Formation of active oxygen species on single-atom Pt catalyst and promoted catalytic oxidation of toluene

Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of active oxygen species generated in this reaction is still a challenging target.Herein,MgO nanosheets and single-atom Pt loaded MgO(Pt SA/MgO)nanosheets were synthesized and used as catalysts in toluene oxidation.The activation process of molecular oxygen and oxidation performance on the two catalysts were contrastively investigated.The Pt SA/MgO exhibited significantly enhanced catalytic activity compared to MgO.The oxygen vacancies can be easily generated on the Pt SA/MgO surface,which facilitate the activation of molecular oxygen and the formation of active oxygen species.Based on the experimental data and theoretical calculations,an active oxygen species promoted oxidation mechanism for toluene was proposed.In the presence of H2O,the molecular oxygen is more favorable to be dissociated to generate•OH on the oxygen vacancies of the Pt SA/MgO surface,which is the dominant active oxygen species.We anticipate that this work may shed light on further investigation of t10.1007/s12274-020-2765-1he oxidation mechanism of toluene and other VOCs over noble metal catalysts.

Active oxygen species and oxidation mechanism over Ce-doped LaMn_(0.8)Ni_(0.2)O_(3)/hierarchical ZSM-5 in pentanal oxidation

Hierarchical ZSM-5(HZ)molecular sieves based on fly ash were synthesized using a method combining water heat treatment with step-by-step calcination.The coupling catalysts between La_(1-x)Ce_(x)Mn_(0.8)-Ni_(0.2)O_(3)(x≤0.5)perovskites and HZ were prepared through the impregnation method,which were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),N_(2)adsorption,X-ray photoelectron spectroscopy(XPS),NH3-temperature programmed desoprtion(NH3-TPD),H_(2)-temperature programmed reduction(H_(2)-TPR)and O_(2)-TPD techniques and investigated regarding pentanal oxidation at 120-390℃to explore the effects of Ce doping on the catalytic activity and the active oxygen species of the coupling catalysts,meanwhile,the reaction mechanism and pathway of pentanal oxidation were also studied.The results reveal that Ce substitution at La sites can change the electronic interactions between all the elements and promote the electronic transfer among La,Ce,Ni,Mn and HZ,influencing directly the physicochemical characteristics of the catalysts.Moreover,the amount and transfer ability of surface adsorbed oxygen(O_(2)-and O-)regarded as the reactive oxygen species and the low temperature reducibility are the main influence factors in pentanal oxidation.Additionally,La_(0.8)Ce_(0.2)Mn_(0.8)Ni_(0.2)O_(3)/HZ exhibits the best catalytic activity and deep oxidation capacity as well as a better water resistance due to its larger amount of surface adsorbed oxygen species and higher low temperature reducibility.What’s more,appropriate Ce substitution can significantly enhance the amount of O_(2)-ions,which can distinctly enhance the catalytic activity of the catalyst,and moderate acid strength and appropriate acid amount can also facilitate the improvement of the pentanal oxidation activity.It is found that there is a synergic catalytic effect between surface acidity and redox ability of the catalyst.According to the in situ DRIFTS and GC/MS analyses,pentanal can be oxidized gradually to CO_(2)and H_(2)O by the surface oxygen species with the form of adsorption in air following the Langmuir-Hinshelwood(L-H)reaction mechanism.Two reaction pathways for the pentanal oxidation process are proposed,and the conversion of the formates to carbonates may be one of the main rate-determining steps.

Effects of Different Cadmium Levels on Active Oxygen Metabolism and H_2O_2-Scavenging System in Brassica campestris L.ssp.chinensis

The effects of different Cd (Cadmium) levels on generation of active oxygen speceies(AOS) and H2O2-scavenging system in the leaves of Brassica campestris L. ssp. chinensiswere studied. The results showed that generation rate, and H2O2 content were enhancedand malondialdehyde (MDA) content increased with the increase of Cd concentrations inthe growth medium. The activities of ascorbate peroxidase (APX), dehydroascorbatereductase (DR) and glutathione reductase (GR) were promoted by the addition of Cd.Exposed to Cd also increased the contents of ascorbate (AsA) and glutathione (GSH) in theleaves.

Au^(δ-)-O_(v)-Ti^(3+):Active site of MO_(x)-Au/TiO_(2) catalysts for the aerobic oxidation of 5-hydroxymethylfurfural

Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of metal oxide modified MO_(x)-Au/TiO_(2)(M=Fe,Co,Ni)catalysts with low Au loading amount of 0.5 wt%were synthesized.Addition of transition metal oxides promotes electron transfer and generation of the Au^(δ-)-O_(v)-Ti^(3+)interface.A combination study reveals that the dual-active site(Au^(δ-)-O_(v)-Ti^(3+))governs the catalytic performance of the ratedetermining step,namely hydroxyl group oxidation.Au^(δ-) site facilitates chemisorption and activation of O_(2) molecules.At the same time,O_(v)-Ti^(3+) site acts as the role of“killing two birds with one stone”:enhancing adsorption of both reactants,accelerating the activation and dissociation of H_(2)O,and facilitating activation of the adsorbed O_(2).Besides,superoxide radicals instead of base is the active oxygen species during the rate-determining step.On this basis,a FDCA yield of 71.2% was achieved under base-free conditions,complying with the“green chemistry”principle.This work provides a new strategy for the transition metal oxides modification of Au-based catalysts,which would be constructive for the rational design of other heterogeneous catalysts.

Role of oxygen vacancies and Sr sites in SrCo_(0.8)Fe_(0.2)O_3 perovskite on efficient activation of peroxymonosulfate towards the degradation of aqueous organic pollutants

Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.

Edaravone protects against oxygen-glucose-serum deprivation/restoration-induced apoptosis in spinal cord astrocytes by inhibiting integrated stress response

We previously found that oxygen-glucose-serum deprivation/restoration（OGSD/R） induces apoptosis of spinal cord astrocytes, possibly via caspase-12 and the integrated stress response, which involves protein kinase R-like endoplasmic reticulum kinase（PERK）, eukaryotic initiation factor 2-alpha（eIF2α） and activating transcription factor 4（ATF4）. We hypothesized that edaravone, a low molecular weight, lipophilic free radical scavenger, would reduce OGSD/R-induced apoptosis of spinal cord astrocytes. To test this, we established primary cultures of rat astrocytes, and exposed them to 8 hours/6 hours of OGSD/R with or without edaravone（0.1, 1, 10, 100 μM） treatment. We found that 100 μM of edaravone significantly suppressed astrocyte apoptosis and inhibited the release of reactive oxygen species. It also inhibited the activation of caspase-12 and caspase-3, and reduced the expression of homologous CCAAT/enhancer binding protein, phosphorylated（p）-PERK, p-eIF2α, and ATF4. These results point to a new use of an established drug in the prevention of OGSD/R-mediated spinal cord astrocyte apoptosis via the integrated stress response.

Effects of Short-Term Chilling Stress on the Photosystems and Chloroplast Ultrastructure in Sweet Pepper

By measuring chlorophyll fluorescence parameters, composition of fatty acids, active oxygen species and activities ofsome antioxidant enzymes, effects of chilling stress (4C) in the low light (100 mmol m-2 s-1) on chilling-sensitive plants werestudied. After 6 h chilling stress (4C) in the low light, the maximal photochemical efficiency of PSII (Fv/Fm) of sweetpepper leaves decreased by 35.6%, and the oxidizable P700 decreased by 60%. However, chilling stress in the dark had noeffect on both of them. Unsaturation of fatty acids in thylakoid membrane was accelerated, which might be helpful tostabilize photosynthetic apparatus. Distortion and swelling of grana caused by chilling in the dark probably decreasedactivities of antioxidant enzymes, which resulted in the accumulation of active oxygen species. On the contrary,photooxidation might be related to the disintegration and unstacking of grana. Chilling stress induced photoinhibition ofPSII and PSI, and active oxygen species might be one of the factors causing the decrease of the oxidizable P700. PSIseemed to be more sensitive to chilling stress in the low light than PSII.

Direct conversion of methane to methanol by electrochemical methods

A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.

Elucidating the effect of barium halide promoters on La_(2)O_(3)/CaO catalyst for oxidative coupling of methane

The industrialization of oxidative coupling of methane(OCM)is restricted by the low once through yield of C_(2)hydrocarbons.Recently,the halogen-assisted OCM process has been attempted to overcome this issue,but the reaction stability was poor due to the rapid loss of gas-phase halides or molten alkali halides.In this work,the barium salts,particularly barium halides(BaCl_(2)and BaF_(2)),were demonstrated to be efficient promoters to improve the OCM reactivity of La_(2)O_(3)/CaO catalyst by increasing both C_(2)selectivity and C_(2)H_(4)/C_(2)H_(6)ratio,and simultaneously achieving outstanding reaction stability.The promoting mechanism can be understood in two aspects.On the one hand,the introduction of barium salts increased the amount of surface electrophilic oxygen species,serving as the alkaline active sites for selective methane activation.On the other hand,the barium halide additives induced the in-situ formation of methyl halide intermediates facilitating C_(2)H_(6)dehydrogenation,and their intimate contact with catalyst substrate restricted the rapid halogen loss and thereby improved the catalytic stability.This work not only provides a class of efficient OCM catalyst,but also offers a highly stable halogen-assisted reaction strategy.

Deciphering active biocompatibility of iron oxide nanoparticles from their intrinsic antagonism

Magnetite nanoparticles （Fe3O4 NPs） are a well proven biocompatible nanomaterial, which hold great promise in various biomedical applications. Interestingly, unlike conventional biocompatible materials （e.g., polyethylene glycol （PEG）） that are chemically and biologically inert in nature, Fe3O4 NPs are known to be catalytically active and exhibit prominent physiological effects. Herein, we report an ＂active＂, dynamic equilibrium mechanism for maintaining the cellular amenity of Fe3O4 NPs. We examined the effects of two types of iron oxide （magnetite and hematite） NPs in rat pheochromocytoma （PC12） cells and found that both induced stress responses. However, only Fe2O3 NPs caused significant programmed cell death; whereas Fe3O4 NPs are amenable to cells. We found that intrinsic catalase-like activity of Fe3O4 NPs antagonized the accumulation of toxic reactive oxygen species （ROS） induced by themselves, and thereby modulated the extent of cellular oxidative stress, autophagic activity, and programmed cell death. In line with this observation, we effectively reversed severe autophagy and cell death caused by Fe2O3 NPs via co-treatment with natural catalase. This study not only deciphers the distinct intrinsic antagonism of Fe3O4 NPs, but opens new routes to designing biocompatible theranostic nanoparticles with novel mechanisms.

Recent progress in synergistic electrocatalysis for generation of valuable products based on water cycle

Given the grim situation of global warming and energy crisis,replacing traditional energy conversions based on carbon cycle with water cycle is a sustainable development trend.The synergistic electrocatalysis for value-added chemical production through oxygen species(O_(ads):OH^(*),O^(*),and OOH^(*))and the active hydrogen species(H_(ads))derived from water splitting powered by“green”electricity from renewable energy resource(wind,solar,etc.)is a promising manner,because of its reduced energy consumption and emission and high Faradaic efficiency.The study and summarization of catalytic mechanism of synergistic electrocatalysis are particularly significant,but are rarely involved.In this review,recent progress of various synergistic electrocatalysis systems for generating valuable products based on water cycle is systematically summarized.Importantly,the catalytic mechanism of synergistic electrocatalysis and the positive effect of O_(ads) and H_(ads) species produced by water splitting during the synergistic electrocatalytsis are detailedly elucidated.Furthermore,the regulation of water-derived O_(ads) and H_(ads) species for achieving efficient matchability of synergistic electrocatalysis is emphatically discussed.Finally,we propose the limitations and future goals of this synergistic system based on water cycle.This review is guidance for design of synergistic electrocatalysis architectures for producing valuable substances based on water cycle.

Effects of Exogenous Spermidine on Antioxidant System Responses of Typha latifolia L. Under Cd^2＋ Stress

The effects of foliar spraying with spermidine (Spd), ranging in concentration from 0.25 to 0.50 mmol/L, on the antioxidant system under Cd2+ stress (range 0.1–0.2 mmol/L Cd2+) in Typha latifolia L. grown hydroponically were investigated in order to offer a referenced evidence for an understanding of the mechanism by which polyamines (PAs) relieve the damage to plants by heavy metal and improve the phytoremediation efficiency of heavy metal-contaminated water. The results showed that Cd2+ stress induced oxidative injury, as evidenced by an increase in the generation of superoxide anion (O2-), as well as the hydrogen peroxide (H2O2) and malondialdehyde (MDA) contents in both leaves and caudices. With the exception of superoxide dismutase (SOD) activity in the leaves, an increase in the activities of catalase (CAT), guaiacol peroxidase (GPX), and glutathione reductase (GR) was observed in both leaves and caudices, SOD activity was increased in caudices, and ascorbate peroxidase (APX) activity was increased in leaves following Cd2+ treatment. The reduced glutathione (GSH) content in both leaves and caudices and the reductive ascorbate content in leaves was obviously increased, which were prompted by the application of exogenous Spd. Spraying with Spd increased the activity of GR and APX in both leaves and caudices, whereas the activity of SOD, CAT, and GPX was increased only in caudices following spraying with Spd. The generation of O2 -. and the H2O2 and MDA content in both leaves and caudices decreased after spraying with Spd. The decrease in MDA was more obvious following the application of 0.25 than 0.50 mmol/L Spd. It is supposed that exogenous Spd elevated the tolerance of T. latifolia under Cd2+ stress primarily by increasing GR activity and the GSH level.

Synergistic catalytic ozonation of toluene with manganese and cerium varies at low temperature

The temperature of waste gas in refuse transfer station,airport smoking area,and RTO terminal is low,which needs deep oxidation.Catalytic ozonation is one of the most effective treatment techniques in these scenarios.In this study,we reported that catalysts were modified under the condition of mag-netic field to simulate the low temperature dynamic conditions of low concentration toluene for catalytic ozonation.This paper aims to explore the relationship between oxygen vacancy and active oxygen species,and the specific pathways of toluene oxidation.The study found that citric acid can enhance the syner-gistic effect between Mn and Ce,and promote the generation of oxygen vacancies.The surface molecule adsorption oxygen is more conducive to catalytic oxidation than subsurface atom adsorption oxygen.Fi-nally,we proposed the main pathways of toluene in this reaction system,which runs through the whole process of the reaction.

Controllable synthesis of argentum decorated CuO_(x)@CeO_(2) catalyst and its highly efficient performance for soot oxidation

In this paper,CuO_(x)@Ag/CeO_(2) catalysts were synthesized by simple wet-chemical method and equal volume impregnation method.The obtained catalysts were subjected to soot temperature programmed oxidation(soot-TPO)activity tests and were further characterized by various techniques such as X-ray diffraction(XRD),transmission electron microscopy/high-resolution transmission electron microscopy(TEM/HR-TEM),N_(2) physisorption,X-ray photoelectron spectroscopy(XPS)and H_(2)-temperature programmed reduction(H_(2)-TPR).The results show that CuO_(x)@Ag/CeO_(2) synthesized presents well controlled core-shell structures,with nano-cube like Cu_(2)O as the core and Ag decorated polycrystalline CeO_(2) grafting layers as the shell.Such core-shell structured CuO_(x)@Ag/CeO_(2) can successfully construct a secondary oxygen delivery channel(CuO_(x)→CeO_(2)→Ag)to effectively transfer bulk oxygen of the catalyst to the soot,resulting in its excellent soot oxidation activity compared to CuO_(x)@CeO_(2).The potential benefiting effect by Ag introduction over Cu@Ag/Ce can be concluded as:(ⅰ)pumping lattice oxygen and accelerating gaseous O_(2) dissociation to generate significantly increased active surface oxygen content;(ⅱ)modulating a moderate surface oxygen vacancies concentration to maintain more highly active O_(2) species.

Recent advances in soot combustion catalysts with designed micro-structures

With the enhancement of the people consciousness of environment protection, soot particulates(PM)elimination has drawn wide attention in recent years. Efficient after-treatment with well-designed catalysts is one of the best ways to eliminate soot particulates that come from diesel engines. Catalysts coated on the DPF(diesel particulate filter) are considered as the main factor to lower soot ignition temperature.Improvement of the structures of the catalysts is significantly important in order to achieve good catalytic performance and high stability. Based on the structures, soot combustion catalysts can be mainly divided into three types: particle-based catalysts, 3 DOM catalysts and nanoarray catalysts. This review mainly summarized recent advances in soot combustion catalysts with different designed micro-structures, each category is explained with critical assessment and several typical examples, aiming to guide the synthesis of advanced soot combustion catalysts.

The photocatalytic ·OH production activity of g-C_(3)N_(4) improved by the introduction of NO

The efficiency of photocatalytic pollutant removal largely depends on the ability of the photocatalytic system to produce hydroxyl radicals(·OH).However,the capability of photocatalyst to produce·OH is not strong at present.Advancing the capacity of photocatalytic system to produce·OH has always been a tough problem and challenge in the field of environmental science.In this research,it was found that introducing nitric oxide(NO)into the graphitic carbon nitride(g-C_(3)N_(4))photocatalytic system could memorably enhance the ability of producing·OH group.This study provides a new idea for improving the capacity of photocatalytic·OH production.

In-situ electro-deposition synthesis of MnO_(x)-NiCo_(2)O_(4) monolithic catalyst with rich phase interfaces

A hierarchically structured MnO_(x)-NiCo_(2)O_(4) monolithic catalyst with rich phase interfaces was designed by a simple,eco-friendly and time-saving in-situ electro-deposition method.The abundance of active oxygen species due to this rich phase interfaces contributed to the excellent benzene combustion performance of MnO_(x)-NiCo_(2)O_(4)-2:2 sample,oxidizing about 90% of benzene(T_(90)) at 198℃ under 12000 h^(-1) gaseous hourly space velocity.This work shed new light on the design of excellent monolithic catalysts,which might pave the way for the industrialization of benzene combustion.