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At least 37 records · Page 2

Nanoscale and Microscale Iron Emulsions for Treating DNAPL

This study demonstrated the feasibility of using emulsified nanoscale and microscale iron particles to enhance dehalogenation of (Dense Non-Aqueous Phase Liquid) DNAPL free-phase. The emulsified system consisted of a surfactant-stabilized, biodegradable oil-in-water emulsion with nanoscale or microscale iron particles contained within the emulsion droplets. It was demonstrated that DNAPLs, such as trichloroethene (TCE), diffuse through the oil membrane of the emulsion particle whereupon they reach an aqueous interior and the surface of an iron particle where dehalogenation takes place. The hydrocarbon reaction by-products of the dehalogenation reaction, primarily ethene (no chlorinated products detected), diffuse out of the emulsion droplet. This study also demonstrated that an iron-emulsion system could be delivered in-situ to the DNAPL pool in a soil matrix by using a simulated push well technique. Iron emulsions degraded pure TCE at a rate comparable to the degradation of dissolved phase TCE by iron particles, while pure iron had a very low degradation rate for free-phase TCE. The iron-emulsion systems can be injected into a sand matrix where they become immobilized and are not moved by flowing water. It has been documented that surfactant micelles possess the ability to pull pooled TCE into emulsion droplets where degradation of TCE takes place.

Geiger, Cherie L.↗

Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

HALOGENATED ALIPHATC HYDROCARBONS↗

Formula for the Removal and Remediation of Polychlorinated Biphenyls in Painted Structures

An activated metal treatment system (AMTS) removes and destroys polychlorinated biphenyls (PCBs) found in painted structures or within the binding or caulking material on structures. It may be applied using a "paint-on and wipe-off" process that leaves the structure PCB-free and virtually unaltered in physical form. AMTS is used in conjunction with a solvent solution capable of donating hydrogen atoms. AMTS as a treatment technology has two functions: first, to extract PCBs from the material, and second, to degrade the extracted PCBs. The process for removing PCBs from structures is accomplished as an independent step to the degradation process. The goal is to extract the PCBs out of the paint, without destroying the paint, and to partition the PCBs into an environmentally friendly solvent. The research to date indicates this can be accomplished within the first 24 hours of AMTS contact with the paint. PCBs are extremely hydrophobic and prefer to be in the AMTS over the hardened paint or binder material. The solvent selected must be used to open, but not to destroy, the paint s polymeric lattice structure, allowing pathways for PCB movement out of the paint and into the solvent. A number of solvent systems were tested and are available for use within the AMTS. The second process of the AMTS is the degradation or dehalogenation of the PCBs. The solvent selection for this process is limited to solvents that are capable of donating a hydrogen atom to the PCB structure. Additional AMTS formulation properties that must be addressed for each site-specific application include viscosity and stability. The AMTS must be thick enough to remain where it is applied. Several thickening agents have been tested. Adding a stabilizing agent ensures that the AMTS will not evaporate and leave unprotected, activated metal exposed. During AMTS formulation testing, a number of reagents were evaluated to ensure the rate of dehalogenation was not inhibited by its addition to the system.

Quinn, Jacqueline↗

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Quinn, Jacqueline↗

Metagenome-Guided Proteomic Quantification of Reductive Dehalogenases in the Dehalococcoides mccartyi -Containing Consortium SDC-9

At groundwater sites contaminated with chlorinated ethenes, fermentable substrates are often added to promote reductive dehalogenation by indigenous or augmented microorganisms. Contemporary bioremediation performance monitoring relies on nucleic acid biomarkers of key organohalide-respiring bacteria, such as Dehalococcoides mccartyi (Dhc). In this work, metagenome sequencing of the commercial, Dhc-containing consortium, SDC-9, identified 12 reductive dehalogenase (RDase) genes, including pceA (two copies), vcrA, and tceA, and allowed for specific detection and quantification of RDase peptides using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Shotgun (i.e., untargeted) proteomics applied to the SDC-9 consortium grown with tetrachloroethene (PCE) and lactate identified 143 RDase peptides, and 36 distinct peptides that covered greater than 99% of the protein-coding sequences of the PceA, TceA, and VcrA RDases. Quantification of RDase peptides using multiple reaction monitoring (MRM) assays with 13 C-/ 15 N-labeled peptides determined 1.8 × 10 3 TceA and 1.2 × 10 2 VcrA RDase molecules per Dhc cell. Ultimately, the MRM mass spectrometry approach allowed for sensitive detection and accurate quantification of relevant Dhc RDases and has potential utility in bioremediation monitoring regimes.

59 BASIC BIOLOGICAL SCIENCES↗

Accessing Photoredox Transformations with an Iron(III) Photosensitizer and Green Light

Efficient excited-state electron transfer between an iron(III) photosensitizer and organic electron donors was realized with green light irradiation. This advance was enabled by the use of the previously reported iron photosensitizer, [Fe(phtmeimb) 2 ]+ (phtmeimb = {phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate}, that exhibited long-lived and luminescent ligand-to-metal charge transfer (LMCT) excited states. A benchmark dehalogenation reaction was investigated with catalytic yieldsthat exceed 90% and an enhanced stability relative to the prototypical photosensitizer [Ru(bpy) 3 ] 2+ . The initial catalytic step is electron transfer from an amine to the photoexcited iron sensitizer that is shown to occur with a large cage-escape yield. For LMCT excited states, this reductive electron transfer is vectoral and may be a general advantage of Fe(III) photosensitizers. In-depth time-resolved spectroscopic methods, that include transient absorption characterization from the ultraviolet to the infrared regions, provided a quantitative description of the catalytic mechanism with associated rate constants and yields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Road Map for Developing Iron Phosphate Waste Forms for Salt Wastes

In this report, issues that must be addressed to advance the technology readiness level of phosphate glass waste forms being developed to immobilize high-level radioactive salt waste streams are identified, the states of understanding various technical aspects of formulation, processing, and performance are summarized, and approaches supporting further development are recommended. Processing results in dehalogenation of the waste salt, capture of the gaseous halide-bearing species, and immobilization of the residual salt components in a phosphate glass waste form. The approach is suitable for high-level salt waste from electrochemical reprocessing and molten salt reactors. The technology has been demonstrated for chloride-based salts and may also be suitable for the treatment and immobilization of fluoride-based and iodide-bearing waste salts. Aspects of the process requiring further development are identified and approaches recommended.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution

Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe 0 ) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application. Here, nFe 0 crystals are designed with electron shuttles and improved hydrophobic nature based on elemental chalcophile-siderophile characteristics, where chalcophile-siderophile S served as a bridge to allow impregnating nFe 0 crystals with weakly siderophile and strongly chalcophile Cu. Even impregnations of lattice chalcophile-siderophile elements into the nFe 0 crystals are evidenced at both intraparticle and individual-particle levels. The modulated Fe microenvironment and physicochemical properties broke the reactivity-selectivity-longevity-stability trade-off. Compared to nFe 0 , superhydrophobic Cu─S─nFe 0 with lattice expansion promoted dechlorination by 20-fold but inhibited HER by 150-fold, utilizing ≈80–100% electrons from the Fe 0 reservoir. This work demonstrates the concept of engineering nFe 0 lattice with tunable structure-property relationships, mimicking reductive dehalogenases by selectively interacting with halocarbon functional groups for efficient dehalogenation and sustainable groundwater remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assembling Phenothiazine into a Porous Coordination Cage to Improve Its Photocatalytic Efficiency for Organic Transformations

Abstract Photo‐catalysis by small‐molecules is often limited by catalyst degradation and low electron‐transfer efficiency. Herein we report a stable N‐phenyl‐phenothiazine (PTH)‐derived porous coordination cage (PCC) as a highly efficient photocatalyst. By the incorporation of the photocatalytic PTH moiety into a PCC, aggregation‐induced quenching (AIQ) was shown to be reduced. An improvement in catalyst stability was discovered, ascribed to the synergistic effects of the PTH moieties. The catalyst, operating through a photolytic single‐electron transfer, was utilized for photo‐catalyzed dehalogenation and borylation. Evaluation of the catalytic mechanism in the borylation reaction showed that the improved performance results from the more efficient formation of the electron donor‐acceptor (EDA) complex with the cage. This discovery provides a potential strategy to improve the photophysical properties and stabilities of small‐molecule organic photocatalysts via supramolecular chemistry.

Chemistry↗

Palladium Single-Atom (In)Stability Under Aqueous Reductive Conditions

Here, we investigate the stability and performance of single-atom Pd on TiO 2 for the selective dechlorination of 4-chlorophenol. A challenge inherent to single atoms is their high surface free energy, which results in a tendency for the surface migration and aggregation of metal atoms. This work evaluates various factors affecting the stability of Pd single-atoms, including atomic dispersion, coordination environment, and substrate properties, under reductive aqueous conditions. The transition from single atoms to clusters vastly enhanced dechlorination kinetics without diminishing carbon–chlorine bond selectivity. X-ray absorption spectroscopy analysis using both in situ and ex situ conditions followed the dynamic transformation of single atoms into amorphous clusters, which consist of a unique unsaturated coordination environment and few nanometer diameter. Importantly, the intricate relationship between stability and performance underscores the vital role of detailed characterization to properly determine the true active species for dehalogenation reactions.

36 MATERIALS SCIENCE↗

Electrochemical Salt Wasteform Development: A Review of Salt Treatment and Immobilization Options

Electrochemical reprocessing, also referred to as pyroprocessing, is a technique for recycling actinides from used nuclear fuel (UNF) to produce fuel for future reactors. Here, UNF is dissolved in a molten salt (e.g., LiCl-KCl eutectic) within an electrorefiner. After UNF dissolution, fission products are released into the electrolyte salt and converted to chlorides. This paper discusses wasteform options for processing the base electrolyte salt with the fission product salts as well as just the rare-earth fission products (as RECl 3 , REOCl, or REO x ) with the intent of finding optimal methods for reducing total waste salt volumes or partitioning the salt for alternate wasteform options. Furthermore, two of the more detailed partitioning options discussed herein include halide removal from the salt (dehalogenation), which accounts for more than half of the salt on a molar basis, and RE fission product removal for wasteforms with high-RE loadings. Wasteform properties are compared with emphasis on wasteform volume starting from a given amount of (1) total salt cations or (2) RE cations. Comparisons are also made of wasteform chemical durabilities, with the data available from like testing methods. A main conclusion from this work is the justification of subsequent salt processing after electrorefiner operations for achieving significant wasteform volume reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pathways of CdS Quantum Dot Degradation during Photocatalysis: Implications for Enhancing Stability and Efficiency for Organic Synthesis

CdS quantum dots (QDs) are widely employed as photocatalysts for reactions such as hydrogen evolution, and their degradation under aerobic aqueous conditions is well understood. However, despite evidence of aggregation and precipitation of CdS QD photocatalysts under anaerobic conditions, catalyst speciation and degradation under such conditions are underexplored. In this work, we demonstrate that during a reductive dehalogenation reaction, CdS QDs undergo surface ligand etching, which leads to a loss of colloidal stability and the formation of microcrystalline cadmium metal deposits. We hypothesize that this results from the accumulation of electrons on the QD surface. In addition, we demonstrate mild surface sulfur oxidation and the formation of an ammonium salt byproduct of a commonly used hole quencher. Furthermore, this work adds to our atomic-level understanding of the reactions occurring at the QD surface during photocatalysis, so that we can design more stable and efficient photocatalysts for organic synthesis.

cadmium sulfide↗

Sterically Encumbered Aryl Isocyanides Extend Excited-State Lifetimes and Improve the Photocatalytic Performance of Three-Coordinate Copper(I) β-Diketiminate Charge-Transfer Chromophores

Copper(I) complexes are prominent candidates to replace noble metal-based photosensitizers. We recently introduced a three-coordinate design for copper(I) charge-transfer chromophores that pair β-diketiminate ligands with aryl isocyanides. The excited-state lifetime in these compounds can be extended using a bichromophoric “triplet reservoir” strategy, which comes at the expense of a decrease in excited-state energy and reducing power. In this work, we introduce a complementary, sterically driven strategy for increasing the excited-state lifetimes of these photosensitizers, which gives a higher-energy, more strongly reducing charge-transfer triplet state than does the bichromophore approach. The compounds presented (Cu1–Cu4) have the general formula Cu(CyNacNac Me )(CN-Ar), where CyNacNac Me is a cyclohexyl-substituted β-diketiminate and CN-Ar is an aryl isocyanide with a variable steric profile. Their structural features and electrochemical and photophysical properties are described. The complexes with sterically encumbered 2,6-diisopropylphenyl or m-terphenyl isocyanide ligands (Cu2–Cu4) exhibit prolonged excited-state lifetimes relative to those of the parent 2,6-dimethylphenyl isocyanide compound Cu1. Specifically, one of the m-terphenyl isocyanide compounds, Cu3, displays an excited-state lifetime of 276 ns, approximately 30 times longer than that of Cu1 (9.3 ns). The photoluminescence quantum yield of Cu3 (0.09) also increases by two orders of magnitude compared to that of Cu1 (0.0008). Furthermore, the strong excited-state reducing power (*E ox = –2.4 V vs Fc +/0 ) and long lifetime of Cu3 lead to higher yields in photoredox and photocatalytic isomerization reactions, which include dehalogenation and/or hydrodgenation of benzophenone substrates, C–O bond activation of a lignin model substrate, and photocatalytic E/Z isomerization of stilbene.

14 SOLAR ENERGY↗

Mechanistic investigation of a visible light mediated dehalogenation/cyclisation reaction using iron( iii ), iridium( iii ) and ruthenium( ii ) photosensitizers

The mechanism of a visible light-driven dehalogenation/cyclization reaction was investigated using ruthenium(II), iridium(III) and iron(III) photosensitizers by means of steady-state photoluminescence, time-resolved infrared spectroscopy, and nanosecond/femtosecond transient absorption spectroscopy. The nature of the photosensitizer was found to influence the product distribution such that the dehalogenated, non-cyclized products were only detected for the iron photosensitizer. Strikingly, with the iron photosensitizer, large catalytic yields required a low dielectric solvent such as dichloromethane, consistent with a previous publication. This low dielectric solvent allowed ultrafast charge-separation to outcompete geminate charge recombination and improved cage escape efficiency. Finally, the identification of reaction mechanisms unique to the iron, ruthenium, and iridium photosensitizer represents progress towards the long-sought goal of utilizing earth-abundant, first-row transition metals for emerging energy and environmental applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating the photophysical and photochemical characteristics of green-emitting cerium(III) mono-cyclooctatetraenide complexes

The photophysical and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(III) complexes: [(C 8 H 8 )Ce(μ-X)(THF) 2 ] 2 X = O 3 SCF 3 - (1), Cl - (2), were studied. Here, in the course of these studies, a new polymorph of [(C 8 H 8 )Ce(μ-O 3 SCF 3 )(THF) 2 ] 2 (1) was described. Photoluminescence (PL) studies of 1 and 2 showed characteristic excitation and emission bands in the visible region, with bright green light emission under light irradiation from states corresponding to the 5d → 4f transition. Complexes 1 and 2 exhibit relatively long lifetime of 205.4 ± 0.2 and 145.8 ± 0.4 ns respectively. And the quantum yields (Φ) for 1 and 2 are 0.180 and 0.068 respectively. Electrochemical studies were performed on complexes 1 and 2 with a reversible Ce(III)/Ce(IV) redox couple recorded at $E_{1/2}$ = -1.53 V versus the Fc/Fc + for 2. Complex 1 shows an irreversible Ce(III/IV) oxidation wave. Complexes 1 and 2 revealed strongly-reducing, estimated, excited state reduction potentials ($E^*_{1/2}$) of -3.31 and -4.02 V versus the Fc/Fc + respectively, with small Stokes shifts of 0.12 eV. With their associated relatively long lifetimes, small Stokes shifts and large, negative $E^*_{1/2}$ values, both complexes were evaluated as potential photosensitisers for halogen atom transfer (XAT) using a test reaction of the dehalogenation of benzyl chloride.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing the activity of Pd ensembles on graphene by manipulating coordination environment

Atomic dispersion of metal catalysts on a substrate accounts for the increased atomic efficiency of single-atom catalysts (SACs) in various catalytic schemes compared to the nanoparticle counterparts. However, lacking neighboring metal sites has been shown to deteriorate the catalytic performance of SACs in a few industrially important reactions, such as dehalogenation, CO oxidation, and hydrogenation. Metal ensemble catalysts (M n ), an extended concept to SACs, have emerged as a promising alternative to overcome such limitation. Inspired by the fact that the performance of fully isolated SACs can be enhanced by tailoring their coordination environment (CE), we here evaluate whether the CE of M n can also be manipulated in order to enhance their catalytic activity. We synthesized a set of Pd ensembles (Pd n ) on doped graphene supports (Pd n /X-graphene where X = O, S, B, and N). We found that introducing S and N onto oxidized graphene modifies the first shell of Pd n converting Pd–O to Pd–S and Pd–N, respectively. Also, we further found that the B dopant significantly affected the electronic structure of Pd n by serving as an electron donor in the second shell. We examined the performance of Pd n /X-graphene toward selective reductive catalysis, such as bromate reduction, brominated organic hydrogenation, and aqueous-phase CO 2 reduction. We observed that Pd n /N-graphene exhibited superior performance by lowering the activation energy of the rate-limiting step, i.e., H 2 dissociation into atomic hydrogen. The results collectively suggest controlling the CE of SACs in an ensemble configuration is a viable strategy to optimize and enhance their catalytic performance.

36 MATERIALS SCIENCE↗

In Situ Remediation of Polychlorinated Bephenyls Using Palladium Coated Iron or Magnesium

The remediation of polychlorinated biphenyls (PCBs) and other chlorinated synthetic aromatic compounds are of great concern due to their toxicity and persistence in the environment. When released into the environment, PCBs are sorbed to particulate matter that can then disperse over large areas. Although the US Environmental Protection Agency (EPA) has banned the manufacture of PCBs since 1979, they are still present in the environment posing possible adverse health affects to both humans and animals. Thus, it is of utmost importance to develop a method that remediates PCB-contaminated soil, sediments, and water. The objective of our research was to develop an in-situ PCB remediation technique that is applicable for the treatment of soils and sediments. Previous research conducted at the University of Central Florida (UCF) proved the feasibility of using an emulsified system to dehalogenate a dense non-aqueous phase liquid (DNAPL) source, such as TCE, in the subsurface by means of an in-situ injection. The generation of a hydrophobic emulsion system drew the DNAPL TCE, through the oil membrane where it diffused to the iron particle and underwent degradation. TCE continued to enter, diffuse, degrade and exit the droplet maintaining a concentration gradient across the membrane, thus maintaining the driving force of the reaction.

Geiger, Cherie L.↗

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

Quinn, Jacqueline W.↗