High Energy Barrier Research Articles

Targeting gut microbiota and metabolism profiles with coated sodium butyrate to ameliorate high-energy and low-protein diet-induced intestinal barrier dysfunction in laying hens

High energy diet are a risk factor for intestinal barrier damage. Butyrate, a major energy source for intestinal epithelial cells, has been shown to improve barrier dysfunction and modulate the gut microbiota. In this trial, we examined the preventative effect of coated sodium butyrate (CSB) on high-energy low-protein (HELP)-induced intestinal barrier injury in laying hens, and also worked to determine the underlying mechanisms by an integrative analysis of gut microbiota and the metabolome. A total of 216 healthy 28-weeks-old Huafeng laying hens were randomly assigned to 3 groups with 6 replicates each: the CON group (normal diet), HELP group (high-energy and low-protein diet) and CH500 group (500 mg/kg CSB added to HELP diet). The duration of the trial encompassed a period of 10 weeks. The results revealed that CSB treatment improved the laying rate (P<0.05) and mitigated the detrimental effects on intestinal barrier function and the inflammatory response induced by the HELP diet in laying hens (P<0.05). Microbial profiling analysis revealed that the CSB treatment reshaped the HELP-perturbed gut microbiota, and promoted the growth of beneficial bacteria (P<0.05). Untargeted metabolomics analysis revealed that CSB reduced the metabolites associated with intestinal inflammation (P<0.05). In conclusion, CSB did not merely modulate alterations in the gut microbiota composition and microbial metabolites but also yielded increased egg production, while mitigating intestinal barrier dysfunction and inflammatory responses induced by HELP in laying hens.

Synthesis of Eu-doped TiO&lt;sub&gt;2&lt;/sub&gt; nanoparticles by hydrothermal method

Purpose of research. Synthesis, characterization and comparison of the photocatalytic properties of europium-doped titanium dioxide nanoparticles. Methods. Europium-doped titanium dioxide nanoparticles were synthesized via a hydrothermal method followed by post-treatment processes including washing and annealing. Characterization was conducted using transmission electron microscopy, X-ray phase analysis, and energy-dispersive analysis. The bandgap width of the nanoparticles was determined through diffuse reflectance spectroscopy. Photoluminescence properties were studied using scanning probe microscopy and Raman spectroscopy. The photocatalytic properties were studied by spectrophotometry to determine the degradation of methylene blue under ultraviolet radiation. Results. Transmission electron microscopy identified the average particle sizes of europium-doped titanium dioxide. Using X-ray phase analysis, it was established that the nanoparticles were in the anatase phase regardless of the europium content percentage. Energy-dispersive spectroscopy confirmed the presence of the dopant in the samples. The photoluminescence intensity peak increased proportionally with the increase in europium content percentage. The strongest photocatalytic properties were exhibited at the lowest europium content among the samples studied. Conclusion. Synthesized and processed europium-doped titanium dioxide nanoparticles with anatase polymorphic modification exhibit photoluminescent properties. The luminescence intensity depends on the concentration of europium in the particles, due to the formation of additional energy levels inside the band gap. The photocatalytic properties of europium-doped nanoparticles are significantly improved in comparison with samples synthesized without impurities. However, a europium concentration above 0,5% leads to the growth of structural defects that reduce the mobility of photogenerated charge carriers and creates a high energy barrier that prevents them from reaching the surface.

Exploring the Activation Mechanism of the GPR183 Receptor.

The G protein-coupled receptors (GPCRs) play a pivotal role in numerous biological processes as crucial cell membrane receptors. However, the dynamic mechanisms underlying the activation of GPR183, a specific GPCR, remain largely elusive. To address this, we employed computational simulation techniques to elucidate the activation process and key events associated with GPR183, including conformational changes from inactive to active state, binding interactions with the Gi protein complex, and GDP release. Our findings demonstrate that the association between GPR183 and the Gi protein involves the formation of receptor-specific conformations, the gradual proximity of the Gi protein to the binding pocket, and fine adjustments of the protein conformation, ultimately leading to a stable GPR183-Gi complex characterized by a high energy barrier. The presence of Gi protein partially promotes GPR183 activation, which is consistent with the observation of GPCR constitutive activity test experiments, thus illustrating the reliability of our calculations. Moreover, our study suggests the existence of a stable partially activated state preceding complete activation, providing novel avenues for future investigations. In addition, the relevance of GPR183 for various diseases, such as colitis, the response of eosinophils to Mycobacterium tuberculosis infection, antiviral properties, and pulmonary inflammation, has been emphasized, underscoring its therapeutic potential. Consequently, understanding the activation process of GPR183 through molecular dynamic simulations offers valuable kinetic insights that can aid in the development of targeted therapies.

Computational Studies of Nucleophilic Substitution at Nitrogen Center: Reactions of NH2Cl with HO-, CH3O- and C2H5O.

The atomic-level mechanisms of the nucleophilic substitution reactions at the nitrogen center (SN2@N) were investigated for the reactions of chloramine (NH2Cl) with the alkoxide ions (RO-, where R = H, CH3, and C2H5) using DFT and MP2 methods. The computed potential energy profiles for the SN2@N pathways involving the back-side attack of the nucleophiles show the typical double-well potential with submerged barriers similar to the SN2@N reactions at the carbon center (SN2@C). However, the pre-reaction and post-reaction complexes are, respectively, the N-H…O and N-H…Cl hydrogen-bonded intermediates, which are different from those generally seen in SN2@C reactions. The SN2@N pathways involving front-side attack of the nucleophiles have high-energy barriers. The potential energy surfaces (PESs) along the proton-transfer pathways were flat. In addition to the proton-transfer and SN2 pathways, we also observed a new path for the methoxide and ethoxide nucleophiles where a hydride transfer from the nucleophile to chloramine resulted in the products Cl- + R'CHO + NH3, (R' = H, CH3), and was the most exoergic. A comparison of the energetics obtained used different DFT and MP2 methods with that of the benchmark coupled-cluster methods reveals that CAM-B3LYP best describes the PESs.

Exploring the Crystal Structure, Thermodynamics, and Molecular Dynamics of NH(CH3)3CuCl3·2H2O Organic-Inorganic Hybrid Perovskite.

Understanding the physical properties of the organic-inorganic hybrid NH(CH3)3CuCl3·2H2O is necessary for its potential applications. Initially, the monoclinic structure of this crystal was discussed via single-crystal X-ray diffraction. Moreover, the previously unknown phase transition temperature was 350 K, as revealed by differential scanning calorimetry and powder X-ray diffraction. Attributed to ferroelasticity, domain walls were observed between the temperatures T c (Low) (223 K) and T c (High) (350 K). Furthermore, changes in chemical shifts for 1H and 13C indicated alterations in the molecular environment, whereas a notable decrease in line width was attributed to increased molecular motion freedom. Subsequently, spin-lattice relaxation times (T 1ρ values) for 1H and 13C (indicative of energy transfer) were influenced by tumbling motions. The high activation energy barrier for molecular reorientation was associated with the tumbling motion of methyl groups around the triple symmetry axis. These foundational properties guide the development of efficient organic-inorganic hybrids suitable for practical applications.

Mechanistic and kinetic insights of the formation of allene and propyne from the C3H3 reaction with water.

Allene (H2C = C = CH2) and propyne (CH3-C≡CH) are important compounds in the combustion chemistry. They can be created from the reaction of proparyl radicals with water. In this study, therefore, a computational study into the C3H3 + H2O potential energy landscape has been carefully conducted. The computed results indicate that the reaction paths forming the products (allene: CH2CCH2 + •OH) and (propyne: HCCCH3 + •OH) prevail under the 300-2000K temperature range, where the latter is much more predominant compared to the former. However, these two products are not easily formed under ambient conditions due to the high energy barriers. In the 300 - 2000K temperature range, the branching ratio for the propyne + •OH product declines from 100 to 86%, whereas the allene + •OH product shows an increase, reaching 14% at 2000K. The overall bimolecular rate constant of the title reaction can be presented by the modified Arrhenius expression of ktotal = 1.94 × 10-12 T0.14 exp[(-30.55kcal.mol-1)/RT] cm3 molecule-1s-1. The total rate constant at the ambient conditions in this work, 2.37 × 10-34 cm3 molecule-1s-1, was found to be over five orders of magnitude lower than the total rate constant of the C3H3 + NH3 reaction, 7.98 × 10-29 cm3 molecule-1s-1, calculated by Hue et al. (Int. J. Chem. Kinet. 2020, 4(2), 84-91). The results in this study contribute to elucidating the mechanism of allene and propylene formation from the C3H3 + H2O reaction, and they can be used for modeling C3H3-related systems under atmospheric and combustion conditions. All the geometric structures of the C3H3 + H2O system were optimized by the B3LYP method in conjunction with the 6-311 + + G(3df,2p) basis set. Single-point energies of these species were calculated at the CCSD(T)/6-311 + + G(3df,2p) level of theory. The CCSD(T)/CBS level has also been used to compute single-point energies for the two major reaction channels (C3H3 + H2O → allene + •OH and C3H3 + H2O → propyne + •OH). Rate constants and branching ratios of the key reaction channels were calculated in the 300-2000K temperature interval using the Chemrate software based on the transition state theory (TST) with Eckart tunneling corrections.

Efficient electrocatalytic nitrate reduction on molecular catalyst with electron-deficient single-atom Cuδ+ sites

Electrocatalytic nitrate (NO3−-N) reduction to ammonia (NH3-N) (ENRR) coupled with NH3-N separation represents a sustainable process for nitrate pollution mitigation. The −(Cuδ+-N4)- moiety-bearing carbon materials (SCMs) are robust ENRR catalysts but suffer from energy-intensive synthetic process. Furthermore, the complexity in altering the coordination environment of Cuδ+ raises the difficulty in optimizing its electron-deficiency for an enhanced ENRR. Herein the copper phthalocyanine (CuPc) and copper perfluorocyanine (CuF16Pc) molecular catalysts, which share the same −(Cuδ+-N4)- moiety with SCMs but are commercially available, are attempted for ENRR. The CuF16Pc, which differs from CuPc by the substitution of the H in Pc with F, shows alleviated intermolecular agglomeration and increased electron-deficiency of.the Cuδ+ center, owing to the electron-withdrawing effect of F. The alleviated intermolecular agglomeration exposes more Cuδ+, which makes CuF16Pc outperform CuPc (2254.9 vs. 1979.3 mg-NH3 h−1 gCu−1) and most of the reported catalysts in the mass activity of ENRR. However, the Cuδ+ with a larger electron-deficiency in CuF16Pc is less active than that in CuPc for ENRR, owing to the higher energy barrier for NO* hydrogenation to NOH* on it. It reminds us that the CuPc is more ideal for ENRR if its agglomeration issue can be addressed. Finally, an integrated continuous-flow system composed of the CuF16Pc-driven ENRR and PVDF fibers-mediated NH3 separation is customized, which enables a steady NO3−-N removal efficiency of 96.4 % and NH3-N recovery efficiency of 97.2 % from simulated nitrate-contaminated water.

Reaction mechanism of antioxidant inhibition of hydroxyl radical in coal oxidation.

To solve the problem of unclear targeted inhibition of key free radicals by antioxidants, this paper took the hydroxyl radical with the highest oxidation activity of coal as the inhibition target and selected five antioxidants such as ethylene diamine tetraacetic acid, tea polyphenol, citric acid, vitamin C, and proanthocyanidins. Based on the theory of quantum chemistry, the characteristics and oxidation pathway of antioxidants inhibiting coal oxidation of hydroxyl radical were analyzed. Analyze the influence characteristics of antioxidants on the evolution of free radicals in coal through an electron paramagnetic resonance experiment (ESR). The results showed that the electron density of antioxidants was mainly distributed in the functional groups of carboxyl and hydroxyl, which played a key inhibitory role, and the vicinity of carboxyl and hydroxyl and other functional groups was positive potential, which was the active site of inhibiting hydroxyl radical. The order of inhibitory capacity of the five antioxidants was determined as GTP > PC > EDTA > CA > VC. It is concluded that the energy barrier of hydroxyl radical inhibition by citric acid is much lower than that of EDTA. For the hydrogen extraction reaction, VC inhibited the hydroxyl radical pathway with a higher energy barrier than the other three antioxidants. The mechanism of five antioxidants inhibiting •OH reaction was comprehensively analyzed. It was found that tea polyphenols have more active sites that can react with •OH to quench it, so the inhibition of tea polyphenols should be the most significant. When antioxidants inhibit coal spontaneous combustion, the type, complexity, concentration, and linewidth of free radicals in coal molecules are lower than those in raw coal, with GTP antioxidants having the best inhibitory effect. The research results have important theoretical and practical significance for revealing the mechanism of coal spontaneous combustion inhibition and developing directional coal spontaneous combustion inhibition technology.

A Biphasic Strategy to Synergistically Accelerate Activation and CO Spillover in Formic Acid Oxidation Catalysis.

Developing highly efficient and carbon monoxide (CO)-tolerant platinum (Pt) catalysts for the formic acid oxidation reaction (FAOR) is vital for direct formic acid fuel cells (DFAFCs), yet it is challenging due to the high energy barrier of direct intermediates (HCOO* and COOH*) as well as the CO poisoning issues associated with Pt alloy catalysts. Here we present a versatile biphasic strategy by creating a hexagonal/cubic crystalline-phase-synergistic PtPb/C (h/c-PtPb/C) catalyst to tackle the aforementioned issues. Detailed investigations reveal that h/c-PtPb/C can simultaneously facilitate the adsorption of direct intermediates while inhibiting CO adsorption, thereby significantly improving the activation and CO spillover. As a result, h/c-PtPb/C showcases an outstanding FAOR activity of 8.1 A mgPt-1, which is 64.5 times higher than that of commercial Pt/C and significantly surpasses monophasic PtPb. Moreover, the h/c-PtPb/C-based membrane electrode assembly exhibits an exceptional peak power density of 258.7 mW cm-2 for practical DFAFC applications.

Angstrom‐scale channels with versatile ion‐membrane interactions enabling precise ion separation via electrodialysis

AbstractIn nature, efficient and selective ion transport is facilitated by ion‐conductive channels in cell membranes; these channels reveal an architectural design with specialized functionality. Drawing inspiration from this, mechanistic insights into the angstrom‐scale‐channel membrane composed of ionic‐crosslinked polybenzimidazole and sulfonated poly(ether ether ketone), exhibiting functional differentiation and efficient ion‐sieving properties are presented. Nanochannels allow for strong hydrogen‐bonding interactions with hydrated ions of higher polarity, while rendering significant electrostatic charge effects that impede the transition of multivalent ions by compressing effective passageways. Both hydrogen bonding and electrostatic interactions synergistically result in high selectivity for monovalent ions over multivalent ions because the latter requires overcoming higher energy barriers for transport compared with the former, thereby causing varying extents of ion dehydration within the nanochannels. The resulting membrane achieves a high monovalent ion permeation rate of 1.35 mol m−2 h−1 with a high mono/multivalent ion selectivity of 56.5 for K+/Mg2+ and 286 for K+/Al3+.

Kinetic modeling of the oxidative dehydrogenation of propane with CO2 over a CrOx/SiO2 catalyst and assessment of CO2 utilization

Oxidative dehydrogenation of propane with carbon dioxide (ODPC) has gained attention as a sustainable process capable of simultaneously producing propylene and reducing carbon dioxide (CO2) emissions. In this study, we developed a kinetic model of the ODPC over a silica-supported chromium oxide catalyst based on the Mars–van Krevelen (MvK) mechanism using the experimental data obtained under controlled conditions. The constructed model estimated both reactant conversions and propylene yield within an absolute error of 3% of the experimental data, confirming the integrity of the kinetic model. The kinetic analysis provides insight into the activation of propane and CO2 via several reactions occurring under ODPC conditions, emphasizing that the ODPC cycle is limited by the high energy barrier for CO2 activation. In addition, it allows comparison of the contributions of non-oxidative and oxidative dehydrogenation reactions, the two main reactions producing propylene under ODPC conditions. The estimation results show a significant increase in the reaction rate of ODPC with increasing CO2 partial pressure, in contrast to a nearly constant reaction rate of non-oxidative dehydrogenation, highlighting the promoting effect of CO2 in enhancing the ODPC reaction. Furthermore, the potential of the ODPC process is assessed by considering propylene productivity, net CO2 emissions, including the energy consumption for the separation process, and the global warming index of the energy grid. A comprehensive investigation of the ODPC process through controlled experiments, kinetic modeling and evaluation of net CO2 utilization provides insight into future strategies for using the ODPC as an efficient and eco-friendly process.

Mechanism Involved in Polyvinyl Chloride Nanoplastics Induced Anaerobic Granular Sludge Disintegration: Microbial Interaction Energy, EPS Molecular Structure, and Metabolism Functions.

Nanoplastics (NPs) are emerging pollutants and have been reported to cause the disintegration of anaerobic granular sludge (AnGS). However, the mechanism involved in AnGS disintegration was not clear. In this study, polyvinyl chloride nanoplastics (PVC-NPs) were chosen as target NPs and their long-term impact on AnGS structure was investigated. Results showed that increasing PVC-NPs concentration resulted in the inhibition of acetoclastic methanogens, syntrophic propionate, and butyrate degradation, as well as AnGS disintegration. At the presence of 50 μg·L-1 PVC-NPs, the hydrophobic interaction was weakened with a higher energy barrier due to the relatively higher hydrophilic functional groups in extracellular polymeric substances (EPS). PVC-NPs-induced ROS inhibited quorum sensing, significantly downregulated hydrophobic amino acid synthesis, whereas it highly upregulated the genes related to the synthesis of four hydrophilic amino acids (Cys, Glu, Gly, and Lys), resulting in a higher hydrophily degree of protein secondary structure in EPS. The differential expression of genes involved in EPS biosynthesis and the resulting protein secondary structure contributed to the greater hydrophilic interaction, reducing microbial aggregation ability. The findings provided new insight into the long-term impact of PVC-NPs on AnGS when treating wastewater containing NPs and filled the knowledge gap on the mechanism involved in AnGS disintegration by PVC-NPs.

Sequentially Regulating Potential‐Determining Step for Lowering CO2 Electroreduction Overpotential over Te‐Doped Bi Nanotips

Electrocatalytic conversion of CO2 into formate is recognized an economically‐viable route to upgrade CO2, but requires high overpotential to realize the high selectivity owing to high energy barrier for driving the involved proton‐coupled electron transfer (PCET) processes and serious ignorance of the second PCET. Herein, we surmount the challenge through sequential regulation of the potential‐determining step (PDS) over Te‐doped Bi (TeBi) nanotips. Computational studies unravel the incorporation of Te heteroatoms alters the PDS from the first PCET to the second one by substantially lowering the formation barrier for *OCHO intermediate, and the high‐curvature nanotips induce enhanced electric field that can steer the formation of asymmetric *HCOOH. In this scenario, the thermodynamic barrier for *OCHO and *HCOOH can be sequentially decreased, thus enabling a high formate selectivity at low overpotential. Experimentally, distinct TeBi nanostructures are obtained via controlling Te content in the precursor and TeBi nanotips achieve &gt;90% of Faradaic efficiency for formate production over a comparatively positive potential window (‐0.57 V to ‐1.08 V). The strong Bi‐Te covalent bonds also afford a robust stability. In an optimized membrane electrode assembly device, the formate production rate at 3.2 V reaches 10.1 mmol h‐1 cm‐2, demonstrating great potential for practical application.

The hybrid Pt nanoclusters/Ru nanowires catalysts accelerating alkaline hydrogen evolution reaction

Water electrolysis via alkaline hydrogen evolution reaction (HER) is a promising approach for large-scale production of high-purity hydrogen at a low cost, utilizing renewable and clean energy. However, the sluggish kinetics derived from the high energy barrier of water dissociation impedes seriously its practical application. Herein, a series of hybrid Pt nanoclusters/Ru nanowires (Pt/Ru NWs) catalysts are demonstrated to accelerate alkaline HER. And the optimized Pt/Ru NWs (10 ​% wt Pt) exhibits exceptional performance with an ultralow overpotential (24 ​mV at 10 ​mA ​cm−2), a small Tafel slope (26.3 ​mV dec−1), and long-term stability, outperforming the benchmark commercial Pt/C-JM-20 ​% wt catalyst. This amazing performance also occurred in the alkaline anion-exchange membrane water electrolysis devices, where it delivered a cell voltage of about 1.9 ​V at 1 ​A ​cm−2 and an outstanding stability (more than 100 ​h). The calculations have revealed such a superior performance exhibited by Pt/Ru NWs stems from the formed heterointerfaces, which significantly reduce the energy barrier of the decisive rate step of water dissociation via cooperative-action between Pt cluster and Ru substance. This work provides valuable perspectives for designing advanced materials toward alkaline HER and beyond.

Facet-switching of rate-determining step on copper in CO2-to-ethylene electroreduction

Reduction of carbon dioxide (CO2) by renewable electricity to produce multicarbon chemicals, such as ethylene (C2H4), continues to be a challenge because of insufficient Faradaic efficiency, low production rates, and complex mechanistic pathways. Here, we report that the rate-determining steps (RDS) on common copper (Cu) surfaces diverge in CO2 electroreduction, leading to distinct catalytic performances. Through a combination of experimental and computational studies, we reveal that C─C bond-making is the RDS on Cu(100), whereas the protonation of *CO with adsorbed water becomes rate-limiting on Cu(111) with a higher energy barrier. On an oxide-derived Cu(100)-dominant Cu catalyst, we reach a high C2H4 Faradaic efficiency of 72%, partial current density of 359 mA cm-2, and long-term stability exceeding 100 h at 500 mA cm-2, greatly outperforming its Cu(111)-rich counterpart. We further demonstrate constant C2H4 selectivity of >60% over 70 h in a membrane electrode assembly electrolyzer with a full-cell energy efficiency of 23.4%.

Active Oxygenated Structure‐Intensified CO2 Capture Enables Efficient Electrochemical Ethylene Production Over Carbon Nanofibers

AbstractThe pursuit of high efficacy C−C coupling during the electrochemical CO2 reduction reaction remains a tremendous challenge owing to the high energy barrier of CO2 activation and insufficient coverage of the desired intermediates on catalytic sites. Inspired by the concept of capture‐coupled CO2 activation, we fabricated quinone‐grafted carbon nanofibers via an in situ oxidative carbonylation strategy. The quinone functionality of carbon nanofibers promotes the capture of CO2 followed by activation. At a current density of 400 mA cm−2, the Faradaic efficiency of ethylene reached 62.9 %, and a partial current density of 295 mA cm−2 was achieved on the quinone‐rich carbon nanofibers. The results of in situ spectroscopy and theoretical calculations indicated that the remarkable selectivity enhancement in ethylene originates from the quinone structure, rather than the electronic properties of Cu particles. The interaction of quinone with CO2 increases the local *CO coverage and simultaneously hinders the co‐adsorption of *H on Cu sites, which greatly reduces the energy barrier for C−C coupling and restrains subsequent *CO protonation. The modulation strategy involving specific oxygenated structure, as an independent degree of freedom, guides the design of functionalized carbon materials for tailoring the selectivity of desired products during the CO2 capture and reduction.

Active Oxygenated Structure-Intensified CO2 Capture Enables Efficient Electrochemical Ethylene Production Over Carbon Nanofibers.

The pursuit of high efficacy C-C coupling during the electrochemical CO2 reduction reaction remains a tremendous challenge owing to the high energy barrier of CO2 activation and insufficient coverage of the desired intermediates on catalytic sites. Inspired by the concept of capture-coupled CO2 activation, we fabricated quinone-grafted carbon nanofibers via an in situ oxidative carbonylation strategy. The quinone functionality of carbon nanofibers promotes the capture of CO2 followed by activation. At a current density of 400 mA cm-2, the Faradaic efficiency of ethylene reached 62.9 %, and a partial current density of 295 mA cm-2 was achieved on the quinone-rich carbon nanofibers. The results of in situ spectroscopy and theoretical calculations indicated that the remarkable selectivity enhancement in ethylene originates from the quinone structure, rather than the electronic properties of Cu particles. The interaction of quinone with CO2 increases the local *CO coverage and simultaneously hinders the co-adsorption of *H on Cu sites, which greatly reduces the energy barrier for C-C coupling and restrains subsequent *CO protonation. The modulation strategy involving specific oxygenated structure, as an independent degree of freedom, guides the design of functionalized carbon materials for tailoring the selectivity of desired products during the CO2 capture and reduction.

Inhibiting Demetalation of Fe─N─C via Mn Sites for Efficient Oxygen Reduction Reaction in Zinc-Air Batteries.

Demetalation caused by the electrochemical dissolution of metallic Fe atoms is a major challenge for the practical application of Fe─N─C catalysts. Herein, an efficient single metallic Mn active site is constructed to improve the strength of the Fe─N bond, inhibiting the demetalation effect of Fe─N─C. Mn acts as an electron donor inducing more delocalized electrons to reduce the oxidation state of Fe by increasing the electron density, thereby enhancing the Fe─N bond and inhibiting the electrochemical dissolution of Fe. The oxygen reduction reaction pathway for the dissociation of Fe─Mn dual sites can overcome the high energy barriers to direct O─O bond dissociation and modulate the electronic states of Fe─N4 sites. The resulting FeMn─N─C exhibits excellent ORR activity with a high half-wave potential of 0.92V in alkaline electrolytes. FeMn─N─C as a cathode catalyst for Zn-air batteries has a cycle stability of 700h at 25°C and a long cycle stability of more than 210h under extremely cold conditions at -40°C. These findings contribute to the development of efficient and stable metal-nitrogen-carbon catalysts for various energy devices.

PENNSYLVANIAN CONODONTS AND MICROFACIES FROM NORTHEASTERN MEXICO (TAMATÁN GROUP, CIUDAD VICTORIA BLOCK)

The biostratigraphic analysis of the Paleozoic sedimentary successions in Mexico is crucial for understanding their age, depositional setting, and paleogeographic implications. This study examined conodonts and microfacies of calcareous strata within the Del Monte Formation of the Tamatán Group in northeastern Mexico. Field observations have led to the identification of three units within the Del Monte Formation: Unit 1, characterized by calcareous sandstone, bioclastic limestone, shale, occasional conglomerate, and dolomitized beds; Unit 2, consisting of conglomerate and/or breccia associated with debris flows; and Unit 3 including turbiditic sandstone and shale. Conodonts were only recognized in Unit 1, with such genera as Idiognathoides, Neognathodus, Idiognathodus and less frequently, Streptognathodus, Adetognathus, and Diplognathodus. The faunal associations include Idiognathoides cf. Id. corrugatus Harris &amp; Hollingsworth, 1933, Idiognathoides sulcatus sulcatus Higgins &amp; Bouckaert, 1968, Idiognathoides convexus (Ellison &amp; Graves, 1941), Idiognathoides asiaticus Nigmadganov &amp; Nemyrovskaya, 1992, Neognathodus cf. N. atokaensis Grayson, 1984, Neognathodus aff. bothrops Merrill, 1972, Neognathodus nataliae Alekseev &amp; Gerelzezeg, 2001 (in Alekseev &amp; Goreva 2001), Streptognathodus parvus Dunn, 1966, Idiognathodus incurvus Dunn, 1966, and Idiognathodus aff. delicatus Gunnell, 1931, suggesting Morrowan and Atokan (Pennsylvanian) ages for the dolomitic limestone and grainstone beds. Five types of microfacies (MF) and several marine facies zone (FZ) have been detected: MF1-bioclastic grainstone and MF2-wackestone deposited at the platform margin (FZ 6 and FZ 7), MF3-dolomitized wackestone representing an inner restricted platform (FZ 8), MF4-mudstone from a deeper water zone (FZ 4), and MF5-siliciclastic beds with bioclasts indicating a high-energy barrier associated with a platform margin (FZ 6). The findings confirm a shallow to deep platform and imply a connection among Mexican peri-Gondwanan basins, including the Tamatán Basin, indicating similarities in sedimentary facies and/or depositional environments linked to the Rheic Ocean during the Early to Middle Pennsylvanian.

Theoretical studies and anharmonic effect analysis on the reaction mechanism of 3-methyl-1-butanol with OH radical

The mechanism of hydrogen abstraction in the reaction of 3-methyl-1-butanol with an OH radical was investigated by quantum chemical calculations. The total reaction consists of five channels (R1–R5), with channel R3 having the lowest energy barrier (5.4 kcal·mol−1) and channel R4 having the highest energy barrier (13.2 kcal·mol−1). All channels are exothermic reactions with lower energy barriers. Thermodynamic parameters, including constant pressure molar heat capacity CPo, enthalpy of formation ΔfHo, and entropy So, for all reactants and products, were researched using the CBS-QB3 level across a temperature scale of 298–5000 K. The harmonic and anharmonic rate constants of all reaction channels were calculated at the CCSD(T)/6-311++G(d,p) level for a temperature range of 223–4000 K. Throughout the temperature range, except for R2, the harmonic rate constant of all reaction channels is consistently higher than the anharmonic one, and it can be seen from the results that the anharmonic effect is significant and cannot be ignored. Meanwhile, the polynomial coefficients a1–a7 for the thermodynamic parameters and the polynomial coefficients A, n, and E for the kinetic parameters were fitted using the principle of least squares.