modified flexible arrayed RuO2 chlorine ion sensor

Highlights: • Sensitivity of the flexible arrayed RuO2/GO chlorine ion sensor was improved with optimal GO concentration, which could increase the reaction area between the chlorine ion and chlorine sensing membrane. • The electrochemical impedance spectroscopy (EIS) and atomic force microscope (AFM) were utilized to explain the relationships among the electron transfer resistance, GO modified amount and sensitivity. • The 30 μL/min flow rate of dynamic measurement for flexible arrayed RuO2/0.010 wt% GO chlorine ion sensor was obtained the best sensitivity and linearity 66.673 mV/pCl and 0.998, respectively. - Abstract: In this study, we used the graphene oxide (GO) solution, in which the concentration was from 0.005 wt% to 0.500 wt%, to modify the flexible arrayed ruthenium dioxide (RuO{sub 2}) chlorine ion sensor. It is found that the flexible arrayed RuO{sub 2}/0.010 wt% GO chlorine ion sensor had the best sensitivity (44.445 mV/pCl) and the linearity was 0.971. The electrochemical impedance spectroscopy (EIS) and atomic force microscope (AFM) were utilized to explain the relationships among the electron transfer resistance, GO modified amount and sensitivity. After that, we used the flexible arrayed RuO{sub 2}/0.010 wt% GO chlorine ion sensor and the microfluidic measurement system to investigate the dynamic sensing characteristics with different flow rates from 5 μL/min to 40 μL/min. According to the experimental results, the best sensitivity and linearity of flexible arrayed RuO{sub 2}/0.010 wt% GO chlorine ion sensor were 66.673 mV/pCl and 0.992 at 30 μL/min.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Chlorination of Side Chains: A Strategy for Achieving a High Open Circuit Voltage Over 1.0 V in Benzo[1,2-b:4,5-b']dithiophene-Based Non-Fullerene Solar Cells

Here, a benzo[1,2-b:4,5-b']dithiophene-based donor material with chlorine atoms substituted on its side chains, named PBClT, was designed and developed for application in non-fullerene solar cells to enhance the open-circuit voltage ( V oc ) without decreasing charge carrier transfer in the corresponding blend films. The results demonstrated that the chlorinated PBClT polymer was an efficient donor in non-fullerene polymer solar cells (PSCs) and exhibited a blue-shifted absorbance, resulting in more complementary light absorption with non-fullerene acceptors, such as ITIC. In addition, the chlorine substitution decreased the HOMO level of PBClT, and as a result, the V oc of the corresponding solar cell increased dramatically to 1.01 V, which is much higher than that of the non-chlorine analog, PTB7-Th, with a V oc of approximately 0.82 V. The 2D-GIWAX results illustrated that the PBClT/ITIC blend film exhibited a “face-on” orientation, which suggested that the chlorine substituents on the side chains favored π-π stacking in the direction perpendicular to the electron flow in photovoltaic devices. Furthermore, the PBClT/ITIC blend film showed a π-π stacking distance of 3.85 Å, which was very close to that of its non-chlorine analog blend film with a distance of approximately 3.74 Å. Based on this result, the introduction of multiple chlorine atoms on the conjugated side chains not only adjusted the energy level of the low-band-gap polymer through the electron withdrawing ability of the chlorine atoms but also subtly avoided obvious morphological changes that could result from strong steric hindrance in the main chain of the polymers. The PBClT/ITIC-based PSCs exhibited a maximum PCE of 8.46% with a V oc of 1.01 V, which is an increase in the PCE of approximately 22% compared to the PTB7-Th-based device based on our parallel experiments.

14 SOLAR ENERGY↗

A carbon nanotube based resettable sensor for measuring free chlorine in drinking water

Free chlorine from dissolved chlorine gas is widely used as a disinfectant for drinking water. The residual chlorine concentration has to be continuously monitored and accurately controlled in a certain range around 0.5–2 mg/l to ensure drinking water safety and quality. However, simple, reliable, and reagent free monitoring devices are currently not available. Here, we present a free chlorine sensor that uses oxidation of a phenyl-capped aniline tetramer (PCAT) to dope single wall carbon nanotubes (SWCNTs) and to change their resistance. The oxidation of PCAT by chlorine switches the PCAT-SWCNT system into a low resistance (p-doped) state which can be detected by probing it with a small voltage. The change in resistance is found to be proportional to the log-scale concentration of the free chlorine in the sample. The p-doping of the PCAT-SWCNT film then can be electrochemically reversed by polarizing it cathodically. This sensor not only shows good sensing response in the whole concentration range of free chlorine in drinking water but is also able to be electrochemically reset back many times without the use of any reagents. This simple sensor is ideally suited for measuring free chlorine in drinking water continuously.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Reduction of Chlorinated Ethenes by Ag- and Cu-Amended Green Rust

Chlorinated ethenes have been used extensively as solvents, degreasers, and dry-cleaning agents in a range of commercial and industrial applications. This has created a legacy of contaminated soils and groundwater, particularly with respect to perchloroethylene (PCE; a.k.a. tetrachloroethene—C 2 Cl 4 ), and trichloroethylene (TCE; a.k.a. trichloroethene—C 2 HCl 3 ), prompting the development of a wide array of treatment technologies for remediation of chlorinated ethene-contaminated environments. Green rusts are highly redox-active layered Fe(II)-Fe(III) hydroxides that have been shown to be facile reductants for a wide range of organic and inorganic pollutants. The reduction of chlorinated ethenes [vinyl chloride (VC); 1,1-dichloroethene(11DCE), cis-1,2-dichloroethene (c12DCE), trans-1,2-dichloroethene (t12DCE), TCE, and PCE] was examined in aqueous suspensions of green rust, alone as well as with the addition of Ag(I) (AgGR) or Cu(II) (CuGR). Green rust alone was ineffective as a reductant for the reductive dechlorination for all of the chlorinated ethenes. Near-complete removal of PCE was observed in the presence of AgGR, but all other chlorinated ethenes were essentially non-reactive. Partial removal of chlorinated ethenes was observed in the presence of CuGR, particularly 11DCE (34%), t12DCE (51%), and VC (66%). Significant differences were observed in the product distributions of chlorinated ethene reduction by AgGR and CuGR. The effectiveness of Ag(I)- and Cu(II)-amended green rusts for removal of chlorinated ethenes may be improved under different conditions (e.g., pH and interlayer anion) and warrants further investigation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗