Spark plasma sintering-densified vanadinite apatite-based chlorine waste forms with high thermal stability and chlorine confinement
Not provided.
nuclear, defects, corrosion↗
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Synergistic effects of chlorine substitution in sulfide electrolyte solid state batteries
All-solid-state battery is considered as one of the most promising competitors to Li ion batteries. Two widely known performance metrics for solid electrolytes, among others, are ionic conductivity and stability. In this study, it is found that both can be improved by the synergistic effects of chlorine substitution in sulfide-based solid electrolytes. Particularly, instabilities arising from both bulk decompositions and interfacial reactions to electrodes can be better inhibited in the chlorine substituted sulfide solid electrolytes through the increased susceptibility to the mechanical constriction induced enhancement of voltage stability. As a result, the stability window of some chlorine-rich Li-argyrodites can be systematically higher than some other chlorine-deficient or chlorine-free electrolytes, especially under the implementation of the mechanical constriction battery assembly and test conditions. Thus, a solid-state battery system of 4 V to 5 V-class cathodes paired with lithium metal anode is demonstrated using these chlorine-rich Li-argyrodites without additional coatings. Furthermore, since Cl composition modulates the stability and instability of Li-argyrodite at low voltages, it allows us to design a multilayer configuration with a hierarchy of Li metal stabilities to demonstrate the stable cycling at relatively high current densities for solid-state batteries. It is found that a moderate Cl composition in the electrolyte is the best to inhibit Li dendrite penetration as the central electrolyte layer, emphasizing a slightly increased “instability” as the hidden performance metric of relevance here, in addition to the two well-known metrics of stability and ionic conductivity. The understanding of the chlorine substitution effect in sulfide electrolytes provides an important design principle for all-solid-state batteries.
25 ENERGY STORAGE↗
Benchmark of the Chlorine Worth Study Experiments in Support of Chlorine Nuclear Data Validation for Nuclear Criticality Safety
The Chlorine Worth Study (CWS) was a critical experiment to address an urgent need for thermal chlorine nuclear data validation in plutonium systems. This urgent need is tied directly to plutonium recycle and recovery operations in the plutonium facility at Los Alamos National Laboratory, where exceptionally conservative criticality safety limits are used because no credit is taken for the neutron capture by chlorine. The experiment used weapons-grade plutonium metal plates clad in stainless steel, known as the PANN (plutonium aluminum no nickel) ZPPR (zero power physics reactor) plates. The plutonium was reflected and moderated by high-density polyethylene and included combinations of polyvinyl chloride (PVC) and chlorinated polyvinyl chloride (CPVC) as absorbers. The experiment and benchmark included three configurations mimicking 30 g 239 Pu/L plutonium, 300 g 239 Pu/L plutonium, and 600 g 239 Pu/L plutonium in an aqueous chloride solution. Uncertainties in the benchmark included five broad categories: (1) criticality measurement, (2) mass and density, (3) dimensions, (4) material compositions, and (5) positioning. The largest contribution to the overall uncertainties for all three cases came from the material compositions, in particular the PVC and CPVC absorber compositions. A detailed model was created to be a near match (that is within expectations of transport code users) and a simplified model was created to minimize offset dimensions and expedite modeling for code validation. Sample calculations were completed in MCNP6.3 with ENDF/B-VIII.0 and ENDF/B-VII.1 nuclear data. For the detailed and simplified models, the average difference between the computed and experimental k eff was 951 pcm. CWS will serve as the key validation experiment for nuclear criticality safety in support of aqueous chloride operations. The sensitivity to the chlorine capture cross section is orders of magnitude greater than other existing benchmarks. The current limits, as defined by nuclear criticality safety, are 520 g Pu per batch, i.e. the minimum critical mass of the Pu solution infinitely reflected by water [Criticality Handbook: Volume II, (1969)]. This extremely conservative critical mass limit does not credit any neutron capture by chlorine (in particular neutron capture by 35 Cl) and greatly impedes the throughput required for current and future operations.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Gas-solid reaction pathway for chlorination of rare earth and actinide metals using hydrogen and chlorine gas
Hydriding and chlorination of buttons of metallic cerium have been tested as a head-end step to separating metal impurities from actinides. The objective here was to achieve complete conversion to chlorides while maintaining high surface area via small particles and open porosity. Hydriding by reaction with 100% H 2 gas at 573 K was successful at reducing cm-scale metal buttons into small particles/fragments. This step was followed by reaction with flowing 99.5% anhydrous Cl 2 gas at temperatures ranging from 423 to 573 K for 60 min. In experiments reported here, up to 92% conversion to cerium chloride was achieved from reacting with the anhydrous chlorine gas. The final chloride product has high porosity coupled with small particle sizes (microns to 1600 μm), which makes it suitable for subsequent purification processes. Higher chlorine concentrations in the gas favor higher conversion to chloride. The optimal temperature to achieve high chlorination is 523 K. Oxygen is a minor impurity in the chlorine gas which appears to prevent complete chlorination from being achieved.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity
A complex role for chlorine radicals Radicals are atoms or molecules that are highly reactive because they have an unpaired electron. A common means of investigating whether they are involved in a particular reaction is to try to trap them with an acceptor compound. Yang et al. reinvestigated a photoinduced alkane oxidation reaction for which a trapping study had previously implicated alkoxy radicals. Their spectroscopic, kinetic, and isotopic labeling studies revealed that chlorine, rather than alkoxy, was the key radical intermediate; the prior trapping results had stemmed from its complexation with alcohols. Science , abd8408, this issue p. 847
Science & Technology - Other Topics↗
Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene
Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here, in this work, we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C–Cl bond breaking, which does not involve protons—a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.
Choi, Chungseok↗
Alkyl chain engineering of chlorinated acceptors for elevated solar conversion
Abstract not provided
Mo, Daize↗
Taming the Chlorine Radical: Enforcing Steric Control over Chlorine-Radical-Mediated C?H Activation
Explore the source record for details and available documents.
Gonzalez, Miguel I.↗
In Situ Chlorine Generation and Rare Earth Chlorination by Molten Salt Electrolysis
Not provided.
Nuclear Science & Technology↗
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↗
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↗
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↗
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↗
Synthesis of (oxo)chlorin dimers chelated with thallium(III)
Two target dimers have been prepared for fundamental studies of hole/electron transfer. Metalation with thallium(III) enables clocking of the rate of hole/electron transfer between the two macrocycles. Each dimer contains a diphenylethyne linker joining two identical hydroporphyrins (chlorin or oxochlorin). The linker is substituted at the 4,4′-positions whereas each (oxo)chlorin is joined at the 10-position. Each (oxo)chlorin is equipped with a gem-dimethyl group at the 18-position to stabilize the hydroporphyrin chromophore toward adventitious dehydrogenation and a 3,5-di-tert-butyl group at the 5-position to achieve increased solubilization in organic media. The dimers parallel a prior set of diphenylethyne-linked (oxo)chlorin constructs containing zinc-free base, zinc-zinc, and copper-copper metalation states that have been examined in studies of electronic communication. The building block (oxo)chlorins for preparing the thallium-containing dimers have been prepared in quantities of 32–404 mg, a scale up to 14-fold larger than previously. Thallation of the free base (oxo)chlorin dimers was achieved with excess TlCl 3 ⋅4H 2 O in CH 2 Cl 2 /CH 3 OH (3–4:1) upon overnight reaction at room temperature. The long-wavelength (Q[Formula: see text] absorption band of (oxo)chlorins lies between that of the zinc(II) and free base counterparts. Absorption spectral comparisons are provided of the thallium(III) and free base (oxo)chlorin monomers and dimers.
Chemistry↗
The chlorination and separation of aluminum using low-temperature sulfur chloride reagents
There is currently no strategy for the permanent waste disposal or recycling for used nuclear fuelsfrom research reactors. For this reason, low-temperature reactions have been developed for thechlorination of the Al alloys and subsequent separation from used nuclear fuels to reducethe volume of high-level waste in storage. Three sulfur chloride reagents – S 2 Cl 2 , SOCl 2 , and SO 2 Cl 2 —were tested, and two were found to quantitatively chlorinate Al metal and Al alloys undermild conditions. Further, these low-temperature reactions proceed between 298 and 411 K, and up to 5 gof metal is chlorinated in 1–3 h. Preliminary results indicate that the reactivity and exothermicity ofthe reaction between the Al and sulfur chloride reagents is highly dependent on the surface area-to-volume ratio of the metal and the volume of solvent. Elemental S is produced as a by-productduring the chlorination with S 2 Cl 2 but can be quantitatively rechlorinated under mild conditions toregenerate the initial chlorination reagent. Therefore, in this case, chlorine is the only elementconsumed in the reaction, thus minimizing the waste generated during the chlorination process.The AlCl 3 may then be separated from other materials present in Al 6061 or Al 8001 because of itshigh solubility in the sulfur chloride reagents. This process may also be extended to chlorinate Alfrom research reactor fuels.
aluminum↗
Widespread detection of chlorine oxyacids in the Arctic atmosphere
Chlorine radicals are strong atmospheric oxidants known to play an important role in the depletion of surface ozone and the degradation of methane in the Arctic troposphere. Initial oxidation processes of chlorine produce chlorine oxides, and it has been speculated that the final oxidation steps lead to the formation of chloric (HClO 3 ) and perchloric (HClO 4 ) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO 3 and HClO 4 . Significant levels of HClO 3 were observed during springtime at Greenland (Villum Research Station), Ny-Ålesund research station and over the central Arctic Ocean, on-board research vessel Polarstern during the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) campaign, with estimated concentrations up to 7 × 10 6 molecule cm -3 . The increase in HClO 3 , concomitantly with that in HClO 4 , was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO 3 and HClO 4 by hydroxyl radicals. HClO 3 and HClO 4 are not photoactive and therefore their loss through heterogeneous uptake on aerosol and snow surfaces can function as a previously missing atmospheric sink for reactive chlorine, thereby reducing the chlorine-driven oxidation capacity in the Arctic boundary layer. Our study reveals additional chlorine species in the atmosphere, providing further insights into atmospheric chlorine cycling in the polar environment.
54 ENVIRONMENTAL SCIENCES↗
Constraining the impact of chlorine as a neutron absorber in next-gen fast reactor designs
The role of chlorine as a neutron poison and as a seed for producing radioactive waste in nuclear systems has driven a renewed interest to improve its nuclear data uncertainties. Additionally, basic and applied science programs that use CLYC (Cs 2 LiYCl 6 :Ce) detectors for neutron spectroscopy and monitoring are also very sensitive to any change in chlorine nuclear data for simulations of the detector response. In this work, sensitivities relevant for these different applications are addressed through simulations of the efficiency of CLYC detectors in a fast fission spectrum when applying new chlorine nuclear data as input. These simulations are validated by an experimental measurement using CLYC detectors coupled to an ionization chamber loaded with a 252 Cf spontaneous fission source. The results are then used to obtain the first reliable direct measurement of the 35 Cl(n,p 0 ) and summed Cl(n,p+n,α) fission spectrum average cross sections, found to be 54.7(32) and 105.0(98) mb, respectively. The results are within uncertainty of calculated fission spectrum averaged cross sections based on recently re-evaluated chlorine nuclear data, which confirm recent impact studies performed for the Molten Chloride Reactor Experiment. Meanwhile, there currently exists only one published criticality benchmark experiment that is sufficiently sensitive to chlorine nuclear data. Discrepancies are found with this set of criticality safety benchmarks, which are more sensitive to thermal and epithermal neutron energies than the energies, above 100 keV, tested in this current work. Hence, there is still a need to re-evaluate the chlorine nuclear data at lower energies to assess these discrepancies. Interpretation of the data from future “faster” criticality benchmarks, which are needed for next-gen fast reactor designs, benefit from the improved constraints on the chlorine nuclear data validated in this work.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
A two-stage strategy for upcycling chlorine-contaminated plastic waste
Abstract Chemical upcycling of polyolefin plastic waste to lubricant, wax and fuel-range hydrocarbons over metal-based catalysts is a crucial technological solution to the enormous environmental threat posed by plastic waste. However, currently available methods are incompatible with chlorine-contaminated feedstocks. Here we report a two-stage strategy for upcycling chlorine-contaminated polypropylene. First, magnesia–alumina mixed oxide at 30 bar H 2 and 250 °C serves as a chlorine trap by rapidly forming solid chloride, resulting in nearly complete chlorine extraction from the polyolefin melt. This enables the upcycling of plastic waste with up to 10% polyvinyl chloride content to lubricants over ruthenium-based catalysts, in the second stage. The strategy is also applicable to chlorinated aromatics and alkanes. The proposed strategy renders hydrocracking and hydrogenolysis catalysts less sensitive to the chlorine impurities in feedstocks while eliminating HCl emissions and chlorine contamination in products. It could incentivize further progress in plastics upcycling.
Environmental Sciences & Ecology↗