Insight into catalytic performance and reaction mechanism for toluene total oxidation over Cu-Ce supported catalyst.

Herein, three supported catalysts, CuO/Al2O3, CeO2/Al2O3, and CuO-CeO2/Al2O3, were synthesized by the convenient impregnation method to reveal the effect of CeO2 addition on catalytic performance and reaction mechanism for toluene oxidation. Compared with CuO/Al2O3, the T50 and T90 (the temperatures at 50% and 90% toluene conversion, respectively) of CuO-CeO2/Al2O3 were reduced by 33 and 39 °C, respectively. N2 adsorption-desorption experiment, XRD, SEM, EDS mapping, Raman, EPR, H2-TPR, O2-TPD, XPS, NH3-TPD, Toluene-TPD, and in-situ DRIFTS were conducted to characterize these catalysts. The excellent catalytic performance of CuO-CeO2/Al2O3 could be attributed to its strong copper-cerium interaction and high oxygen vacancies concentration. Moreover, in-situ DRIFTS proved that CuO-CeO2/Al2O3 promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene. This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.

The role of sulfur cycle in new particle formation: Cycloaddition reaction of SO3 to H2S.

The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process, which is the first step of new particle formation (NPF). In the present study, cycloaddition reaction mechanism of sulfur trioxide (SO3) to hydrogen sulfide (H2S) which is a typical air pollutant and toxic gas detrimental to the environment were comprehensively investigate through theoretical calculations and Atmospheric Cluster Dynamic Code simulations. Gas-phase stability and nucleation potential of the product thiosulfuric acid (H2S2O3, TSA) were further analyzed to evaluate its atmospheric impact. Without any catalysts, the H2S + SO3 reaction is infeasible with a barrier of 24.2 kcal/mol. Atmospheric nucleation precursors formic acid (FA), sulfuric acid (SA), and water (H2O) could effectively lower the reaction barriers as catalysts, even to a barrierless reaction with the efficiency of cis-SA > trans-FA > trans-SA > H2O. Subsequently, the gas-phase stability of TSA was investigated. A hydrolysis reaction barrier of up to 61.4 kcal/mol alone with an endothermic isomerization reaction barrier of 5.1 kcal/mol under the catalytic effect of SA demonstrates the sufficient stability of TSA. Furthermore, topological and kinetic analysis were conducted to determine the nucleation potential of TSA. Atmospheric clusters formed by TSA and atmospheric nucleation precursors (SA, ammonia NH3, and dimethylamine DMA) were thermodynamically stable. Moreover, the gradually decreasing evaporation coefficients for TSA-base clusters, particularly for TSA-DMA, suggests that TSA may participate in NPF where the concentration of base molecules are relatively higher. The present new reaction mechanism may contributes to a better understanding of atmospheric sulfur cycle and NPF.

In situ DRIFTs-based comprehensive reaction mechanism of photo-thermal synergetic catalysis for dry reforming of methane over Ru-CeO2 catalyst.

Solar-driven photo-thermal dry reforming of methane (DRM) is an environmentally friendly production route for high-value-added chemicals. However, the lack of thorough understanding of the mechanism for photo-thermal reaction has limited its further development. Here, we systematically investigated the mechanism of photo-thermal DRM reaction with the representative of Ru/CeO2 catalyst. Through in situ DRIFTs and transient experiments, comprehensive investigation into the reaction steps and their reactive sites in the process of DRM reaction were conducted. Besides, the excitation and migration direction of photo-electron was determined by ISI-XPS experiments, and the change of surface defect structure induced by light was characterized by ISI-EPR experiments. Based on the above results, the photo-enhancement effect on each micro-reaction step was determined. This study provides a theoretical basis for the industrialization of photo-thermal DRM reaction and its development of catalysts.

Regulating the valence and size of the active center of Co/Al2O3 catalyst improved the performance and selectivity of NH3-SCO.

To improve the activity of Co/Al2O3 catalysts in selective catalytic oxidation of ammonia (NH3-SCO), valence state and size of active centers of Al2O3-supported Co catalysts were adjusted by conducting H2 reduction pretreatment. The NH3-SCO activity of the adjusted 2Co/Al2O3 catalyst was substantially improved, outperforming other catalysts with higher Co-loading. Fresh Co/Al2O3 catalysts exhibited multitemperature reduction processes, enabling the control of the valence state of the Co-active centers by adjusting the reduction temperature. Changes in the state of the Co-active centers also led to differences in redox capacity of the catalysts, resulting in different reaction mechanisms for NH3-SCO. However, in situ diffuse reflectance infrared Fourier transform spectra revealed that an excessive O2 activation capacity caused overoxidation of NH3 to NO and NO2. The NH3-SCO activity of the 2Co/Al2O3 catalyst with low redox capacity was successfully increased while controlling and optimizing the N2 selectivity by modulating the active centers via H2 pretreatment, which is a universal method used for enhancing the redox properties of catalysts. Thus, this method has great potential for application in the design of inexpensive and highly active catalysts.

Self-Adaptive Electrochemistry of Phosphate Cathodes toward Improved Calcium Storage.

Polyanion phosphates exhibit great potential as calcium-ion battery (CIB) cathodes, boasting high working voltage and rapid ion diffusion. Nevertheless, they frequently suffer from capacity decay with irreversible phase transitions; the underlying mechanisms remain elusive. Herein, we report an adaptively layerized structure evolution from discrete NaV2O2(PO4)2F nanoparticles (NPs) to interconnected VOPO4 nanosheets (NSs), triggered by electrochemical (de)calcification, leading to an improvement in Ca2+ storage performance. This electrochemistry-driven self-adapted layerization occurs over approximately 200 cycles, during which NPs undergo a "deform/merge-layerization" process, transitioning from a three-dimensional to a two-dimensional atomic structure, with a distinct 0.68 nm lattice spacing. The transition mechanism is demonstrated to be linked to the gradual separation of structural Na+ and F-. The resultant VOPO4 NSs exhibit exceptional Ca2+ diffusion kinetics (3.19 × 10-9 cm2 s-1, currently the optimal value among inorganic cathode materials for CIBs), enhanced capacity (∼100 mA h g-1), longevity (over 1000 cycles at 50 mA g-1), and high rate (84% retention rates when increasing current density from 50 to 200 mA g-1). Employing advanced electron microscopy, this study reveals an electrochemical activation-induced structure evolution at the atomic level, providing valuable insights into the design of high-performance CIB cathodes.

Kinetic research of red mud waste oxidative pyrolysis and comparison under different atmospheres.

Red mud, as a solid waste with high alkalinity, had a detrimental impact on the environment and required urgent attention. Currently, the mass processing and consumption of red mud were typically conducted under thermal conditions, so it was essential to gain a comprehensive understanding of the oxidative pyrolysis process. The thermogravimetric experiments were conducted at multiple heating rates in air and exhibited three obvious stages. The activation energy and reaction mechanism of three oxidative pyrolysis stages were explored using model-free and model-fitting methods, revealing the activation energies of 162.2, 265.8, 214.1 kJ/mol and the most suitable reaction mechanisms of g(α)=[-ln(1-α)]³, g(α)=1-(1-α)1/4, g(α)=[-ln(1-α)]1/2 for each stage, respectively. Furthermore, the estimated kinetic parameters and reaction mechanisms were applied to extra heating rate to verify the accuracy. More important, the effect of air on the pyrolysis process of red mud was examined by comparing the results with those obtained from pure nitrogen pyrolysis. The obtained oxidative pyrolysis characteristics of red mud could provide valuable insights of its co-pyrolysis or combustion for resources recycling.

Understanding the Electrochemical Carbon Dioxide Reduction Reaction Mechanism of Lattice Tuning of Copper by Silver Single-Crystal Surface.

Intermolecular interactions and adsorbate coverage on a metal electrode's surface/interface play an important role in CO2 reduction reaction (CO2RR). Herein, the activity and selectivity of CO2RR on bimetallic electrode, where a full monoatomic Cu layer covers on Ag surface (CuML/Ag) are investigated by using density functional theory calculations. The surface geometric and electronic structure results indicate that there is high electrocatalytic activity for CO2RR on the CuML/Ag electrode. Specifically, the CuML/Ag surface can accelerate the H2O and CO2 adsorption and hydrogenation while lowering the reaction energy of the rate-determining step. The structure parameters of chemisorbed CO2 with and without H2O demonstrate that activated H2O not only promotes the C-O dissociation but also provides the protons required for CO2RR on the CuML/Ag electrode surface. Furthermore, the various reaction mechanism diagrams indicate that the CuML/Ag electrode has high selectivity for CO2RR, and the efficiency of products can be regulated by modulating the reaction's electric potential.

Research Progress in Structure Evolution and Durability Modulation of Ir- and Ru-Based OER Catalysts under Acidic Conditions.

Green hydrogen energy, as one of the most promising energy carriers, plays a crucial role in addressing energy and environmental issues. Oxygen evolution reaction catalysts, as the key to water electrolysis hydrogen production technology, have been subject to durability constraints, preventing large-scale commercial development. Under the high current density and harsh acid-base electrolyte conditions of the water electrolysis reaction, the active metals in the catalysts are easily converted into high-valent soluble species to dissolve, leading to poor structural durability of the catalysts. There is an urgent need to overcome the durability challenges under acidic conditions and develop electrocatalysts with both high catalytic activity and high durability. In this review, the latest research results are analyzed in depth from both thermodynamic and kinetic perspectives. First, a comprehensive summary of the structural deactivation state process of noble metal oxide catalysts is presented. Second, the evolution of the structure of catalysts possessing high durability is discussed. Finally, four new strategies for the preparation of stable catalysts, "electron buffer (ECB) strategy", combination strength control, strain control, and surface coating, are summarized. The challenges and prospects are also elaborated for the future synthesis of more effective Ru/Ir-based catalysts and boost their future application.

Amine Exchange of Aminoalkylated Phenols as Dynamic Reaction in Benzoxazine/Amine-Based Vitrimers.

Bisfunctional benzoxazine and polyether diamine-based polymers show Arrhenius-like stress-relaxation varying with stoichiometry and polymerization temperatures proving vitrimeric behavior. Molecular structural investigations reveal the presence of different aminoalkylated phenols occurring at varying ratios depending on polymer composition and polymerization conditions. The vitrimeric mechanism is found to involve an amine exchange reaction of aminoalkylated phenols in an equilibrium reaction like a nucleophilic substitution reaction. As determined by molecular studies and dissolution experiments in reactive solvents, aliphatic and aromatic primary as well as aliphatic secondary amines in the polybenzoxazine structure can act as nucleophiles in reaction with electrophilic methylene bridges. Thus, aminoalkylated phenols proved to be a relevant structural motif resulting in a vitrimeric polybenzoxazine due to amine exchange reaction.

MnCe-based catalysts for removal of organic pollutants in urban wastewater by advanced oxidation processes - A critical review.

With Advanced oxidation processes (AOPs) widely promoted, MnCe-based catalysts have received extensive attention under the advantages of high efficiency, stability and economy for refractory organic pollutants present in urban wastewater. Driven by multiple factors such as environmental pollution, technological development, and policy promotion, a systematic review of MnCe-based catalysts is urgently needed in the current research situation. This research provides a critical review of MnCe-based catalysts for removal of organic pollutants in urban wastewater by AOPs. It is found that co-precipitation and sol-gel methods are more appropriate methods for catalyst preparation. Among a host of influence factors, catalyst composition and pH are crucial in the catalytic oxidation processes. The synergistic effect of the free radical pathway and surface catalysis results in better pollutants degradation. It is more valuable to utilize multiple systems for oxidation (e.g., photo-Fenton technology) to improve the catalytic efficiency. This review provides theoretical guidance for MnCe-based catalysts and offers a reference direction for future research in the AOPs of organic pollutants removal from urban wastewater.

Crystalline-Amorphous IrOx Supported on Perovskite Nanotubes for pH-Universal OER.

Designing catalysts with desirable oxygen evolution reaction (OER) performance under pH-universal conditions is of great significance to promote the development of hydrogen production. Herein, we successfully synthesized a crystalline-amorphous IrOx supported on perovskite oxide nanotubes to obtain IrOx@La0.6Ca0.4Fe0.8Ni0.2O3 with superior OER performance in whole pH media. The overpotential of the IrOx@La0.6Ca0.4Fe0.8Ni0.2O3 catalyst in media of pH 14, 7.2, and 1 has been demonstrated to be 120, 400, and 143 mV, respectively, with no significant element dissolution as well as double-layer capacitance decay after the durability test. Through comparative experiments with IrOx@CNT and the physical mixture of IrOx and La0.6Ca0.4Fe0.8Ni0.2O3, it is found that the strong metal-support interaction (SMSI) in IrOx@La0.6Ca0.4Fe0.8Ni0.2O3 makes IrOx exist in an amorphous state rich in Ir3+, which is closely associated with the surface-active species Ir-OH. Through the regulation of Ir by a perovskite oxide support at the heterointerface, the reaction breaks through the limitation of the adsorbate evolution mechanism (AEM) and converts to a lattice-oxygen-mediated mechanism (LOM), which was fully demonstrated by the addition of the probe tetramethylammonium cation (TMA+), a LOM reaction intermediate, to the electrolyte. This work fills the research gap of perovskite oxide supported Ir-based catalysts with heterogeneous structures, providing an excellent strategy for the structural design of efficient pH-universal OER catalysts for hydrogen production systems.

Shannon entropy variation as a global indicator of electron density contraction at interatomic regions in chemical reactions.

CONTEXT: The negative of the Shannon entropy derivative is proposed to account for electron density contraction as the chemical bonds are breaking and forming during a chemical reaction. We called this property the electron density contraction index, EDC, which allows identifying stages in a reaction that are dominated by electron contraction or expansion. Four different reactions were analyzed to show how the EDC index changes along the reaction coordinate. The results indicate that the rate of change of Shannon entropy is directly related to the rate of change of the electron density at the bond critical points between all the atomic pairs in the molecular systems. It is expected that EDC will complement the detailed analysis of reaction mechanisms that can be performed with the theoretical tools available to date. METHODS: Density functional theory calculations at the B3LYP/6-31G(d,p) level of theory were carried out using Gaussian 16 to analyze the reaction mechanisms of the four reactions studied. The reaction paths were obtained via the intrinsic reaction coordinate method, which served as the reaction coordinate to obtain the reaction force and the EDC profiles in each case. Shannon entropy and electron density at the bond critical points were calculated using the Multiwfn 3.7 package.

Recent advancements in Fe-based catalysts for the efficient reduction of NOx by CO.

The technology of CO selective catalytic reduction of NOx (CO-SCR) showcases the potential to simultaneously eliminate CO and NOx from industrial flue gas and automobile exhaust, making it a promising denitrification method. The development of cost-effective catalysts is crucial for the widespread implementation of this technology. Transition metal catalysts are more economically viable than noble metal catalysts. Among these, Fe emerges as a prominent choice due to its abundant availability and cost-effectiveness, exhibiting excellent catalytic performance at moderate reaction temperatures. However, a significant challenge lies in achieving high catalytic activity at low temperatures, particularly in the presence of O2, SO2, and H2O, which are prevalent in specific industrial flue gas streams. This review examines the use of Fe-based catalysts in the CO-SCR reaction and elucidates their catalytic mechanism. Furthermore, it also discusses various strategies devised to enhance low-temperature conversion, taking into account factors such as crystal phase, valence states, and oxygen vacancies. Subsequently, the review outlines the challenges encountered by Fe-based catalysts and offers recommendations to improve their catalytic efficiency for use in low-temperature and oxygen-rich environments.

Selectively recovering rare earth elements with carboxyl immobilized metal-organic framework from ammonium-rich wastewater.

The material with high adsorption capacity and selectivity is essential for recovering rare earth elements (REES) from ammonium (NH4+-N)-rich wastewater. Although the emerging metal-organic framework (MOF) has gained intensive attention in REES recovery, there are scientific difficulties unsolved regarding restricted adsorption capacity and selectivity, hindering its extensive engineering applications. In this work, a diethylenetriamine pentaacetic (DTPA)-modified MOF material (MIL-101(Cr)-NH-DTPA) was prepared through an amidation reaction. The MIL-101(Cr)-NH-DTPA showed enhanced adsorption capacity for La(III) (69.78 mg g-1), Eu(III) (103.01 mg g-1) and Er(III) (83.41 mg g-1). The adsorption isotherm and physical chemistry of materials indicated that the adsorption of REEs with MIL-101(Cr)-NH-DTPA was achieved via complexation instead of electrostatic adsorption. Such complexation reaction was principally governed by -COOH instead of -NH2 or -NO2. Meanwhile, the resulting material remained in its superior activity even after five cycles. Such a constructed adsorbent also exhibited excellent selective adsorption activity for La(III), Eu(III), and Er(III), with removal efficiency reaching 70% in NH4+-N concentrations ranging from 100 to 1500 mg L-1. This work offers underlying guidelines for exploitation an adsorbent for REEs recovery from wastewater.

Ni(0)-Catalyzed Rearrangement of Vinylcyclobutanones (VCBOs) to Synthesize Six-Membered Non-Conjugated Enones.

We report here the first nickel-catalyzed rearrangement of vinylcyclobutanones (VCBOs) under mild conditions to synthesize non-conjugated cyclohexenone derivatives, which so far do not have many ways to be accessed. The reaction exhibits a wide substrate scope with reaction yields up to 98%. This VCBO rearrangement can also be used to access various n/6 (n = 5-8) bicyclic products efficiently. Furthermore, mechanism of this rearrangement has been investigated using DFT calculations, showing that vinyl group-assisted cyclobutanone C-C cleavage is easy with a computed activation free energy of 18.1 kcal/mol.

Rational Linker Design for Enhanced Performance of MOF-Derived Catalysts in Electrochemical Urea Synthesis.

2D metal-organic frameworks (2D MOFs) offer promising electrocatalytic potential for urea synthesis, yet the underlying reaction mechanisms and structure-activity relationships remain unclear. Using Cu-BDC as a model, density functional theory (DFT) calculations to elucidate these aspects are conducted. The results reveal a novel coupling mechanism involving *NO─CO and *NO─*ONCO, emphasizing the impact of linker modifications on Cu spin states and charge distribution. Notably, Cu-BDC-NH2 and Cu─BDC─OH emerge as promising catalysts. Additionally, structure-activity relationships through descriptors like d-band center, IE ratio, and L(Cu─O), providing insights for rational catalyst design is established. These findings pave the way for optimized catalysts and sustainable urea production, opening avenues for future research and technological advancements.

Flow-Chemistry Based Green Synthesis of Graphene Oxide at Minutes Timescale.

Graphene oxide (GO) is broadly investigated in the electrochemical field. However, for industrial applications, it still suffer from high pollution, low efficiency, poor production quality, and safety concerns associated with traditional synthesis methods. Herein, guided by theoretical analyses, a new oxygen-atom-transfer (OAT) mechanism for periodate oxidizing graphite is revealed, exhibiting controllable reaction activity, strong orbital interaction, and abundant electron transfer. Moreover, a flow chemistry strategy with high mass/heat transfer rates is designed to enhance interlayer diffusion and reaction dynamics between oxidants and graphite, ensuring the efficient synthesis of GO within several minutes. As a result, both low oxygen-content GO with large size, and high oxygen-content GO with adequate active sites can be precisely and safely synthesized. Benefitting from the controllability of oxygen content and lateral size, the as-prepared GO sheets can be facilely assembled into fiber/film electrodes that present high mechanical flexibility, large electrical conductivity, and outstanding electrochemical performance.

Development of Novel Fluorescent Probes for Specific Detection of Hypochlorous Acid.

Hypochlorous acid (HClO) is widely used in everyday life for bleaching and disinfecting tap water, and also in human metabolism, where it plays an important role in destroying foreign bacterial invaders and pathogens as well as immune defense and cellular functioning maintenance. Abnormal levels of hypochlorous acid have the potential to cause joint inflammation, neuronal degeneration, and even life-threatening cancer. Specific identification and effective detection of hypochlorous acid are important for monitoring human health and the environment. In recent years, organic fluorescent probes have attracted much attention because of their simple synthesis, easy operation, high sensitivity, and high specificity, and a variety of hypochlorous acid fluorescent probes based on low-cost, easy-to-operate, and rapid identification have been developed. In this paper, we review the fluorescent probes that have been developed in the past five years for the specific recognition of hypochlorous acid based on different fluorophores, such as triphenylamine, coumarin, 1,8-naphthalize, etc., as well as recognition units, such as N-N dimethyl thiosemicarbazone, and describe how the probes and hypochlorous acid interact for identification in the same manner as other fluorescent probes. In addition, the reaction mechanism between the probe and hypochlorous acid, the fluorescence change of the probe, and the detection limit are described to illustrate the progress in the detection of hypochlorous acid in recent years and to provide ideas for the development of hypochlorous acid fluorescent probes in the future.

Kinetic and Catalytic Mechanism of the Methionine-Derived Glucosinolate Biosynthesis Enzyme Methylthioalkylmalate Synthase.

In Brassica plants, methionine-derived aliphatic glucosinolates are chemically diverse natural products that serve as plant defense compounds, as well as molecules with dietary health-promoting effects. During their biosynthesis, methylthioalkylmalate synthase (MAMS) catalyzes the elongation reaction of the aliphatic chain. The MAMS catalyzed condensation of 4-methylthio-2-oxobutanoic acid (4-MTOB) and acetyl-CoA generates a 2-malate derivative that either enters the pathway for synthesis of C3-glucosinolates or undergoes additional extension reactions, which lead to C4- to C9-glucosinolates. Recent determination of the x-ray crystal structure of MAMS from Brassica juncea (Indian mustard) provided insight on the molecular evolution of MAMS, especially substrate specificity changes, from the leucine biosynthesis enzyme α-isopropylmalate synthase (IPMS) but left details of the reaction mechanism unanswered. Here we use the B. juncea MAMS2A (BjMAMS2A) isoform to analyze the kinetic and catalytic mechanism of this enzyme. Initial velocity studies indicate that MAMS follows an ordered bi bi kinetic mechanism, which based on the x-ray crystal structure, involves binding of 4-MTOB followed by acetyl-CoA. Examination of the pH-dependence of kcat and kcat/Km are consistent with acid/base catalysis. Site-directed mutagenesis of three residues originally proposed to function in the reaction mechanism - Arg89 (R89A, R89K, R89Q), Glu227 (E227A, E227D, E227Q), and His388 (H388A, H388N, H388Q, H388D, and H388E) - showed that only two mutants (E227Q and H388N) retained activity. Based on available structural and biochemical data, a revised reaction mechanism for MAMS-catalyzed elongation of methionine-derived aliphatic glucosinolates is proposed, which is likely also conserved in IPMS from leucine biosynthesis in plants and microbes.

LaCo0.95Mo0.05O3/CeO2 composite can promote the effective activation of peroxymonosulfate via Co3+/Co2+ cycle and realize the efficient degradation of hydroxychloroquine sulfate.

Hydroxychloroquine sulfate (HCQ) is extensively utilized due to its numerous therapeutic effects. Because of its properties of high solubility, persistence, bioaccumulation, and biotoxicity, HCQ can potentially affect water bodies and human health. In this study, the LaCo0.95Mo0.05O3-CeO2 material was successfully prepared by the sol-gel process, and it was applied to the experiment of degrading HCQ by activating peroxymonosulfate (PMS). The results of characterization analysis showed that LaCo0.95Mo0.05O3-CeO2 material had good stability, and the problem of particle agglomeration had been solved to some extent. Compared with LaCo0.95Mo0.05O3 material, it had a larger specific surface area and more oxygen vacancies, which was helpful to improve the catalytic activity for PMS. Under optimal conditions, the LaCo0.95Mo0.05O3-CeO2/PMS system degraded 95.5 % of HCQ in 10 min. The singlet oxygen, superoxide radicals, and sulfate radicals were the main radicals for HCQ degradation. The addition of Mo6+/Mo4+ and Ce4+/Ce3+ promoted the redox cycle of Co3+/Co2+ and enhanced the degradation rate of HCQ. Based on density functional theory and experimental analysis, three HCQ degradation pathways were proposed. The analysis of T.E.S.T software showed that the toxicity of HCQ was obviously reduced after degradation. The LaCo0.95Mo0.05O3-CeO2/PMS system displayed excellent reusability and the ability to remove pollutants in a wide range of real-world aqueous environments, with the ability to treat a wide range of pharmaceutical wastewater. In summary, this study provides some ideas for developing heterogeneous catalysts for advanced oxidation systems and provide an efficient, simple, and low-cost method for treating pharmaceutical wastewater that has good practical application potential.