Chemical Oxidation Research Articles

In English

Biopolymer matrices has been synthesized on the basis of ED-20 epoxy resin and soybean oil (SbO) bearing cyclocarbonate and epoxy groups. Mono(cyanoethyl)diethylenetriamine (UP) and tris(2-hydroxyethyl)amine (TEA) were used as hardeners. Chemical structure, mechanical properties, thermo-oxidative resistance of the samples and their changes after contact with distilled water, alkaline or acidic environment were studied. By means of ATR-FTIR the possible formation of H-NIPU (hybrid non-isocyanate polyurethane) fragments between cyclocarbonate groups of SbO and amino groups of the hardener was demonstrated. Influence of the curing mode and the type of hardener on water absorption, chemical and thermal oxidation resistance of the developed biopolymer matrices was thoroughly investigated. UP-based biopolymer matrices showed water and alkali resistance similar to the ones of neat epoxy polymers, while TEA-based biopolymer matrices showed better resistance to the acidic medium. The thermo-oxidative stability of the chosen samples was revealed by the TGA method in an air atmosphere. It was demonstrated that epoxy polymer cured with TEA hardener were more stable than the one cured with UP hardener. The similar dependence is observed for biopolymer matrices based on TEA hardener. At the same time, the curing mode has almost no effect on ultimate tensile strength value of the samples with ED-20/UP composition. However, the addition of functionalized SbO to the epoxy matrix cured with both TEA and UP hardeners increases the ultimate tensile strength values regardless of the type of oil functionalization. As expected, all biopolymer matrices exhibited higher ultimate tensile strength compared with unmodified epoxy polymers, which provides the possibility of their further application to obtain multi-layered bioplastics.

Non-Invasive Multi-Gas Detection Enabled by Cu-CuO/PEDOT Microneedle Sensor.

Metal-oxide-based gas sensors are extensively utilized across various domains due to their cost-effectiveness, facile fabrication, and compatibility with microelectronic technologies. The copper (Cu)-based multifunctional polymer-enhanced sensor (CuMPES) represents a notably tailored design for non-invasive environmental monitoring, particularly for detecting diverse gases with a low concentration. In this investigation, the Cu-CuO/PEDOT nanocomposite was synthesized via a straightforward chemical oxidation and vapor-phase polymerization. Comprehensive characterizations employing X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and micro Raman elucidated the composition, morphology, and crystal structure of this nanocomposite. Gas-sensing assessments of this CuMPES based on Cu-CuO/PEDOT revealed that the response current of the microneedle-type CuMPES surpassed that of the pure Cu microsensor by nearly threefold. The electrical conductivity and surface reactivity are enhanced by poly (3,4-ethylenedioxythiophene) (PEDOT) polymerized on the CuO-coated surface, resulting in an enhanced sensor performance with an ultra-fast response/recovery of 0.3/0.5 s.

Copper-Catalyzed Tunable Oxygenative Rearrangement of Tetrahydrocarbazoles.

Herein, we report a general copper-catalyzed method for the tunable oxygenative rearrangement of tetrahydrocarbazoles to cyclopentyl-bearing spiroindolin-2-ones and spiroindolin-3-ones. The method demonstrates excellent chemoselectivity, regioselectivity, and product control simply by using the H2O and O2 as oxygen source, respectively. This open-flask method is safe and simple to operate, and no other chemical oxidants are required. Besides, inspired from the unique pathway of 1, 2-migration rearrangement, a highly controllable hydroxylation of indoles for the construction of C3a-hydroxyl iminium indolines was also developed. Mechanistic experiments suggest that a single-electron transfer-induced oxidation process is responsible for the tunable selectivity control.

Effect of Potassium Ferrocyanide on CMP Performance of Ruthenium in H2O2-based Slurries

As feature size of integrated circuits develops to 7 nm, ruthenium is considered the preferred material to replace traditional Ta/TaN barrier layers. Ruthenium can be electroplated without the need for copper seed crystal layers. However, the removal of the ruthenium barrier layer during the polishing process must be addressed. Therefore, this article studies the promoting effect of potassium ferrocyanide (K4Fe(CN)6) and hydrogen peroxide (H2O2) containing silicon slurries on the rate of ruthenium chemical mechanical polishing. Experiments have shown that the polishing rate of ruthenium is significantly improved by the combined action of K4Fe(CN)6 and H2O2. The stronger hydroxyl radicals is the main factor in achieving a high Ru polishing rate, which accelerates the dissolution and removal of Ru layers by converting the hard Ru layer into softer RuO2 and RuO3 oxide layers. The dependencies of the chemical properties (such as electrochemical impedance spectroscopy and surface morphology) proved that the CMP mechanism using Fenton reaction principally performs chemical oxidation and etching dominant CMP simultaneously. This study is expected to provide ideas and insights for the development and design of a new alkaline polishing solution for ruthenium, which is beneficial for the wider application of ruthenium in the field of integrated circuits.

The Enhanced Photoluminescence Properties of Carbon Dots Derived from Glucose: The Effect of Natural Oxidation.

The investigation of the fluorescence mechanism of carbon dots (CDs) has attracted significant attention, particularly the role of the oxygen-containing groups. Dual-CDs exhibiting blue and green emissions are synthesized from glucose via a simple ultrasonic treatment, and the oxidation degree of the CDs is softly modified through a slow natural oxidation approach, which is in stark contrast to that aggressively altering CDs' surface configurations through chemical oxidation methods. It is interesting to find that the intensity of the blue fluorescence gradually increases, eventually becoming the dominant emission after prolonging the oxidation periods, with the quantum yield (QY) of the CDs being enhanced from ~0.61% to ~4.26%. Combining the microstructure characterizations, optical measurements, and ultrafiltration experiments, we hypothesize that the blue emission could be ascribed to the surface states induced by the C-O and C=O groups, while the green luminescence may originate from the deep energy levels associated with the O-C=O groups. The distinct emission states and energy distributions could result in the blue and the green luminescence exhibiting distinct excitation and emission behaviors. Our findings could provide new insights into the fluorescence mechanism of CDs.

Efficient cadmium removal from industrial wastewater generated from smelter using chemical precipitation and oxidation assistance.

The effective treatment of cadmium (Cd) in smelting wastewater is of great industrial importance. This study investigates the efficient removal of Cd from real industrial smelting wastewater via chemical precipitation using a series of experiments. In particular, the effects of different precipitants, agitation conditions, and the addition of NaOCl on Cd removal and pH variation are investigated. CaO (3.75 g/L), NaOH (3.50 g/L), and Ca(OH)2 (3.75 g/L) are found to be effective in elevating the wastewater pH and achieving high Cd removal rates (>99.9%), while the use of NaOH as a precipitant maintains a high Cd removal rate even at low agitation intensities. The properties of the produced sludge and supernatant are also determined using moisture content, particle size, and sludge leaching analyses due to the importance of economic and environmental sustainability in filtration, dewatering, and waste disposal processes. In addition, the addition of 2% NaOCl is tested, revealing that it can improve the Cd removal efficiency of Ca(OH)2, thus potentially reducing processing costs and enhancing the environmental benefits. Overall, these findings offer valuable insights into the removal of Cd from smelting wastewater, with potential implications for both environmental sustainability and economic viability. PRACTITIONER POINTS: CaO, NaOH, and Ca(OH)2 effectively remove Cd (>99.9%) from smelting wastewater. The use of NaOH leads to high Cd removal rates even at low agitation speeds. Adding 2% NaOCl can reduce the Ca(OH)2 dose for more economical Cd removal.

XPS analysis of molecular contamination and sp2 amorphous carbon on oxidized (100) diamond

The efficacy of oxygen (O) surface terminations on diamond is an important factor for the performance and stability for diamond-based quantum sensors and electronics. Given the wide breadth of O-termination techniques, it can be difficult to discern which method would yield the highest and most consistent O coverage. Furthermore, the interpretation of surface characterization techniques is complicated by surface morphology and purity, which if not accounted for will yield inconsistent determination of the oxygen coverage. We present a comprehensive approach to consistently prepare and analyze oxygen termination of surfaces on (100) single-crystalline diamond. We report on x-ray photoelectron spectroscopy (XPS) characterization of diamond surfaces treated with six oxidation methods that include various wet chemical oxidation techniques, photochemical oxidation with UV illumination, and steam oxidation using atomic layer deposition (ALD). Our analysis entails a rigorous XPS peak-fitting procedure for measuring the functionalization of O-terminated diamond. The findings herein have provided molecular-level insights on oxidized surfaces in (100) diamond, including the demonstration of clear correlation between the measured oxygen atomic percentage and the presence of molecular contaminants containing nitrogen, silicon, and sulfur. We also provide a comparison of the sp2 carbon content with the O1s atomic percentage and discern a correlation with the diamond samples treated with dry oxidation which eventually tapers off at a max O1s atomic percentage value of 7.09 ± 0.40%. Given these results, we conclude that the dry oxidation methods yield some of the highest oxygen amounts, with the ALD water vapor technique proving to be the cleanest technique out of all the oxidation methods explored in this work.

Synthesis and characterization of yttrium iron oxide/PPy nanocomposites for supercapacitor application by chemical oxidative polymerization method

ABSTRACT Polypyrrole (PPy)/Yttrium Iron oxide (YIG) nanocomposite was synthesized by the chemical oxidation polymerization method. Yttrium iron oxide is also known as iron yttrium oxide or yttrium iron garnet denoted as YIG (Y3Fe5O12). YIG is a familiar material among the rare earth garnets and is also commonly used in electronic devices. Fourier transform infrared (FT-IR) spectroscopy analysis reveals the strong interaction between PPy and YIG nanoparticles. The crystal structure for the PPy and PPy nanocomposites is observed by X-ray Diffraction (XRD) and the average crystalline size calculated by Scherrer’s formula for PPy/n-YIG is 27.47 nm. Surface morphology of the samples identified by scanning electron microscopy. Optical properties were studied by UV–Vis spectroscopy. From the 2-probe method, AC electrical conductivity for n-YIGPPy is found to be 1.05 × 10−5 S/cm, higher than that of the polypyrrole. The electrochemical performance of PPy and YIG/PPy nanocomposites was observed by cyclic voltammetry (CV). The combination of optical, electrical properties of YIG/PPy nanocomposites suits supercapacitor applications.

Development of Technology for the Bioleaching of Uranium in a Solution of Bacterial Immobilization

This study presents findings regarding the kinetics of ferrous iron oxidation in solution mediated by Acidithiobacillus ferrooxidans bacteria within a continuous-flow bioreactor employing diverse types of immobilizers. The objective is to augment the rate of ferrous iron oxidation in solutions utilizing an immobilizer for Acidithiobacillus ferrooxidans strains. Immobilization represents a promising avenue for enhancing the efficiency of Fe2⁺ oxidation via acidophilic ferrooxidizing bacteria, leading to a several-fold increase in oxidation rate. A comparative analysis was conducted to evaluate the efficacy of different types of immobilizer in facilitating iron oxidation within a continuous-flow bioreactor, including the application of wood chips coated with Fe(OH)3. The results indicate that wood chips coated with iron hydroxide serve as effective type of immobilizer, facilitating the robust attachment of Acidithiobacillus ferrooxidans via electrostatic interactions between negatively charged bacteria and positively charged surfaces. Experimental investigations were conducted using novel immobilization matrices in pilot-scale tests simulating the underground borehole leaching (UBL) of uranium. The bioactivation of leaching solutions enhances the efficiency and environmental compatibility of UBL compared to conventional chemical oxidation methods. The relationships between redox potential and ferric iron content in bioactivated solutions during the UBL of uranium were delineated. The significance of this study lies in its elucidating the pivotal role of Fe2⁺ oxidation in uranium extraction processes, particularly in the context of UBL. By employing bioactivation mediated by Acidithiobacillus ferrooxidans, the study demonstrates not only enhanced uranium extraction efficiency, but also markedly improved environmental sustainability compared to traditional chemical oxidation methods. The findings reveal crucial correlations between redox potential and ferric iron concentration in bioactivated solutions.

Effective strategy for alleviation of oil contamination in marine via the superhydrophobic biochar: Performances, mechanisms and environmental recalcitrance

The performance of layered double hydroxides (LDH)-biochar composite on alleviating oil spill pollution is poorly understood. A superhydrophobic biochar (NCY) was synthesized from the pristine wood chips biochar (WCB) after the surface deposition of NiCo-LDH (NCB) and hydrophobic modification with stearate. The oil removal potential of the designed biochars was investigated via the diesel oil/crude oil adsorption experiments and the environmental recalcitrance evaluation. The compared characterization results revealed that NiCo-LDH was successfully deposited onto biochar matrix via the electrostatic attraction and pore filling effect, which facilitated a special flower-like hierarchical architecture rough surface for biochar and hinder the multi-layer stacking of LDH. Benefit from the constructed hierarchical architecture, the occupancy of oxygen-containing functional groups and hydrophobic modification of stearate, the water contact angle of NCY (156°) was remarkably larger than NCB (117°) and WCB (50.1°), which exhibit a superhydrophobic. The maximum diesel oil sorption capacities of biochars increased from 3.28 g/g in WCB to 5.64 g/g in NCB and 11.6 g/g in NCY, as well as the maximum crude oil sorption capacities of biochars showed a similar trend (WCB: 4.64 g/g, NCB: 8.74 g/g, NCY: 18.6 g/g). Accordingly, NCY showed higher oil adsorption capacity than NCB and WCB mainly due to the enhanced hydrophobic forces and the π-π electron donor-acceptor interaction resulted from lower amount of O-containing functional groups and superhydrophobic surface wettability. Furthermore, the application of LDH remarkably improved the environmental recalcitrance of biochar (resist to the chemical oxidation and thermal decomposition in marine) due to the coating of NiCo-LDH could enhance the bulk stability of biochar and increase the liable carbon content in biochar. This study proved that the application of NiCo-LDH and stearate could be an effective approach for improve the oil pollution remediation capacity and the environmental recalcitrance of biochar.

Surface Finish Enhancement of Si(100) with Single Pole Magnetic Abrasive Finishing using Chemical Oxidizers and Alumina Slurry

Surface Finish Enhancement of Si(100) with Single Pole Magnetic Abrasive Finishing using Chemical Oxidizers and Alumina Slurry

Enhanced reactivity over Ce2(SO4)3/MgO with NiO modification for chemical looping partial oxidation of methane

Chemical looping partial oxidation of methane to syngas is a promising process. Thermodynamic and kinetic analysis both forecast the NiO/Ce2(SO4)3–MgO is a prospective oxygen carrier (OC) to this process, which enables with 100% syngas selectivity, 2.15H2/CO ratio, excellent methane conversion and stable cycling characteristic. Compared with Ce2(SO4)3, the methane conversion rate rise by 73.19% because of the excellent lattice oxygen availability, less carbon deposit, and large specific surface area. The distinctive pore structure also provides a favorable reaction environment. Through the density functional theory, Ni doping can lower the energy barrier (Eb), promote lattice oxygen activation and diffusion, and the oxygen vacancy (Ov) can further promote these processes. CH3 → CH2 + H (TS2) is the rate-limiting step. Compared with Ce2(SO4)3, the Ni doping can reduce Eb by 16.8%, and the Ov can further reduce it by 43.0%. It does not change when the Ov concentration is more than 1.96%.

Electrodeposition of polyaniline on reduced graphene oxide/cotton yarn with tunable electrochemical performance for flexible textile supercapacitors

Graphene/cotton fibers show significant promise in wearable energy storage due to their low cost, porous structure, and exceptional integration ability into wearable systems. However, the eco-unfriendly reductants and standalone electric double-layer capacitor hindered their application. Herein, a green and rapid hydrothermal-electrodeposition method was proposed to fabricate polyaniline (PANI) decorated reduced graphene oxide (rGO)/cotton yarns without using any chemical reductants and oxidants. The PANI/rGO/cotton (PRC) yarn exhibited porous conductive network, structural controllability, and mechanical flexibility. Additionally, the PRC yarn electrode delivers a fast electron transport and ion migration, synergistic energy storage contribution, and a controllable capacitance (up to 81.2 mF cm−1 at 0.2 mA cm−1). The assembled yarn supercapacitor shows a good capacitance (19.8 mF cm−1 at 0.08 mA cm−1), excellent energy-power density (2.7 μWh cm−1 at 40 μW cm−1), and great capacitance retention. This green fabrication of PRC yarns brings new insights into the development of wearable energy storage.

Self-aligned formation of superconducting sub-5 nm PtSi films

Platinum silicide (PtSi) presents a promising superconductor for achieving silicon-based Josephson field-effect transistors (JoFETs). In a viable process flow to realize self-aligned PtSi formation, thermal oxidation at 600 °C is required to form a protective oxide layer on the surface of the as-formed PtSi selectively against Pt to facilitate subsequent selective etch in aqua regia. However, sub-10 nm PtSi films tend to agglomerate and even break into discrete PtSi islands upon thermal treatments above 500 °C. To achieve nanoscale JoFETs, we have developed a simple alternative with chemical oxidation at room temperature leading to the formation of homogeneous sub-5 nm PtSi films. The critical temperature of the resultant superconducting PtSi films is found to increase from 0.66 to 0.90 K when the PtSi thickness is raised from 3.1 to 12.7 nm, while, concurrently, the PtSi grains grow larger in thicker films. The critical temperature also increases from 0.53 to 0.66 K for the 3.1 nm PtSi film when the formation temperature is raised from 400 to 500 °C.

Impact of TEMPO-Oxidation Pretreatment of Red Ginseng Residual on Nanofibrillation

Red ginseng extract is one of the most widely used herbal medicines to prevent and cure various diseases. Among the processed products derived from red ginseng, the water-insoluble part as red ginseng residual (RGR) becomes waste, even though it contains important ingredients. TEMPO-oxidation (TO) can be used as a pre-treatment with different degrees of oxidation (DO) (0 to 0.4) in red ginseng residual (RGR-TO) by introducing chemical oxidation and high-pressure homogenizer (HPH) as a nanofibrillation process. 1H NMR was used to determine the carbohydrate composition and calculate DO, size was examined using a nanoparticle analyzer, and the zeta potential was used to determine surface charge density. RGR-TO with different concentrations had different compositions; glucose and uronic acid were the main ingredients. All treated RGR-TO showed higher oxidant levels than the untreated counterpart (RGR-TO 0). As the oxidant levels increased, the zeta potential and uronic acid increased, but the size of the nanofibril from RGR-TO decreased. The results of this study showed that TEMPO-oxidation pretreatment was effective in producing RGR cellulose nanofibril (CNF) with a variety of properties by adjusting the level of oxidation pretreatment and the number of HPH passes.

Dual-Step Redox Engineering of 2D CoNi-Alloy Embedded B, N-Doped Carbon Layers Toward Tunable Electromagnetic Wave Absorption and Light-Weight Infrared Stealth Heat Insulation Devices.

2D layered metallic graphite composites are promising electromagnetic wave absorption materials (EWAMs) for their combined properties of abundant interlayer free spaces, rich metallic polarized sites, and high conductivity, but the controllable synthesis remains rather challenging. Herein, a dual-step redox engineering strategy is developed by employing cobalt boron imidazolate framework (Co-BIF) to construct 2D CoNi-alloy embedded B, N-doped carbon layers (2D-CNC) as a promising EWAM. In the first step, a chemical etching oxidation process on Co-BIF is used to obtain an optimized 2D-CoNi-layered double hydroxide (2D-CoNi-LDH) intermediate and in the second, high-temperature calcination reduction is implemented to modify graphitization of the degree of the 2D-CNC. The obtained sample delivers superior reflection loss (RLmin) of -60.1dB and wide effective absorption bandwidth (EAB) of 6.24GHz. The synergy mechanisms of interfacial/dipole polarization and magnetic coupling are in-depth evidenced by the hologram and Lorentz electron microscopy, revealing its significant contribution on multireflection and impedance matching. Further theoretical evaluation by COMSOL simulation in different fields based on the dynamic loss process toward the test ring reveals the in situ EW attenuation process. This work presents a strategy to develop multifunctional light-weight infrared stealthy aerogel with superior pressure-resistant, anti-corrosion, and heat-insulating properties for future applications.

Iridium‐Catalyzed Electrooxidative Annulation of Naphthol with Acrylate via C−H Bond Activation for the Synthesis of Naphtho[1,8‐bc]furan

AbstractIridium catalyzed electrochemical coupling of naphthols with acrylates for the syntheses of naphtho[1,8‐bc]furan derivatives are herein reported. Ir‐catalyzed electrochemical C−H annulation is accomplished within a supportive catalysis manifold, paving the way for electrooxidative C−H acrylation via weak O‐coordination. The merge of iridium catalysts and electric current not only minimizes the need for a stoichiometric amount of chemical oxidants but also confirms broad reaction compatibility with a variety of electronically and sterically diverse substrates. This utility provides a valuable method for producing a wide range of naphtho[1,8‐bc]furan derivatives in good to moderate yields.

Sustainable lindane waste remediation: Surfactant-driven residual DNAPL extraction and oxidation in a real landfill (LIFE SURFING)

The LIFE SURFING Project was carried out at the Bailin Landfill in Sabiñánigo, Spain (2020-2022), applying Surfactant Enhanced Aquifer Remediation (SEAR) and In Situ Chemical Oxidation (S-ISCO) in a 60-meter test cell beneath the old landfill, to remediate a contaminated aquifer with dense non-aqueous phase liquid (DNAPL) from nearby lindane production. The project overcame traditional extraction limitations, successfully preventing groundwater pollution from reaching the river.In spring 2022, two SEAR interventions involved the injection of 9.3 m3 (SEAR-1) and 6 m3 (SEAR-2) of aqueous solutions containing 20 g/L of the non-ionic surfactant E-Mulse 3®, with bromide (around 150 mg/L) serving as a conservative tracer. 7.1 and 6.0 m3 were extracted in SEAR-1 and SEAR-2, respectively, recovered 60–70 % of the injected bromide and 30–40 % of the surfactant, confirming surfactant adsorption by the soil. Approximately 130 kg of DNAPL were removed, with over 90 % mobilized and 10 % solubilized. A surfactant-to-DNAPL recovery mass ratio of 2.6 was obtained, a successful value for a fractured aquifer. In September 2022, the S-ISCO phase entailed injecting 22 m3 of a solution containing persulfate (40 g/L), E-Mulse 3® (4 g/L), and NaOH (8.75 g/L) in pulses over 48 h, oxidizing around 20 kg of DNAPL and ensuring low toxicity levels after that.Preceding the SEAR and S-ISCO trials, 2020 and 2021 were dedicated to detailed groundwater flow characterizations, including hydrological and tracer studies. These preliminary investigations allowed the design of a barrier zone between 317 and 557 m from the test cell and the river, situated 900 m away. This zone, integrating alkali dosing, aeration, vapor extraction, and oxidant injection, effectively prevented the escape of fluids to the river. Neither surfactants nor contaminants were detected in river waters post-treatment. The absence of residual phase in test cell wells and reduction of chlorinated compound levels in groundwater were noticed till one year after S-ISCO.

Sequential oxidation-composting-phytoremediation treatment for the management of an oily sludge from petroleum refinery

Oily sludges are generated in large quantities in petroleum refinery wastewater treatment plants. Given their complex composition, they are classified as hazardous waste. Selecting a single treatment technique for their remediation is challenging.This work aims to assess the extent of composting followed by phytoremediation on an oily sludge from an API separator unit, pre-treated by chemical oxidation with alkaline activated persulfate (PS). 18% of total petroleum hydrocarbons (TPH) were determined by IR spectroscopy. The aliphatic hydrocarbon content was 4714 ± 250 ppm by GC-FID, and aromatics were not detectable, suggesting a high amount of non-chromatographable complex hydrocarbons. The density of generalist and hydrocarbon-degrading populations of the oily sludge estimated by quantitative polymerase chain reaction (qPCR) evidenced an autochthonous microbiota with hydrocarbon-degrading capacity. The oxidative treatment with PS removed 31% of the TPH determined by IR after 20 days. The significant reduction of the native bacterial community was counterbalanced by coupling a composting treatment. Co-composting the sludge with goat manure and oat straw produced, after a year, a 96% reduction in TPH content, regardless of the oxidative pretreatment. Organic matter transformation was evidenced by the decrease of dissolved organic carbon (DOC) and the variation in E4/E6 ratio. The matrices obtained of composting were used as substrates for phytoremediation for 4 months. Ryegrass seeds were planted in both PS-treated and untreated sludge substrates. The presence of the plant grown in the pre-oxidised and composted substrate resulted in a higher aerial biomass of ryegrass (67%), an increase in enzymatic activities, and higher concentration of DOC, although without evidence of additional dissipation of TPH.The dynamics of the bacterial communities of the different substrates generated during the biological treatment were analyzed by Illumina NovaSeq DNA sequencing of 16S rRNA amplicons. The findings mirrored a succession compatible with that described in contaminated matrices, but also in other non-contaminated ones.According to these findings, an organic matter transformation process occurred, which included the complex hydrocarbons of the oily sludge, resulting in an active substrate that promoted the retention of nutrients and water and provided the necessary support for plant development.

Computational Analysis of Low Overpotential Ammonia Oxidation by Metal-Metal Bonded Ruthenium Catalysts, and Predictions for Related Osmium Catalysts.

The catalyzed electrochemical oxidation of ammonia to nitrogen (AOR) is an important fuel-cell half-reaction that underpins a future nitrogen-based energy economy. Our laboratory has reported spontaneous chemical and electrochemical oxidation of ammonia to dinitrogen via reaction of ammonia with the metal-metal bonded diruthenium complex Ru2(chp)4OTf (chp- = 2-chloro-6-hydroxypyridinate, TfO- = trifluoromethanesulfonate). This complex facilitates electrocatalytic ammonia oxidation at mild applied potentials of -255 mV vs ferrocene, which is the [Ru2(chp)4(NH3)]0/+ redox potential. We now report a comprehensive computational investigation of possible mechanisms for this reaction and electronic structure analysis of key intermediates therein. We extend this analysis to proposed second-generation electrocatalysts bearing structurally similar fhp and hmp (2-fluoro-6-hydroxypyridinate and 2-hydroxy-6-methylpyridinate, respectively) equatorial ligands, and we further expand this study from Ru2 to analogous Os2 cores. Predicted M24+/5+ redox potentials, which we expect to correlate with experimental AOR overpotential, depend strongly on the identity of the metal center, and to a lesser degree on the nature of the equatorial supporting ligand. Os2 complexes are easier to oxidize than analogous Ru2 complexes by ∼640 mV, on average. In contrast to mono-Ru catalysts, which oxidize ammonia via a rate-limiting activation of the strong N-H bond, we find lowest-energy reaction pathways for Ru2 and Os2 complexes that involve direct N-N bond formation onto electrophilic intermediates having terminal amido, imido, or nitrido groups. While transition state energies for Os2 complexes are high, those for Ru2 complexes are moderate and notably lower than those for mono-Ru complexes. We attribute these lower barriers to enhanced electrophilicity of the Ru2 intermediates, which is a consequence of their metal-metal bonded structure. Os2 intermediates are found to be, surprisingly, less electrophilic, and we suggest that Os2 complexes may require access to oxidation states higher than Os25+ in order to perform AOR at reasonable reaction rates.