Oxidation Reaction Research Articles

Raman activities of nitrogen reduction and ammonia oxidation intermediates on the high-entropy alloy CoCuFeMoNi catalytic surface.

We developed a computational framework to extract the Raman spectra of nitrogen reduction and ammonia oxidation intermediates on high-entropy alloy (HEA) surfaces, integrating density functional theory with microstructural representations to account for the inherent lattice randomness in these materials. As a case study, we computed the Raman activities of intermediates (N2*, NNH*, N*, NH*, and NH3*) and H* adsorption on CoCuFeMoNi HEA surfaces. A comprehensive map of Raman peaks was generated and assigned to specific vibrational modes. The method highlighted the effects of lattice randomness on the Raman spectra compared to those of adsorbates on single-element catalysts. For instance, our results showed that the adsorbed N2 exhibits Raman modes that are dependent on whether the adsorption is vertical or horizontal. These peak differences could serve as unique fingerprints to identify nitrogen reduction reaction pathways. Moreover, it is also possible to detect surface poisoning by hydrogen, a common issue in reductive environments, due to the high-frequency peaks of H* compared to the typical N-metal stretching and bending frequencies. These results provide valuable references for identifying intermediates in nitrogen reduction and ammonia oxidation reactions, offering insights into reaction mechanisms and potential surface poisoning. This approach is generalizable to other reactions and surfaces in catalysis, provided that the relevant intermediates can be identified.

Recent development towards the novel applications and future prospects for cellulose-metal organic framework hybrid materials: a review.

The hybrid material created by combining cellulose and MOF is highly promising and possesses a wide range of useful properties. Cellulose-based metal-organic frameworks (CelloMOFs) combine the inherent biocompatibility and sustainability of cellulose with the tunable porosity and diverse metal coordination chemistry of MOFs. Cellulose-MOF hybrids have countless applications in various fields, such as energy storage, water treatment, air filtration, gas adsorption, catalysis, and biomedicine. They are particularly remarkable as adsorbents that can eliminate pollutants from wastewater, including metals, oils, dyes, antibiotics, and drugs, and act as catalysts for oxidation and reduction reactions. Furthermore, they are highly efficient air filters, able to remove carbon dioxide, particulate matter, and volatile organic compounds. When it comes to energy storage, these hybrids have demonstrated exceptional results. They are also highly versatile in the realm of biomedicine, with applications such as antibacterial and drug delivery. This article provides an in-depth look at the fabrication methods, advanced applications of cellulose-MOF hybrids, and existing and future challenges.

Fe-Doped Ni3S2 Induces Self-Reconstruction for Urea-Assisted Water Electrolysis Enhancement.

Urea oxidation reaction (UOR) is an attractive alternative anodic reaction to oxygen evolution reaction (OER) for its low thermodynamic potential (0.37 V vs RHE). A major challenge that prohibits its practical application is the six-electron transfer process during UOR, demanding enhancements in the catalytic activity. Herein, a Fe-doped Ni3S2 catalyst with a uniform flower-like structure is synthesized in situ on nickel foam via a simple one-step hydrothermal method. The electrochemical properties of Fe-Ni3S2 are significantly improved since a current density of 10 mA cm-2 only requires a 1.33 V potential and remains stable for 60 h. The structural characterization demonstrates a strong interaction between Fe and Ni3S2. After Fe doping, the active site increases, which promotes the formation of NiOOH on the catalyst surface, thus speeding up the UOR process. These changes are beneficial to charge transfer and optimize the adsorption energy of the intermediates. In situ EIS further confirms that Fe promotes electron transfer during the UOR process, reduces the interface resistance between the catalyst and the electrolyte, and lowers the driving voltage.

N-glycosylation Modification Reveals Insights into the Oxidative Reactions of Liver in Wuzhishan Pigs

Although porcine liver contributes to their growth and development by nutrition production and energy supply, oxidative stress-induced hepatocyte damage is inevitable during metabolism. N-glycosylation is a common modification in oxidation; nevertheless, the effects of N-glycosylation on pig liver oxidative reactions remain undefined. In this study, liver proteins with N-glycosylation were detected in Wuzhishan (WZS) pigs between 4 and 8 months old and Large White (LW) pigs at 4 months old based on LC-MS/MS. The results showed that the number of differentially expressed proteins (DEPs) was larger between different pig cultivars than that between WZS pigs at various growth periods. The enriched pathways of DEPs were mainly related to oxidative reactions, and 10 proteins were finally selected that primarily consisted of CYPs, GSTs and HSPs with expressions significantly correlating to liver size and weight. The oxidative genes shared N-glycosylation-modified models of N-x-S and N-G. Five out of 10 proteins were upregulated in WZS pigs compared to LW pigs at 4 months old, while five proteins increased in WZS pigs from 4 to 8 months old. In conclusion, this research provides valuable information on the N-glycosylation motifs in liver oxidation genes of WZS pigs.

Hydrogen Oxidation and Evolution Reaction on Platinum in Alkaline Electrolyte: Fixed Reference vs. Overpotential and the Effect of H2 Concentration

Abstract Understanding the kinetics of the hydrogen oxidation and evolution reaction (HOR/HER) in alkaline media is of great interest, but the underlying mechanism and the dependency on the hydrogen pressure are still debated. Herein, we investigated the HOR/HER on polycrystalline platinum in alkaline electrolyte using a rotating disk electrode (RDE). Unlike typically done, we performed the data analysis on a fixed potential scale, which has implications for the assessment of RDE mass-transport corrections and the definition of reaction orders. Analyzing the kinetic currents on a fixed potential, we find hydrogen reaction orders of essentially one and zero for the HOR and HER, respectively, at larger overpotentials. In contrast, fitting the kinetic currents in a potential around equilibrium with a Butler-Volmer model yields differing kinetic parameters and fractional reaction orders. Our findings can be explained with a potential-dependent transition in the HOR mechanism from Tafel–Volmer at small overpotentials to Heyrovsky–Volmer at higher overpotentials, with a concomitant change in the H2 reaction order from fractional to unity, thus reconciling previous propositions on the alkaline HOR/HER mechanism. Our results demonstrate the strength of using a fixed potential scale, and we expect this approach to be beneficial for studies of other electrocatalytic reactions.

Surface Reconstruction of Single-Twinned AgPdIr Nanoalloy during the Formate Oxidation and Dehydrogenation Reactions

Surface Reconstruction of Single-Twinned AgPdIr Nanoalloy during the Formate Oxidation and Dehydrogenation Reactions

Surface‐Interface Engineering of Electrocatalysts for Two‐Electron Water Oxidation Reaction to Produce H2O2

AbstractElectrochemical two‐electron water oxidation reaction (2e− WOR) driven by renewable energy offers an attractive route to produce H2O2, while the corresponding electrocatalyst still requires further improvement for the activity, selectivity, and the resulting H2O2 yield. Surface‐interface engineering of electrocatalysts has great potential to advance 2e− WOR performance. This review provides a succinct yet comprehensive insight into the functional mechanisms of surface‐interfacial properties affecting 2e− WOR performance on electrocatalyst. The Gibbs free energy theoretical framework related to surface electronic structure and interfacial reactive kinetics mechanism related to electrolyte, electrode–electrolyte interface structure, and interfacial microenvironment properties are firstly discussed. Afterward, various surface‐interface engineering strategies toward high performance electrocatalysts including the regulation of surface electronic structure, the electrode–electrolyte interface structure, and the interfacial microenvironment have been overviewed. Rational manipulations of the above surface‐interfacial engineering strategies are critical to design highly efficient 2e− WOR electrocatalysts, leading to the development of the green H2O2 production.

Detectability of biosignatures in warm, water-rich atmospheres

Warm rocky exoplanets within the habitable zone of Sun-like stars are favoured targets for current and future missions. Theory indicates these planets could be wet at formation and remain habitable long enough for life to develop. However, it is unclear to what extent an early ocean on such worlds could influence the response of potential biosignatures. In this work we test the climate-chemistry response, maintenance, and detectability of biosignatures in warm, water-rich atmospheres with Earth biomass fluxes within the framework of the planned LIFE mission. We used the coupled climate-chemistry column model 1D-TERRA to simulate the composition of planetary atmospheres at different distances from the Sun, assuming Earth's planetary parameters and evolution. We increased the incoming instellation by up to 50 percent in steps of 10 percent, corresponding to orbits of 1.00 to 0.82 AU. Simulations were performed with and without modern Earth’s biomass fluxes at the surface. Theoretical emission spectra of all simulations were produced using the GARLIC radiative transfer model. LIFEsim was then used to add noise to and simulate observations of these spectra to assess how biotic and abiotic atmospheres of Earth-like planets can be distinguished. Increasing instellation leads to surface water vapour pressures rising from 0.01 bar (1.31<!PCT!>, S = 1.0) to 0.61 bar (34.72<!PCT!>, S = 1.5). In the biotic scenarios, the ozone layer survives because hydrogen oxide reactions with nitrogen oxides prevent the net ozone chemical sink from increasing. Methane is strongly reduced for instellations that are 20<!PCT!> higher than that of the Earth due to the increased hydrogen oxide abundances and UV fluxes. Synthetic observations with LIFEsim, assuming a 2.0 m aperture and resolving power of a R = 50, show that ozone signatures at 9.6 mu m reliably point to Earth-like biosphere surface fluxes of O$_2$ only for systems within 10 parsecs. The differences in atmospheric temperature structures due to differing H$_2$O profiles also enable observations at 15.0 mu m to reliably identify planets with a CH$_4$ surface flux equal to that of Earth's biosphere. Increasing the aperture to 3.5 m and increasing instrument throughput to 15<!PCT!> increases this range to 22.5 pc.

Modulating N−H Bond Cleavage in Catalytic Ammonia Oxidation Reaction

AbstractThe ammonia oxidation reaction (AOR) exhibits significant potential for environmental remediation and energy utilization. Nevertheless, the complex reaction mechanism of the AOR poses numerous challenges to its application. To overcome these challenges and realize an efficient AOR process, a thorough understanding of every elementary reaction step, especially the cleavage of N−H bonds, is crucial. This review delves into the influence of N−H bond cleavage on the rate and selectivity of AOR, and summarizes the latest advancements in promoting this crucial step. Furthermore, we discuss the challenges faced by N−H bond cleavage and provide insights into the design of efficient catalytic AOR systems.

Role of Active Centers in Predicting the Catalyst Turnover: A Theoretical Study.

Water oxidation catalysis has garnered significant attention due to its potential for sustainable energy conversion. Among molecular catalysts, [Fe(OTf)2 (Me2Pytacn)] complexes have exhibited notable turning-over rates. Although various [M(OTf)2 (Me2Pytacn)] complexes (M = Mn, Co, Ni) have been synthesized, however, the role of active centres has not been thoroughly investigated. In this study, we apply our newly developed catalytic models, efficiency conceptualization model (ECM) and the maximum kinetic efficiency MaxKinEff framework to assess the role of the active centres in its catalytic performance. Our computational analysis identifies cobalt-based [Co(OTf)2 (Me2Pytacn)] as a superior alternative for water oxidation reactions. Notably, cobalt catalysts exhibit a longer lifespan (~ 44 days) and higher turnover numbers (TON), with computed values of (ECM) = 3.30 h-1, (ECM) = 3456, (MaxKinEff) = 12.43 h-1, and (MaxKinEff) = 3616. These findings suggest that cobalt could play a pivotal role in improving the efficiency of molecular catalysts for water oxidation.

Effect of Phycocyanin and Butylated Hydroxytoluene on the Oxidative Stability of Safflower Oil: A Comprehensive Kinetic Investigation

ABSTRACTSafflower includes both saturated and unsaturated fatty acids especially high levels of polyunsaturated fatty acid (PUFA). The addition of antioxidants during oil processing is one of the most effective methods. The aim of this research was to evaluate the oxidative stability of safflower oil supplemented with phycocyanin (PC) (200, 300, and 400 ppm), or butylated hydroxytoluene (BHT) (200 ppm), at 80, 90, and 100°C during the storage time. Oxidative stability of oil was measured through the assay of primary and secondary oxidation products: Peroxide value (PV) and thiobarbituric acid reactive substances (TBARS) were evaluated, respectively. Results showed that the addition of PC at 300 and 400 ppm caused the lowest peroxide levels. In addition, the oxidation reactions of this oil followed a first‐order kinetic model for PV and TBARS. The amounts of PV and TBARS were dependent on the storage temperature; according to the Arrhenius equation, the activation energy (Ea) of the samples that contain 300 and 400 ppm PC decreased in all the tested temperatures compared to control. Results of the oxidative stability indicated that PC may have superior antioxidant properties than BHT and can potentially inhibit the oil oxidation. The sample containing 300 ppm PC demonstrated heightened efficacy in suppressing primary oxidation. Moreover, the results of sensory evaluation test showed that the 300 ppm PC sample received the highest rating for overall quality, which confirm that 300 ppm PC sample could be the best sample to decrease the oxidative stability in safflower oil.

The Activation of Oxygen Species on the Pt/CeO2 Catalyst by H2 for NO Oxidation

The Pt/CeO2 catalyst has attracted significant attention due to its exceptional performance in NO oxidation. This study comprehensively examines the effects of calcination temperature and H2 pretreatment on the structure and activity of the Pt/CeO2 catalyst. Experimental findings indicate that the calcination temperature significantly affects the catalyst’s redox performance, thereby modulating its efficacy in NO oxidation reactions. H2 pretreatment facilitates the creation of oxygen vacancies on the catalyst, assisted by the reduction in PtOx to Pt, enhancing the formation of activated oxygen and thereby improving NO oxidation. This study offers valuable insights into the design and optimization of Pt/CeO2 catalysts for environmental applications, particularly in the development of exhaust gas after-treatment technologies.

Kinetic Modeling of Brilliant Blue Discoloration by Ozonation

This paper presents the results of investigations on the kinetic modeling of Brilliant Blue FCF (BB) discoloration reactions in aqueous solutions with different ozone concentrations and pH conditions. Kinetic studies involve knowledge of the structure and properties of dye and ozone, as well as of the experimental conditions. In general, scientists admit that the predominant oxidation pathway is direct (by free oxygen atoms) or indirect (by free hydroxyl radicals); this will depend on influencing factors such as the physicochemical properties of the dye, the pH of the aqueous solution, ozone concentration, reaction time, and the contact mode with/without stirring. In this experimental research, two pathways were chosen following CBB = f(t)—1. a constant dye concentration and different ozone concentrations, in the concentration range of 100–250 mg/L, in three pH media (acidic, neutral, and basic), with and without stirring; 2. a constant concentration of ozone and different dyes in the concentration range of 2.5–10 mg/L, under the conditions of point 1. With the obtained experimental data, the curves CBB = f(t) were drawn and processed according to the integral method of classical kinetics, based on first- and second-order equations. Unfortunately, this simple procedure did not give any results for the pH values studied. The rate constants were negative, and/or the reaction order depended on the initial conditions. Due to its structure, the BB dye has several chromophore groups, and thus multiple attack centers, resulting in several oxidation by-products, which is why the 1H-NMR spectrum was recorded for the discoloration of BB with ozone. Since the stoichiometry of the overall oxidation reaction, as well as the relationship between the rate constant and the reaction conditions mentioned above, is not known, a kinetic model based on mass transfer coupled with a chain reaction in the bulk liquid phase was proposed and successfully tested at pH = 7. This research approach also involves the consolidation of the theoretical bases of the ozonation process through the kinetic study carried out, as well as the proposal of a kinetic model. These systematics lead to results that are applicable to other aqueous systems that are impure with dyes, allowing for generalizations and the development of the field, ensuring the sustainability of the research.

Non-Noble Metal Catalysts for Electrooxidation of 5-Hydroxymethylfurfural.

2,5-Furandicarboxylic acid (FDCA) is a class of valuable biomass-based platform compounds. The creation of FDCA involves the catalytic oxidation of 5-hydroxymethylfurfural (HMF). As a novel catalytic method, electrocatalysis has been utilized in the 5-hydroxymethylfurfural oxidation reaction (HMFOR). Common noble metal catalysts show catalytic activity, which is limited by price and reaction conditions. Non-noble metal catalyst is known for its environmental friendliness, affordability and high efficiency. The development of energy efficient non-noble metal catalysts plays a crucial role in enhancing the HMFOR process. It can greatly upgrade the demand of industrial production, and has important research significance for electrocatalytic oxidation of HMF. In this paper, the reaction mechanism of HMF undergoes electrocatalytic oxidation to produce FDCA are elaborately summarized. There are two reaction pathways and two oxidation mechanisms of HMFOR discussed deeply. In addition, the speculation on the response of the electrode potential to HMFOR is presented in this paper. The main non-noble metal electrocatalysts currently used are classified and summarized by targeting metal element species. Finally, the paper focus on the mechanistic effects of non-noble metal catalysts in the reaction, and provide the present prospects and challenges in the electrocatalytic oxidation reaction of HMF.

Genome-Wide Analysis of the Class III Peroxidase Gene Family in Physcomitrium patens and a Search for Clues to Ancient Class III Peroxidase Functions

Plant class III peroxidases (PRXs) catalyze generation of reactive oxygen species and oxidation of various compounds including lignin precursors. PRXs function in cell wall metabolism, defense, and stress responses. However, gene redundancy and catalytic versatility have impeded detailed functional characterization of PRX genes. The genome of the model moss Physcomitrium patens harbors a relatively small number (49) of PRX genes. Conserved architecture of four exons and three ‘001’ introns, found in some algal PRX genes and in the PpPRX family, suggests that this architecture predated divergence of the green algal and land plant lineages. The PpPRX family expanded mainly through whole-genome duplications. All duplicated pairs but one were under purifying selection and generally exhibited similar expression profiles. An expanded phylogenetic tree revealed a conserved land plant-wide clade that contained PRXs implicated in stress responses in non-lignifying cells, providing a clue to ancient functions of land plant PRXs. Functional clustering was not observed, suggesting convergent evolution of specific PRX functions (e.g., lignification) in different plant lineages. With its small complement of PRXs, P. patens may be useful for functional characterization of land plant PRXs. Several PpPRXs were proposed for further study, including PpPRX34 and PpPRX39 in the ancient land plant-wide clade.

Oxygen Defect Site Filling Strategy Induced Moderate Enrichment of Reactants for Efficient Electrocatalytic Biomass Upgrading.

The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) provides a feasible approach for the efficient utilization of biomass. Defect regulation is an effective strategy in the field of biomass upgrading to enhance the adsorption capacity of reactants and thus increase the activity. However, how to select appropriate strategies to regulate the over-enrichment of reactants induced by excessive oxygen vacancy is still a huge challenge. In this work, the defect-filling strategy to design and construct an element-filled oxygen vacancy site layered double hydroxide (S─Ov─LDH) is adopted, which achieves a significant reduction in the electrolysis potential of biomass platform molecule HMF oxidation reaction and a significant increase in current density. Physical characterizations, electrochemical measurements, and theoretical calculations prove that the formation of metal─S bond in the second shell effectively regulates the electronic structure of the material, thus weakening the over-strong adsorption of HMF and OH- induced by excessive oxygen vacancy, promoting the formation of high-valence Co3+ during the reaction, and forming new adsorption sites. This work discusses the catalytic enhancement mechanism of defect filling in detail, fills the gap of defect filling in the field of biomass upgrading, and provides favorable guidance for the further development of defect regulation strategies.

Metastable Oxygen-Induced Light-Enhanced Doping in Mixed Sn-Pb Halide Perovskites.

Mixed Sn-Pb halide perovskites are promising absorber materials for solar cells due to the possibility of tuning the bandgap energy down to 1.2-1.3 eV. However, tin-containing perovskites are susceptible to oxidation affecting the optoelectronic properties. In this work, we investigated qualitatively and quantitatively metastable oxygen-induced doping in isolated ASnxPb1-xI3 (where A is methylammonium or a mixture of formamidinium and cesium) perovskite thin films by means of microwave conductivity, structural and optical characterization techniques. We observe that longer oxygen exposure times lead to progressively higher dark conductivities, which slowly decay back to their original levels over days. Here oxygen acts as an electron acceptor, leading to tin oxidation from Sn2+ to Sn4+ and creation of free holes. The metastable oxygen-induced doping is enhanced by exposing the perovskite simultaneously to oxygen and light. Next, we show that doping not only leads to the reduction in the photoconductivity signal but also induces long-term effects even after loss of doping, which is thought to derive from consecutive oxidation reactions leading to the formation of defect states. On prolonged exposure to oxygen and light, optical and structural changes can be observed and related to the formation of SnOx and loss of iodide near the surface. Our work highlights that even a short-term exposure to oxygen immediately impairs the charge carrier dynamics of the perovskite, while structural perovskite degradation is only noticeable upon long-term exposure and accumulation of oxidation products. Hence, for efficient solar cells, exposure of mixed Sn-Pb perovskites to oxygen during production and operation should be rigorously blocked.

GmTRAB1, a Basic Leucine Zipper Transcription Factor, Positively Regulates Drought Tolerance in Soybean (Glycine max. L)

The basic leucine zipper (bZIP) transcription factors play crucial roles in plant resistance to environmental challenges, but the biological functions of soybean bZIP members are still unclear. In this study, a drought-related soybean bZIP gene, GmTRAB1, was analyzed. The transcript of GmTRAB1 was upregulated under drought, ABA, and oxidative stresses. Overexpression of GmTRAB1 improved the osmotic stress tolerance of transgenic Arabidopsis and soybean hairy roots associated with increased proline content and activity of antioxidant enzymes and reduced accumulations of malonaldehyde and reactive oxide species. However, RNA interference silencing of GmTRAB1 in the soybean hairy roots improved drought sensitivity. Furthermore, GmTRAB1 increased the sensitivity of transgenic plants to ABA and participated in modulating ABA-regulated stomatal closure upon drought stress. In addition, GmTRAB1 stimulated the transcript accumulation of drought-, ABA-, and antioxidant-related genes to respond to drought. Collectively, this research will contribute to understanding the molecular mechanisms of bZIP transcription factors in soybean’s resistance to drought.

Kinetic analysis on low‐temperature oxidation of wood pellets by isothermal microcalorimetry

AbstractLow‐temperature chemical oxidation is the major driver of self‐heating during storage of wood pellets and its kinetics is essential to describe the heat evolution. In the present work, isothermal microcalorimetry was used to characterize heat generation behavior of three types of wood pellets (pine, fir, and redwood pellets) at 30–70°C. The obtained data were employed to derive the kinetics of low‐temperature oxidation by the peak power, iso‐conversional method, and non‐steady analysis. The consistency and applicability of the kinetics derived by the three methods were evaluated. Kinetic parameters determined by the peak power method were observed to match those from the iso‐conversional method at lower conversions of the oxidation for heat generation. The kinetics derived by the iso‐conversional method indicated the oxidation reactivity generally decreasing and activation energy increasing with the conversion because of O2 consumption and reaction mechanism changing. With the impact of O2 consumption considered separately, the kinetics from the non‐steady analysis is capable of describing the evolution of heat power with the conversion and also consistent with that from the peak power method in describing intrinsic reactivity of pellet materials. The kinetics from the peak power and iso‐conversional methods lump the impact of O2 concentration with the reaction reactivity, suggesting their applications requiring additional models for connecting with O2 consumption.

Elicitors fortifies the plant resilience against metal and metalloid stress.

This review addresses plant interactions with HMs, emphasizing defence mechanisms and the role of chelating agents, antioxidants and various elicitor molecules in mitigating metal toxicity in plants. To combat soil contamination with HMs, chelate assisted phytoextraction using application of natural or synthetic aminopolycarboxylic acids is an effective strategy. Plants also employ diverse signaling pathways, including hormones, calcium, reactive oxygen species, nitric oxide, and Mitogen-Activated Protein Kinases influencing gene expression and defence mechanisms to counter HM stress. Phytohormones enhance the enzymatic and non-enzymatic antioxidant defence mechanism and the level of secondary metabolites in plants when exposed to HM stress. Also it activates genes responsible for DNA repair mechanism. In addition, the plant hormones can also regulate the activity of several transporters of HMs, thereby preventing their entry into the cell. Elicitor molecules regulate metal and metalloid absorption, sequestration and transport in plants. Combining of different elicitors like jasmonic acid, calcium, salicylic acid etc. effectively mitigates metal and metalloid stress in plants. Moreover, microbes including bacteria and fungi, offer eco-friendly and efficient solution for HM remediation. Understanding these elicitors, microbes and various signaling pathways is crucial for developing strategies to enhance plant resilience to metal and metalloid stress.