Agostic Research Articles

T-shaped 14 Electron Rhodium Complexes: Potential Active Species in C-H Activation.

Two T-shaped 14-electron rhodium complexes 2a and 2b, "framed" and thus stabilized by PNP pincer ligands have been synthesized. The bis(t-butyl)phosphine derived PNPtBu-rhodium 2a was isolated from pentane as the more stable cyclometalated Rh(III) hydrido complex and found to be in equilibrium with the T-shaped 14e-Rh(I) complex 2aT which itself could be directly crystallized upon change of the solvent. The cyclometallation is suppressed using an adamantyl substituted PNPAd ligand to give the analogous T-shaped Rh(I) species 2b, stabilized through an agostic interaction with one of the adamantyl C-Hs. Depending on the solvent, complex 2a reacted with ethylene either by π-coordination (4a) or C-H activation giving a hydrido-vinyl Rh(III) species 4b, both isomers being in equilibrium in solution. Complex 2b C-H was found to reversibly activate arenes to form the hydrido-aryl Rh(III) complexes.

T‐shaped 14 Electron Rhodium Complexes: Potential Active Species in C‐H Activation

Two T‐shaped 14‐electron rhodium complexes 2a and 2b, "framed" and thus stabilized by PNP pincer ligands have been synthesized. The bis(t‐butyl)phosphine derived PNPtBu‐rhodium 2a was isolated from pentane as the more stable cyclometalated Rh(III) hydrido complex and found to be in equilibrium with the T‐shaped 14e‐Rh(I) complex 2aT which itself could be directly crystallized upon change of the solvent. The cyclometallation is suppressed using an adamantyl substituted PNPAd ligand to give the analogous T‐shaped Rh(I) species 2b, stabilized through an agostic interaction with one of the adamantyl C‐Hs. Depending on the solvent, complex 2a reacted with ethylene either by π‐coordination (4a) or C‐H activation giving a hydrido‐vinyl Rh(III) species 4b, both isomers being in equilibrium in solution. Complex 2b C‐H was found to reversibly activate arenes to form the hydrido‐aryl Rh(III) complexes.

Synergistic bioremediation of petroleum-contaminated soil using immobilized consortium of Rhodococcus rhodochrous and Bacillus subtilis laccase

Petroleum-contaminated soil represents a significant environmental and public health challenge on a global scale. Microbial bioremediation has shown potential, yet the role of enzymes in enhancing petroleum degradation remains underexplored. In this study, the synergistic effects of Rhodococcus rhodochrous (R.rh) and Bacillus subtilis-derived laccase (BsLac) was investigated in the remediation of petroleum-contaminated soil. Immobilized R.rh (PSIMRH) and BsLac (ADIMLac) exhibited higher petroleum degradation rates than their free state, achieving 78.3% and 56.3% degradation in liquid systems, respectively. The combined treatment of PSIMRH and ADIMLac demonstrated a synergistic effect on petroleum degradation, achieving 43.6% with a maximum degradation constant of 0.0335 d−1, representing a 202.7% improvement over untreated soil. PSIMRH enhanced petroleum degradation through microbial metabolism, while ADIMLac accelerated the initial breakdown of complex hydrocarbons into simpler, more bioavailable ones via enzymatic oxidation, providing growth substrates for microbes and significantly improving petroleum degradation rates. The microbial analysis revealed an increase abundance of known petroleum-degrading bacterial genera, including Rhodococcus, Lysobacter, Micromonospora, and Streptomyces. However, the presence of BsLac appeared to reduce the competitive advantage of Rhodococcus, promoting the proliferation of indigenous strains like Lysobacter and Streptomyces. These results suggest that enzyme-microbe synergy can enhance the bioremediation process by altering microbial community dynamics and accelerating petroleum degradation. This study attempts to remediate petroleum-contaminated pollution with the combined use of strains and enzymes, providing a new approach for the remediation of other pollution problems.

Mathematical Modelling of the Impact of IR Laser Radiation on an Oncoming Flow of Nanoparticles with Methane

Introduction. The study is devoted to the numerical investigation of laser radiation’s effect on an oncoming two-phase flow of nanoparticles and multicomponent hydrocarbon gases. Under such exposure, the hydrogen content in the products increases, and methane is bound into more complex hydrocarbons on the surface of catalytic nanoparticles and in the gas phase. The hot walls of the tube serve as the primary source of heat for the reactive two-phase medium containing catalytic nanoparticles. Materials and Methods. The main method used is mathematical modelling, which includes the numerical solution of a system of equations for a viscous gas-dust two-phase medium, taking into account chemical reactions and laser radiation. The model accounts for the two-phase gas-dust medium’s multicomponent and multi-temperature nature, ordinary differential equations (ODEs) for the temperature of catalytic nanoparticles, ODEs of chemical kinetics, endothermic effects of radical chain reactions, diffusion of light methyl radicals CH3 and hydrogen atoms H, which initiate methaneconversion, as well as absorption of laser radiation by ethylene and particles. Results. The distributions of parameters characterizing laminar subsonic flows of the gas-dust medium in an axisymmetric tube with chemical reactions have been obtained. It is shown that the absorption of laser radiation by ethylene in the oncoming flow leads to a sharp increase in methane conversion and a predominance of aromatic compounds in the product output. Discussion and Conclusion. Numerical modelling of the dynamics of reactive two-phase media is of interest for the development of theoretical foundations for the processing of methane into valuable products. The results obtained confirm the need for joint use of mathematical modelling and laboratory experiments in the development of new resource-saving and economically viable technologies for natural gas processing.

Hydrocarbonoclastic Biofilm-Based Microbial Fuel Cells: Exploiting Biofilms at Water-Oil Interface for Renewable Energy and Wastewater Remediation.

Microbial fuel cells (MFCs) represent a promising technology for sustainable energy generation, which leverages the metabolic activities of microorganisms to convert organic substrates into electrical energy. In oil spill scenarios, hydrocarbonoclastic biofilms naturally form at the water-oil interface, creating a distinct environment for microbial activity. In this work, we engineered a novel MFC that harnesses these biofilms by strategically positioning the positive electrode at this critical junction, integrating the biofilm's natural properties into the MFC design. These biofilms, composed of specialized hydrocarbon-degrading bacteria, are vital in supporting electron transfer, significantly enhancing the system's power generation. Next-generation sequencing and scanning electron microscopy were used to characterize the microbial community, revealing a significant enrichment of hydrocarbonoclastic Gammaproteobacteria within the biofilm. Notably, key genera such as Paenalcaligenes, Providencia, and Pseudomonas were identified as dominant members, each contributing to the degradation of complex hydrocarbons and supporting the electrogenic activity of the MFCs. An electrochemical analysis demonstrated that the MFC achieved a stable power output of 51.5 μW under static conditions, with an internal resistance of about 1.05 kΩ. The system showed remarkable long-term stability, which maintained consistent performance over a 5-day testing period, with an average daily energy storage of approximately 216 mJ. Additionally, the MFC effectively recovered after deep discharge cycles, sustaining power output for up to 7.5 h before requiring a recovery period. Overall, the study indicates that MFCs based on hydrocarbonoclastic biofilms provide a dual-functionality system, combining renewable energy generation with environmental remediation, particularly in wastewater treatment. Despite lower power output compared to other hydrocarbon-degrading MFCs, the results highlight the potential of this technology for autonomous sensor networks and other low-power applications, which required sustainable energy sources. Moreover, the hydrocarbonoclastic biofilm-based MFC presented here offer significant potential as a biosensor for real-time monitoring of hydrocarbons and other contaminants in water. The biofilm's electrogenic properties enable the detection of organic compound degradation, positioning this system as ideal for environmental biosensing applications.

Development of deep learning software to improve HPLC and GC predictions using a new crown-ether based mesogenic stationary phase and beyond

The application of AI to analytical and separative sciences is a recent challenge that offers new perspectives in terms of data prediction. In this work, we report an AI-based software, named Chrompredict 1.0, which based on chromatographic data of a novel mesogenic crown ether stationary phase (CESP). Its molecular design represents a significant advancement due to the unique combination of properties and binding capabilities, including the formation of a cavity, mesogenic behavior via mobile chains, and a range of polar and non-polar interactions (aromatic rings, N=N and O=O double bonds, alkyl chains, π–π interactions, and hydrogen bonding). The mesogenic phase is effective in both normal and reversed-phase chromatography, enhancing the software's adaptability across diverse datasets.Here we introduce for the first time an unprecedented scientific approach, integrating deep learning techniques with the novel CESP, which demonstrates exceptional thermal and analytical performance in both liquid chromatography modes, especially in the separation of complex hydrocarbon isomers. This ability enables the results obtained with CESP to extend across various types of stationary phases.Leveraging these insights, a comprehensive chromatographic dataset on a series of aromatic and polyaromatic molecules interacting with our CESP was used to train a Deep Learning Model (DLM). This model is embedded within a user-friendly software, Chrompredict 1.0, designed for predicting chromatographic parameters (MAE = 0.042, R² = 0.95) by selecting chemical descriptors directly from SMILES notation. It offers a deeper understanding of molecular structure and interactions through exploratory data analysis, identifying key factors affecting model accuracy and chromatographic behavior.Users can configure hyperparameters, choose from six machine learning models, and compare their performance with DLM. Chrompredict 1.0 excels in retention behavior prediction for compounds with known structures, and it accurately predicts chromatographic retention and thermal characteristics for different temperatures in HPLC and GC. The model has been successfully tested with METLIN database of 1,023 small molecules of diverse structures and polarities (R² > 0.75, error range ±7.8 s). Overall, the CESP, combined with Chrompredict 1.0, offers a robust tool for intelligent chromatographic analysis, encompassing chemo-informatics, statistical analysis, and graphical capabilities across a broad range of compounds and stationary phases.

The Dustiest Galactic S Stars: Mid-infrared Spectra from SOFIA/FORCAST

We present spectra of 12 of the reddest, and hence dustiest, S stars in the Milky Way, observed with the FORCAST grisms on SOFIA. S stars are asymptotic giant branch (AGB) stars with C/O ∼ 1, so their molecular and dust chemistries are dominated by neither O nor C, often leading to atypical spectral features from their molecules and dust grains. All of the stars in our sample have strong dust emission features at 10–11 μm, but the shape of the feature in most of the stars differs from the shapes commonly observed in either oxygen-rich or carbon-rich AGB stars. Two stars also show the 13 μm feature associated with crystalline alumina. Two have a water absorption band at ∼6.5–7.5 μm, and a third has a tentative detection, but only one of these three has the more common SiO absorption band at 7.5 μm. Three others show a red 6.3 μm emission feature from complex hydrocarbons consistent with “Class C” objects, and in a fourth it appears at 6.37 μm, redder than even the standard Class C hydrocarbon feature. Class C spectra typically indicate complex hydrocarbons that have been less processed by UV radiation, resulting in more aliphatic bonds relative to aromatic bonds. None of the S stars show a strong 11.3 μm hydrocarbon feature, which is also consistent with the presence of aliphatic hydrocarbons.

Isolation, Characterization and Optimization of Indigenous Petrol Degrading Bacteria from Oil Contaminated Soil

Petroleum-derived products like petrol, containing complex hydrocarbons, have catastrophic environmental effects, posing a universal challenge. Bioremediation is known as eco-friendly and safe technique for removal of hydrocarbon pollutants. In this study, indigenous bacteria were isolated from oil contaminated soils and screened for their biodegradation potential. The bacterial enrichment and isolation were done using selective media Bushnell-Haas supplemented with petrol as a sole carbon source. Out of fifteen isolated strains best two isolates S4P2 and S14P1 were selected on basis of DCPIP screening method. These isolates were identified as Pseudomonas chengduensis & Pseudomonas donghuensis by 16S rRNA gene sequencing. The growth parameters were optimized by one factor at a time. The optimum growth temperature for P.chengduensis & P. donghuensis was found to be 37°C at pH 7 with a substrate concentration of 1%.

Spontaneous ignition and flame propagation in hydrogen/methane wrinkled laminar flames at reheat conditions: Effect of pressure and hydrogen fraction

Direct numerical simulations (DNS) with detailed chemical kinetics and chemical explosive mode analysis (CEMA) are performed to investigate the effect of operating pressure and hydrogen–methane blending on laminar wrinkled flames at reheat combustion conditions. Building upon previous three-dimensional DNS datasets of reheat hydrogen flames, the present work considers two-dimensional configurations that render computationally-feasible simulations of high-pressure combustion and significantly more complex hydrocarbon chemistry. A geometrically-simplified representation of the reheat combustor is adopted and the thermodynamic states considered in the simulations are carefully chosen to mimic gas turbine operation conditions, which are constrained to achieve a target flame position and flame temperature. The two-dimensional DNS results are first assessed against the available three-dimensional data and then analyzed to extract the main trends exhibited by the reheat combustion process with respect to the fraction of the fuel consumed by spontaneous ignition and flame propagation, for increasing pressures and hydrogen fractions. Due to significant differences in the characteristic features of the velocity and thermal boundary layers between the three-dimensional and the two-dimensional configurations, a different global flame shape is observed (V-shaped flame vs W-shape flame) together with a ∼10% bias in the fraction of fuel consumed by spontaneous ignition. Crucially, results from the scaling studies reveal very clear trends with a significant decrease in the fuel consumption by spontaneous ignition for increasing pressures and hydrogen fractions, at the conditions investigated. Finally, this study highlights the important role that first-principle direct numerical simulations, even when conducted in computationally affordable two-dimensional simplified geometrical configurations, can play in obtaining detailed insights and quantitative trends useful for the characterization of complex reactive flows.Novelty and significanceThe reheat burners of the two-stage sequential gas turbine combustors are designed to stabilize flames primarily due to spontaneous ignition. However, prior numerical simulations revealed the presence of an additional assisted-ignition mode aided by recirculation zones. In this study, we used practically feasible two-dimensional direct numerical simulations of premixed hydrogen–air mixtures under lean conditions to quantify the roles of the two flame stabilization modes at different operating pressures. Achieving fundamental understanding of the effect of pressure and hydrogen fraction on flame stabilization is crucial to the development of two-stage sequential combustion and the present two-dimensional calculations provide important new insights. We show that at high pressures, both modes consume fuel to a similar extent. We also investigated the effect of methane blending on flame stabilization. This study also discusses how two-dimensional direct numerical simulations can be leveraged in the design optimization of reheat burners at low technology readiness levels.

Unravelling the history of a complex hydrocarbon play through petroleum systems modelling – Catcher area development (CAD), UK Central North Sea region

Significant uncertainty exists with regards to the migration history of hydrocarbons in the Catcher Area Development (CAD) region, West Central Shelf, UK Central North Sea. In this study, petroleum system modelling is carried out to understand the pathways, timing and processes involved in hydrocarbons migration from the Jurassic Kimmeridge Clay to the injectite dominated sandstone reservoirs of the CAD region. The Cromarty sandstones are identified as the lateral carrier of hydrocarbons from the graben area to the CAD reservoirs. Out of the six CAD fields, five were charged along a fill spill chain. During the charging process, the CAD system was mostly seal limited, with significant hydrocarbon leakage into the overburden. Hydrocarbon migration and gas leakage in the region continues today. The present-day accumulations of the CAD region are spill limited suggesting the potential for more discoveries westward. This study provides an understanding of why gas chimneys are widespread in the CAD region and how the quality of hydrocarbons in the different fields relates to one another and those of the wider region. It also supports the presence of prospects further SW of the CAD region.

Rovibrational Line Lists of Triplet and Singlet Methylene.

The methylene molecule (CH2) is a short-lived radical with lacking data on its spectral line intensities. Although the lifetime of CH2 is extremely short under Earth's conditions, it exists in a free form in interstellar media. CH2 is an important intermediate species in chemical reactions associated with the formation and destruction of complex hydrocarbons. We present the first rovibrational line lists of CH2 in its ground triplet and first excited singlet electronic state. To this end, our previously developed accurate ab initio potential energy surface (PES) was used for the ground electronic triplet state [Egorov et al. J. Comp. Chem. 2024. V. 45. (2). P. 83] while a new PES for the singlet state was constructed in this work using the single-reference coupled cluster approach [CCSD(T)] combined with the extrapolation to the complete basis set (CBS) limit based on the correlation-consistent orbital basis sets with the core-valence electron correlation effects [aug-cc-pCVXZ, X = T, Q, 5, and 6]. In addition, the contributions to the correlation energy from highly excited Slater determinants [CC(n), n = 3-5] were included as well as the scalar relativistic effects and DBOC. The most accurate description of the infrared band origins of singlet CH2 was thus achieved for the energy range where the impact of the nonadiabatic coupling due to the Renner-Teller effect can be neglected. To obtain the probabilities of the rovibrational transitions, new ab initio DMSs were constructed both for the triplet and singlet CH2 using the CCSD(T)/aug-cc-pCVQZ approach. Finally, the absorption spectra of triplet and singlet methylene were predicted from the variationally computed line lists.

Astrochemistry and Astrobiology over the last 20 years

A review of the achievements of astrochemistry and astrobiology over the past 20 years is given. Advances in astrochemistry in understanding the processes of emergence and survival high molecular weight chemical compounds are directly related to the conditions of prebiomolecules origin, like -amino acids and complex hydrocarbons. And if on the case of amino acids and hydrocarbons synthesis , the astrophysical picture seems quite clear, then on the case of the emergence of chiral amino acids, of which the proteins of living organisms are composed, there is no generally accepted point of view. Probably they occurred in certain photochemical transformations under the influence of circularly polarized radiation in the conditions of star formation regions of molecular clouds.

Elucidating the biotechnological potential of the genera Parageobacillus and Saccharococcus through comparative genomic and pan-genome analysis

BackgroundThe genus Geobacillus and its associated taxa have been the focal point of numerous thermophilic biotechnological investigations, both at the whole cell and enzyme level. By contrast, comparatively little research has been done on its recently delineated sister genus, Parageobacillus. Here we performed pan-genomic analyses on a subset of publicly available Parageobacillus and Saccharococcus genomes to elucidate their biotechnological potential.ResultsPhylogenomic analysis delineated the compared taxa into two distinct genera, Parageobacillus and Saccharococcus, with P. caldoxylosilyticus isolates clustering with S. thermophilus in the latter genus. Both genera present open pan-genomes, with the species P. toebii being characterized with the highest novel gene accrual. Diversification of the two genera is driven through the variable presence of plasmids, bacteriophages and transposable elements. Both genera present a range of potentially biotechnologically relevant features, including a source of novel antimicrobials, thermostable enzymes including DNA-active enzymes, carbohydrate active enzymes, proteases, lipases and carboxylesterases. Furthermore, they present a number of metabolic pathways pertinent to degradation of complex hydrocarbons and xenobiotics and for green energy production.ConclusionsComparative genomic analyses of Parageobacillus and Saccharococcus suggest that taxa in both of these genera can serve as a rich source of biotechnologically and industrially relevant secondary metabolites, thermostable enzymes and metabolic pathways that warrant further investigation.

10 keV electron irradiation of methane ices at ocean world surface temperatures

The surface environmental conditions of many of the icy ocean worlds in the Solar System are outside of the thermal stability field of methane ice. However, mechanisms may exist that entrain or trap methane within water ice that arrives at the surface via plume eruptions or resurfacing events. At the surface, the ice grains may experience charged particle irradiation that could lead to the production of new complex hydrocarbons. We investigated the irradiation products of 12CH4 versus 13CH4, the temperature dependence of CH4 radiation processing and product stability, and the temperature stability of CH4 when mixed with H2O in a cryogenic vacuum environment. Significantly, methane ice experimentally encased in water ice was irradiated at 100 K in an ultra-high vacuum environment and produced similar radiation-formed secondary phases as pure methane ice irradiated at 20 K. The methane radiation products produced outside of the methane ice thermal stability field, while encased in a water ice film, were most notably 13CO2 and a candidate hydrocarbon feature. Evidence for complex hydrocarbons, such as C2H6, was observed during warming and sublimation of the sample.

A hybrid modeling approach: dynamic simulation of two-phase fluid flow in compacting gas condensate reservoirs using potential flow theory

Simulating the flow processes of complex hydrocarbon mixtures, such as gas condensate mixtures and volatile oils, in deep reservoirs is one of the most challenging problems in reservoir hydrodynamics. The challenge lies in meeting three requirements simultaneously when creating a simulator: high accuracy, low computational cost, and high reliability. These metrics determine the performance of the simulation. Meeting all these requirements at the same time necessitates a hybrid approach to solving the problem and optimizing the computational algorithm in terms of CPU time. A new technique has been developed for hybrid modeling of the development of deposits of complex hydrocarbon mixtures. This technique integrates the theory of potential flow, the Binary Flow Model (which accounts for rock compaction, PVT properties of reservoir fluids, phase transformation, and mass transfer between phases), and the material balance equations of the hydrocarbon system using time discretization. In this case, to linearize nonlinear differential equations for the flow of a gascondensate mixture, the method of averaging reservoir pressure along the radial coordinate was used. By introducing the Khrestianovich function, an algorithm was obtained to determine the rate of inflow of the gas-condensate mixture to the well. Using material balance equations for gas and condensate, it was possible to obtain differential equations that describe changes in reservoir pressure and condensate saturation over time. Based on this technique, a simulator for a gas condensate reservoir was created, enabling computer studies to be conducted. The results demonstrated the proposed technique's good accuracy compared with the results of the semi-analytical solution. Keywords: dynamic modeling; simulation; monitoring; streamline; hybrid modeling; binary model.

Unveiling the Unusual Mn(CO)3 Migration in a Manganese Cyclohexenyl Complex by DFT Computations.

Homogeneous catalysis involving a transition metal agostic interaction (TM…H…C) is an attractive strategy for C-H bond activation, in which the transition metal agostic intermediates serve as the critical component. To investigate the roles of manganese agostic intermediates in the unusual migration of the Mn(CO)3 fragment in the (exo-phenyl)(η3-cyclohexenyl)manganese tricarbonyl [(Ph)(η3-C6H8)Mn(CO)3] (complex 1) under the protonation of tetrafluoroboric acid-diethyl ether (HBF4.Et2O), a comprehensive density functional theory (DFT) theoretical study was performed. The computational results showed that formation of the [(cyclohex-3-enyl)-η6-benzene]manganese tricarbonyl complex [(C6H9)(η6-Ph)Mn(CO)3+][BF4] (complex 2) was achieved via a series of mono-agostic and di-agostic intermediates. The overall rate-limiting step for this unusual migration of the Mn(CO)3 fragment is the formation of the di-agostic (η2-phenyl)manganese complex 8 (4 → 5 → 8) with a Gibbs barrier of 15.4 kcal mol-1. The agostic intermediates with TM…H…C agostic interactions were well-characterized by geometry parameters, Atoms-In-Molecules (AIM) analyses, and the Natural Adaptive Orbitals (NAdOs). The located pathways in the current study successfully explained the experimental observations, and the findings on the TM…H…C agostic interaction provided a new aspect of the catalytic reaction with the manganese complex.

Detailed Reaction Kinetics for Hydrocarbon Fuels: The Development and Application of the ReaxFFCHO-S22 Force Field for C/H/O Systems with Enhanced Accuracy.

Efficient and accurate reactive force fields (e.g., ReaxFF) are pivotal for large-scale atomistic simulations to comprehend microscopic combustion processes. ReaxFF has been extensively utilized to describe chemical reactions in condensed phases, but most existing ReaxFF models rely on quantum mechanical (QM) data nearly two decades old, particularly in hydrocarbon systems, constraining their accuracy and applicability. Addressing this gap, we introduce a reparametrized ReaxFFCHO-S22 for C/H/O systems, tailored for studying the pyrolysis and combustion of hydrocarbon fuel. Our approach involves high-level QM benchmarks and large database construction for C/H/O systems, global ReaxFF parameter optimization, and molecular dynamics simulations of typical hydrocarbon fuels. Density functional theory (DFT) computations utilized the M06-2X functional at the meta-generalized gradient approximation (meta-GGA) level with a large basis set (6-311++G**). Our new ReaxFFCHO-S22 model exhibits a minimum 10% enhancement in accuracy compared to the previous ReaxFF models for a large variety of hydrocarbon molecules. This advanced ReaxFFCHO-S22 not only enables efficient large-scale studies on the microscopic chemical reactions of more complex hydrocarbon fuel but also can extend to biofuels, energetic materials, polymers, and other pertinent systems, thus serving as a valuable tool for studying chemical reaction dynamics of the large-scale hydrocarbon condensed phase at an atomistic level.

Comparisons of Different Representative Species Selection Schemes for Reduced-Order Modeling and Chemistry Acceleration of Complex Hydrocarbon Fuels

The simulation of engine combustion processes, such as autoignition, an important process in the co-optimization of fuel-engine design, can be computationally expensive due to the large number of thermo-chemical scalars needed to describe the full chemical system. Yet, the inherent correlations between the different chemical species during oxidation can significantly reduce the complexity of representing this system. One strategy is to select a subset of representative species that accurately captures the combustion process at a fraction of the computational cost of the full system. In this study, we compare the performance of four different techniques to select these species. They include the two-step principal component analysis (PCA) approach, directed relation graphs (DRGs), the global pathway selection (GPS) approach, and the manifold-informed species selection method. A parametric study of the representative species selection is carried out on data from the simulation of homogeneous and perfectly stirred reactors by investigating seven cumulative variances and 47 different cut-off percentages for the two-step PCA, and 65 and 51 thresholds for the DRGs and GPS, respectively. Results show that these selection methods capture key important species that can accurately describe the chemical system and track each stage of oxidation. The two-step PCA is sensitive to the cumulative variance, and DRGs and GPS are sensitive to the choice of target variables. By selecting key representative species and reducing the number of thermo-chemical scalars, these three methods can be used to develop computationally efficient hybrid chemistry schemes.

An oxo‐acetato‐bridged trinuclear cobalt(III) cluster‐persuaded cobalt oxide active electrocatalyst for efficient hydrogen evolution activity

This study presents the synthesis and electrocatalytic performance of the cobalt(III) complex [Co3(μ1,1,1‐O)(μ1,3‐CH3CO2)(L)3]2(DMF)3 (Cotri), featuring a double deprotonated (N,O)‐donor ligand (L2‐), where the protonated form of it (H2L) is 2,2′‐(hydrazine‐1,2‐diylidenebis(ethan‐1‐yl‐1‐ylidene))diphenol. The X‐ray structure reveals a trinuclear cobalt cluster formed with three cobalt(III) centers interlinking through oxido (μ1,1,1‐O) and acetato (μ1,3‐O2CCH3) bridges in coupling with bis‐congregator‐type chelating ligands. Cotri adopts cobalt centers of octahedral and trigonal bipyramidal coordination geometries and bears a dominant Co(2)…H(DMF) agostic interactions appraised by lattice dimethyl formamide (DMF) molecules. Further, Cotri shows promising heterogeneous electrocatalytic hydrogen evolution activity in 1 M KOH, with an overpotential of 441 mV to achieve 10 mA/cm2 current density. Tafel slope analysis suggests the Volmer–Heyrovsky step as the rate‐determining step. The number of active sites and TOF for Cotri were estimated at 4.010 × 10−8 mol and 0.2467 s−1, respectively, ensuring its excellent hydrogen generation activity. Stability assessments through controlled potential electrolysis (CPE) and cyclic voltammetry (CV) for multiple cycles addressed the transformation of Cotri to Co2O3 nanoparticles, which turned out to be a more active Co2O3 electrocatalyst. The morphology and particle size of the in situ developed Co2O3 active catalyst under the electrochemical conditions attributes to the superior hydrogen evolution activity.

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.