Microbial oxidation and the mechanism of Sb(Ⅲ)are key governing elements in biogeochemical cycling.A novel Sb oxidizing bacterium,Klebsiella aerogenes HC10,was attracted early and revealed that extracellular metaboli...Microbial oxidation and the mechanism of Sb(Ⅲ)are key governing elements in biogeochemical cycling.A novel Sb oxidizing bacterium,Klebsiella aerogenes HC10,was attracted early and revealed that extracellular metabolites were the main fractions driving Sb oxidation.However,linkages between the extracellular metabolite driven Sb oxidation process and mechanism remain elusive.Here,model phenolic and quinone compounds,i.e.,anthraquinone-2,6-disulfonate(AQDS)and hydroquinone(HYD),representing extracellular oxidants secreted by K.aerogenes HC10,were chosen to further study the Sb(Ⅲ)oxidation mechanism.N_(2)purging and free radical quenching showed that oxygen-induced oxidation accounted for 36.78%of Sb(Ⅲ)in the metabolite reaction system,while hydroxyl free radicals(·OH)accounted for 15.52%.·OH and H_(2)O_(2)are the main driving factors for Sb oxidation.Radical quenching,methanol purification and electron paramagnetic resonance(EPR)analysis revealed that·OH,superoxide radical(O_(2)^(•-))and semiquinone(SQ-•)were reactive intermediates of the phenolic induced oxidation process.Phenolic-induced ROS are one of the main oxidants in metabolites.Cyclic voltammetry(CV)showed that electron transfer of quinone also mediated Sb(Ⅲ)oxidation.Part of Sb(V)was scavenged by the formation of the secondary Sb(V)-bearing mineral mopungite[NaSb(OH)6]in the incubation system.Our study demonstrates the microbial role of oxidation detoxification and mineralization of Sb and provides scientific references for the biochemical remediation of Sb-contaminated soil.展开更多
Palladium-based catalysts have long been considered the benchmark for methane combustion;however,the authentic phase of catalytic active sites remains a subject of ongoing debate.Additionally,challenges like water-poi...Palladium-based catalysts have long been considered the benchmark for methane combustion;however,the authentic phase of catalytic active sites remains a subject of ongoing debate.Additionally,challenges like water-poisoning and long-term stability need to be addressed to advance catalyst performance.Herein,we investigate Pd on Co_(3)O_(4) nanorods as a highly effective catalyst for catalytic oxidation of methane,demonstrating long-term stability and water tolerance during a 100-h continuous operation at 350℃.Comprehensive characterizations reveal the presence of an active Pd-oxygen vacancy(Ov)-cobalt interface in Pd/Co_(3)O_(4),which effectively adsorbs molecular O_(2).The absorbed oxygen species on this interface are activated and directly participate in methane combustion.Moreover,near-ambient pressure X-ray photoelectron spectroscopy demonstrates that Pd nanoparticles undergo a rapid phase transition and predominantly remain in the metallic state during the reaction.This behavior is attributed to the electronic metal-support interaction between Pd and Co_(3)O_(4).Furthermore,in situ Fourier transformed infrared spectrum reveals that under reaction conditions,HCO3*species are formed initially and subsequently transformed into formate species,indicating that the formate pathway is the dominant mechanism for CH_(4) oxidation.展开更多
During the course of mungbean (Phaseolus radiatus L.) germination, the rate of ethylene production and the activity of ACC synthase (1_aminocyclopropane_1_carboxylic acid synthase, EC4.4.1.4) began to increase in the ...During the course of mungbean (Phaseolus radiatus L.) germination, the rate of ethylene production and the activity of ACC synthase (1_aminocyclopropane_1_carboxylic acid synthase, EC4.4.1.4) began to increase in the 5th day of germination, and reached its peak in the 10th day and then decreased. The ethylene production and the activity of ACC synthase were obviously promoted by 10 μmol/L exogenous IAA (indole_3_acetic acid). The production of superoxide radical (O -· 2) and hydrogen peroxide (H 2O 2) were also promoted by exogenous IAA, suggesting that there was some relationship between active oxygen production and the activity of ACC synthase induced by exogenous IAA. The production of ethylene and the activity of ACC synthase increased dramatically when the seedlings were treated with exogenous O -· 2, whereas the exogenous H 2O 2 had no effects on the production of ethylene and the activity of ACC synthase. Exogenous SOD (superoxide dismutase, one scavenger of O -· 2) could inhibit the production of ethylene and the activity of ACC synthase, but exogenous CAT (catalase) could not. So it was possible that IAA would stimulate the activity of ACC synthase by inducing the production of O -· 2 in germinating mungbean seedlings, and this might be one of the regulating mechanism of ethylene synthesis in higher plants; the production of H 2O 2 induced by IAA was not the cause of the increase of the activity of ACC synthase and the production of ethylene.展开更多
In order to understand the role of active oxygen species in mediating plant injuries induced by far-UV radiation, seedlings of Taxus cuspidata Sieb. et Zucc. were irradiated by far-UV rays in laboratory for 4 weeks. T...In order to understand the role of active oxygen species in mediating plant injuries induced by far-UV radiation, seedlings of Taxus cuspidata Sieb. et Zucc. were irradiated by far-UV rays in laboratory for 4 weeks. The production of organic free-radicals in detached needles, and the production of O-2(radical anion) and O-1(2) in isolated chloroplasts were detected weekly by electron spin resonance (ESR) to evaluate their relative importance. The results show that the cumulative effect of far-UV irradiation, is best indicated by the production of organic free radicals in the needles, O-2(radical anion) production in chloroplasts is the next. The enhancement of O-1(2) production in chloroplasts by the cumulative far-UV irradiation seems to be not so important as O-2(radical anion) in mediating injuries induced by, far-UV radiation because of its high background value.展开更多
Peach fruits [Prumus persica （L.） Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species （ROS） and related enzymes in mitochondria respiration during storage and then...Peach fruits [Prumus persica （L.） Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species （ROS） and related enzymes in mitochondria respiration during storage and then their influence on senescence of harvested Peach fruits was studied. The results showed that low temperature （5℃） strongly inhibited the reduction of firmness and the increase in respiration rate. During storage at ambient temperature （20℃）, ROS had a cumulative process while malondialdehye （MDA） content continued to increase in associated with enhanced membrane lipid peroxidation. Lipoxygenase （LOX） activity was strongly inhibited under the low temperature condition. The activities of succinic dehydrogenase （SDH）, cytochrome C oxidase （CCO）, and Ca^2＋-ATPase declined to a certain extent at ambient temperature, while they showed higher activities at low temperature, which may be related to lower membrane lipid peroxidation at low temperature. Higher Ca^2＋ content at ambient temperature may be responsible for impairment of mitochondrial function, thus, leading to fruit senescence. The results showed that under low temperature condition, the low accumulation of ROS and the low level of membrane lipid peroxidation could maintain the function of mitochondria that would help to delay the senescence of peach fruits. These suggested a close relationship existed between ROS metabolism and mitochondrial respiration. It can be inferred that the low temperature helps to delay senescence of peach fruits via suppression of ROS and related enzymes, maintain better homeostasis of Ca^2＋ in mitochondria and thus better mitochondrial functions.展开更多
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)(...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.展开更多
La_(2)O_(3) catalyzed oxidative coupling of methane(OCM) is a promising process that converts methane directly to valuable C_(2)(ethylene and ethane) products. Our online MS transient study results indicate that prist...La_(2)O_(3) catalyzed oxidative coupling of methane(OCM) is a promising process that converts methane directly to valuable C_(2)(ethylene and ethane) products. Our online MS transient study results indicate that pristine surface without carbonate species demonstrates a higher selectivity to C_(2) products, and a lower light-off temperature as well. Further study is focused on carbonate-free La_(2)O_(3) catalyst surface for identification of active oxygen species associated with such products behavior. XPS reveals unique oxygen species with O 1 s binding energy of 531.5 e V correlated with OCM catalytic activity and carbonates removal. However, indicated thermal stability of this species is much higher than the surface peroxide or superoxide structures proposed by earlier computation models. Motivated by experimental results,DFT calculations reveal a new more stable peroxide structure, formed at the subsurface hexacoordinate lattice oxygen sites, with energy 2.18 e V lower than the previous models. The new model of subsurface peroxide provides a perspective for understanding of methyl radicals formation and C_(2) products selectivity in OCM over La_(2)O_(3) catalyst.展开更多
The changes in content of Ca2 + and CaM, Ca2 + -ATPase activity and active oxygen metabolism during strawberry (Fragaria ananassa Duch. cv. Chunxing) fruits maturation and senescence were investigated in this study. T...The changes in content of Ca2 + and CaM, Ca2 + -ATPase activity and active oxygen metabolism during strawberry (Fragaria ananassa Duch. cv. Chunxing) fruits maturation and senescence were investigated in this study. The results showed that the soluble Ca2+ content and SOD activity in fruits tended to decline and O2 production rate to increase, the Ca2 + -ATPase activity peaked at first and then declined during fruits maturation and senescence. There were the highest CaM content at white stage in preharvest fruits and at marked senescence stage in postharvest ones. The above biochemical changes in fruits stored at low temperature (4℃)were slower than those stored at normal temperature(25℃). Thus, it indicated that the stimulation of calcium messenger system and accumulation of active oxygen free radical were closely related to fruits maturation and senescence.展开更多
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 met...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.展开更多
Under artificially-simulated complex salt-alkali stress, the levels of active oxygen metabolism in roots were studied using three-year-old cutting seedlings of Spiraea × bumalda ‘Gold Mound＇ and Spiraea × ...Under artificially-simulated complex salt-alkali stress, the levels of active oxygen metabolism in roots were studied using three-year-old cutting seedlings of Spiraea × bumalda ‘Gold Mound＇ and Spiraea × bumalda ‘Gold Flame＇. The present study aimed at exploring the antioxidant capacity in roots of spiraeas and revealing their adaptability to salt-alkali stress. Results indicate that the oxygen free radicals contents, electrolyte leakage rates and MDA contents in roots of Spiraea × bumalda ＇Gold Mound＇ and Spiraea × bumalda ＇Gold Flame＇ show an increasing tendency with the increases of the salinity and pH value, whereas the activities of superoxide dismutase （SOD）, peroxidase （POD） and catalase （CAT） all increased firstly and then decreased. With the increase in intensity of salt-alkali stress, the CAT activity in roots of Spiraea × bumalda ‘Gold Flame＇ is higher and the increasing extents in the oxygen free radicals contents, electrolyte leakage rates as well as MDA contents are lower compared with Spiraea × bumalda ‘Gold Mound＇, indicating that Spiraea × bumalda ‘Gold Flame＇ has a stronger antioxidant capacity.展开更多
This study was focused on the influence of active oxygen on the performance of Pt/CeO2 catalysts for CO oxidation. A series of CeO2 supports with different contents of active oxygen were obtained by adding surfactant ...This study was focused on the influence of active oxygen on the performance of Pt/CeO2 catalysts for CO oxidation. A series of CeO2 supports with different contents of active oxygen were obtained by adding surfactant at different synthesis steps. 0.25 wt% Pt was loaded on these CeO2 supports by incipientwetness impregnation methods. The catalysts were characterized by N2 adsorption, X-ray diffraction（XRD）, high-resolution transmission electron microscopy（HRTEM）, H2 temperature-programmed reduction（H2-TPR）, dynamic oxygen storage capacity（DOSC） and in-situ DRIFTS technologies. For S-f supports, the surfactant was added into the solution before spray-drying in the synthesis process, which facilitates more active oxygen formation on the surface of CeO2. After loading Pt, the more active oxygen on CeO2 contributes to dispersing Pt species and enhancing the CO oxidation activity. As for the aged samples,Pt-R-h shows the highest activity above 190 ℃ because of the presence of more partly oxidized Pt^（δ＋） species. Thus the activity is also influenced by the states of Pt and the Pt^（δ＋） species may contribute to the high activity at elevated temperature.展开更多
The effect of oxygen partial pressure （Po2） during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide （a-IGZO） thin film transistors （TFTs） is investigated. As Po2 increases fr...The effect of oxygen partial pressure （Po2） during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide （a-IGZO） thin film transistors （TFTs） is investigated. As Po2 increases from 10% to 30%, it is found that the device shows enhanced bias stress stability with significantly reduced threshold voltage drift under positive gate bias stress. Based on the x-ray photoelectron spectroscopy measurement, the concentration of oxygen vacancies （Or） within the a-IGZO layer is suppressed by increasing Po2. Meanwhile, the low-frequency noise analysis indicates that the average trap density near the channel/dielectric interface continuously drops with increasing Po2. Therefore, the improved interface quality with increasing Po2 during the channel layer deposition can be attributed to the reduction of interface Ov-related defects, which agrees with the enhanced bias stress stability of the a-IGZO TFTs.展开更多
Applying quantitative temporal analysis of products reactor measurements, we studied the reactive removal of active oxygen present on Au/TiO2 catalysts after calcination at elevated temperatures （400 ＆#176;C） by CO...Applying quantitative temporal analysis of products reactor measurements, we studied the reactive removal of active oxygen present on Au/TiO2 catalysts after calcination at elevated temperatures （400 ＆#176;C） by CO pulses and its replenishment by O2 pulses at 80 ＆#176;C, focusing on the nature of the active oxygen species. In contrast to previous studies, which mainly focused on and clarified the nature of the active oxygen species for the catalytic CO oxidation, which is reversibly formed and replenished under typical reaction conditions, this study demonstrates that directly after calcina‐tion an additional oxygen species is present. This species is also active for the CO oxidation, but it is not or only very little formed under typical reaction conditions. Implications of these results on the mechanistic understanding of the CO oxidation on Au/TiO2, in particular on the role of different active oxygen species, will be discussed.展开更多
Two series of layered mixed oxides La4BaCu5-xMxO13+(M=Mn, Co, x=05) were prepared and characterized by means of XRD, XPS, O2TPD and chemical analysis. The results show that their structures are 5layered ABO3 perovskit...Two series of layered mixed oxides La4BaCu5-xMxO13+(M=Mn, Co, x=05) were prepared and characterized by means of XRD, XPS, O2TPD and chemical analysis. The results show that their structures are 5layered ABO3 perovskite, and the XPS and O2TPD investigation confirms that there exists synergistic effect between Cu ion and M when M ion is doped into the lattice of La4BaCu5O13+, and the synergistic effect between Mn and Cu is stronger than that of CuCo.展开更多
Employing nutrient solution hydroponic method,the effects of exogenous nitric oxide（NO）on the growth and active oxygen metabolism in cucumber（Cucumis sativus L.）seedlings under NaCl stress were investigated.The re...Employing nutrient solution hydroponic method,the effects of exogenous nitric oxide（NO）on the growth and active oxygen metabolism in cucumber（Cucumis sativus L.）seedlings under NaCl stress were investigated.The results indicated that NaCl treatment significantly inhibited the growth of cucumber seedlings,while exogenous NO could significantly alleviate the inhibitory effects of NaCl stress on seedling growth.Especially,0.1 mmol/L SNP treatment exhibited better effects than 0.5 mmol/L SNP treatment on alleviating NaCl stress.Under 0.1 mmol/L NaCl stress,adding 0.1 mmol/L exogenous NO could significantly decrease the generation rate of O·-2and MDA content,significantly improve soluble protein content and enhance the activities of SOD,POD and CAT,thus reducing the damage of salt stress to cucumber seedlings.展开更多
To investigate the enhancing effect of Mn on the performance of simultaneous catalytic oxidation of AsH_(3)and PH_(3)by CuO-Al_(2)O_(3)in a reducing atmosphere under micro-oxygen conditions,Cu-Mn modifiedγ-Al_(2)O_(3...To investigate the enhancing effect of Mn on the performance of simultaneous catalytic oxidation of AsH_(3)and PH_(3)by CuO-Al_(2)O_(3)in a reducing atmosphere under micro-oxygen conditions,Cu-Mn modifiedγ-Al_(2)O_(3)catalysts were prepared.The characteristics of the catalysts showed that Mn reduced the crystallinity of the active CuO component,increased the number of oxygen vacancies and acidic sites on the catalyst surface,enhanced the mobility of surface oxygen,and the interaction between copper and manganese promoted the redox cycling ability of the catalysts and improved their oxidation performance,which increased the conversion frequency(TOF)by 2.54×10^(-2)to 3.07×10^(-2)sec^(-1).On the other hand,the introduction of Mn reduced the production of phosphate and As_(2)O_(3)on the catalyst surface by30.96%and 44.9%,which reduced the coverage and inerting of the active sites by phosphate and As_(2)O_(3),resulting in an 8 hr(6 hr)improvement in the stability of PH_(3)(AsH_(3))removal.展开更多
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 generat...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.展开更多
Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy densi...Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy density.However,the all-solid-state batteries with nickel-rich oxide cathodes suffer from performance degradation due to the reactions between the highly reactive surface oxygen of the cathode and the electrolyte,as well as the instability of the bulk oxygen structure in the cathode.Herein,we propose a synergistic modification design scheme to adjust the oxygen activity from surface to bulk.The LiBO_(2)coating inhibits the reactivity of surface lattice oxygen ions.Meanwhile,Zr doping in the bulk phase forms strong Zr-O covalent bonds that stabilize the bulk lattice oxygen structure.The synergistic effect of these modifications prevents the release of oxygen,thus avoiding the degradation of the cathode/SE interface.Additionally,the regulation of surface-to-bulk oxygen activity establishes a highly stable interface,thereby enhancing the lithium ion diffusion kinetics and mechanical stability of the cathode.Consequently,cathodes modified with this synergistic strategy exhibit outstanding performance in sulfide-based ASSLBs,including an ultra-long cycle life of 100,000 cycles,ultra-high rate capability at 45C,and 85% high active material content in the composite cathode.Additionally,ASSLB exhibits stable cycling under high loading conditions of 82.82 mg cm^(-2),achieving an areal capacity of 17.90 mA h cm^(-2).These encouraging results pave the way for practical applications of ASSLBs in fast charging,long cycle life,and high energy density in the future.展开更多
Gasoline soot particles pose a severe threat to the ecological environment and human health,but they can be potentially filtered out by using catalytic gasoline particulate filter(cGPF),whose core component is a catal...Gasoline soot particles pose a severe threat to the ecological environment and human health,but they can be potentially filtered out by using catalytic gasoline particulate filter(cGPF),whose core component is a catalyst coating.To develop more effective catalyst coatings with excellent activity,stability,and water resistance,a kind of composite oxide MnO_(x)/CeO_(2)-ZrO_(2) was synthesized using different methods,and its soot oxidation performance was evaluated under low O_(2) concentrations.Herein,MnO_(x)/CeO_(2)-ZrO_(2) prepared by impregnation(abbreviated as MCZ-IM)exhibits a T_(50)(temperature required for 50% soot conversion)of 329℃in 1%O_(2) and 370℃ in 0.5%O_(2),displaying better comprehensive performance when compared to catalysts prepared by high-energy ball milling(abbreviated as MCZ-HB)and co-precipitation(abbreviated as MCZ-CP).Structure-activity relationship reveals that soot oxidation under low O_(2) concentrations is weakly correlated with textural and structural properties,but strongly depends on the generation and migration of active oxygen species(AOS),especially superoxide(O_(2)^(-))and peroxide(O_(2)^(2-))anions,which are linked to redox properties,oxygen storage and release capacity,as well as amount of oxygen vacancies.The impregnation method enhances oxygen species adsorption,activation and desorption more effectively,endowing it with a more effective approach to enhancing AOS generation and mobility.Therefore,this study not only provides a preparation strategy for particulate matter oxidation catalysts applicable to actual operating conditions,but also offers insights into the migration of AOS at low O_(2) concentrations.展开更多
NO catalytic oxidation is the key performance of the diesel oxidation catalyst(DOC).We present a facile deposition method for the core-shell rare-earth manganese-zirconium composite oxide that shows the Mn mullite pha...NO catalytic oxidation is the key performance of the diesel oxidation catalyst(DOC).We present a facile deposition method for the core-shell rare-earth manganese-zirconium composite oxide that shows the Mn mullite phase uniform loading on the surface of zirconium-based composite(YMO/CYZO),which demonstrates a superior NO oxidation catalytic performance in simulated diesel combustion conditions and better thermal stability than mullite phase YMn_(2)O_(5)oxide.The NO oxidation at 250℃over YMO/CYZO-a approaches 25.2%in contrast to 13.52%over YMn_(2)O_(5)-a.Then the catalytic performance of YMO/CYZO,YMO and commercial 1 wt%Pt/Al_(2)O_(3)in a NO+O_(2)atmosphere was compared.The maximum conversion rate of YMO/CYZO to NO oxidation is 89.6%at 274℃with a GHSV of 50000 h^(-1),and the performance is superior to that of YMO(82.8%at 293℃)and 1 wt%Pt/Al_(2)O_(3)(68.6%,335℃).The NO-temperature programmed desorption(NO-TPD)and diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)results reveal that YMO/CYZO has multiple NO adsorption sites and high storage capacity.Furthermore,density functional theory(DFT)calculation indicates that YMO/CYZO has lower oxygen vacancy formation energies(E_(v)=0.93 eV)and favorable NO adsorption energies(E_(ads)=2.1 eV).Moreover,in situ X-ray photoelectron spectroscopy(XPS)characterization shows that the core-shell structure of YMO/CYZO has the potential to transmit active oxygen species to help realize Mn3+to Mn4+during the reaction process to enhance the conversion of NO*molecules,while NO oxidation reactions follow the MvK mechanism.展开更多
基金supported by the National Natural Science Foundation of China(No.42267001)the College Young and Middle-aged Teachers’Basic Ability Improvement Project of Guangxi,China(No.2023KY0393).
文摘Microbial oxidation and the mechanism of Sb(Ⅲ)are key governing elements in biogeochemical cycling.A novel Sb oxidizing bacterium,Klebsiella aerogenes HC10,was attracted early and revealed that extracellular metabolites were the main fractions driving Sb oxidation.However,linkages between the extracellular metabolite driven Sb oxidation process and mechanism remain elusive.Here,model phenolic and quinone compounds,i.e.,anthraquinone-2,6-disulfonate(AQDS)and hydroquinone(HYD),representing extracellular oxidants secreted by K.aerogenes HC10,were chosen to further study the Sb(Ⅲ)oxidation mechanism.N_(2)purging and free radical quenching showed that oxygen-induced oxidation accounted for 36.78%of Sb(Ⅲ)in the metabolite reaction system,while hydroxyl free radicals(·OH)accounted for 15.52%.·OH and H_(2)O_(2)are the main driving factors for Sb oxidation.Radical quenching,methanol purification and electron paramagnetic resonance(EPR)analysis revealed that·OH,superoxide radical(O_(2)^(•-))and semiquinone(SQ-•)were reactive intermediates of the phenolic induced oxidation process.Phenolic-induced ROS are one of the main oxidants in metabolites.Cyclic voltammetry(CV)showed that electron transfer of quinone also mediated Sb(Ⅲ)oxidation.Part of Sb(V)was scavenged by the formation of the secondary Sb(V)-bearing mineral mopungite[NaSb(OH)6]in the incubation system.Our study demonstrates the microbial role of oxidation detoxification and mineralization of Sb and provides scientific references for the biochemical remediation of Sb-contaminated soil.
文摘Palladium-based catalysts have long been considered the benchmark for methane combustion;however,the authentic phase of catalytic active sites remains a subject of ongoing debate.Additionally,challenges like water-poisoning and long-term stability need to be addressed to advance catalyst performance.Herein,we investigate Pd on Co_(3)O_(4) nanorods as a highly effective catalyst for catalytic oxidation of methane,demonstrating long-term stability and water tolerance during a 100-h continuous operation at 350℃.Comprehensive characterizations reveal the presence of an active Pd-oxygen vacancy(Ov)-cobalt interface in Pd/Co_(3)O_(4),which effectively adsorbs molecular O_(2).The absorbed oxygen species on this interface are activated and directly participate in methane combustion.Moreover,near-ambient pressure X-ray photoelectron spectroscopy demonstrates that Pd nanoparticles undergo a rapid phase transition and predominantly remain in the metallic state during the reaction.This behavior is attributed to the electronic metal-support interaction between Pd and Co_(3)O_(4).Furthermore,in situ Fourier transformed infrared spectrum reveals that under reaction conditions,HCO3*species are formed initially and subsequently transformed into formate species,indicating that the formate pathway is the dominant mechanism for CH_(4) oxidation.
文摘During the course of mungbean (Phaseolus radiatus L.) germination, the rate of ethylene production and the activity of ACC synthase (1_aminocyclopropane_1_carboxylic acid synthase, EC4.4.1.4) began to increase in the 5th day of germination, and reached its peak in the 10th day and then decreased. The ethylene production and the activity of ACC synthase were obviously promoted by 10 μmol/L exogenous IAA (indole_3_acetic acid). The production of superoxide radical (O -· 2) and hydrogen peroxide (H 2O 2) were also promoted by exogenous IAA, suggesting that there was some relationship between active oxygen production and the activity of ACC synthase induced by exogenous IAA. The production of ethylene and the activity of ACC synthase increased dramatically when the seedlings were treated with exogenous O -· 2, whereas the exogenous H 2O 2 had no effects on the production of ethylene and the activity of ACC synthase. Exogenous SOD (superoxide dismutase, one scavenger of O -· 2) could inhibit the production of ethylene and the activity of ACC synthase, but exogenous CAT (catalase) could not. So it was possible that IAA would stimulate the activity of ACC synthase by inducing the production of O -· 2 in germinating mungbean seedlings, and this might be one of the regulating mechanism of ethylene synthesis in higher plants; the production of H 2O 2 induced by IAA was not the cause of the increase of the activity of ACC synthase and the production of ethylene.
文摘In order to understand the role of active oxygen species in mediating plant injuries induced by far-UV radiation, seedlings of Taxus cuspidata Sieb. et Zucc. were irradiated by far-UV rays in laboratory for 4 weeks. The production of organic free-radicals in detached needles, and the production of O-2(radical anion) and O-1(2) in isolated chloroplasts were detected weekly by electron spin resonance (ESR) to evaluate their relative importance. The results show that the cumulative effect of far-UV irradiation, is best indicated by the production of organic free radicals in the needles, O-2(radical anion) production in chloroplasts is the next. The enhancement of O-1(2) production in chloroplasts by the cumulative far-UV irradiation seems to be not so important as O-2(radical anion) in mediating injuries induced by, far-UV radiation because of its high background value.
基金funded by the National Natural Science Fundation of China (30840016)the Natural Science Fundation of Jiangsu Province, China (BK 2010310)the Natural Science Fundation for Colleges and Universities in Jiangsu Province, China (10KJB550004)
文摘Peach fruits [Prumus persica （L.） Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species （ROS） and related enzymes in mitochondria respiration during storage and then their influence on senescence of harvested Peach fruits was studied. The results showed that low temperature （5℃） strongly inhibited the reduction of firmness and the increase in respiration rate. During storage at ambient temperature （20℃）, ROS had a cumulative process while malondialdehye （MDA） content continued to increase in associated with enhanced membrane lipid peroxidation. Lipoxygenase （LOX） activity was strongly inhibited under the low temperature condition. The activities of succinic dehydrogenase （SDH）, cytochrome C oxidase （CCO）, and Ca^2＋-ATPase declined to a certain extent at ambient temperature, while they showed higher activities at low temperature, which may be related to lower membrane lipid peroxidation at low temperature. Higher Ca^2＋ content at ambient temperature may be responsible for impairment of mitochondrial function, thus, leading to fruit senescence. The results showed that under low temperature condition, the low accumulation of ROS and the low level of membrane lipid peroxidation could maintain the function of mitochondria that would help to delay the senescence of peach fruits. These suggested a close relationship existed between ROS metabolism and mitochondrial respiration. It can be inferred that the low temperature helps to delay senescence of peach fruits via suppression of ROS and related enzymes, maintain better homeostasis of Ca^2＋ in mitochondria and thus better mitochondrial functions.
基金Project supported by the National Key Research and Development Program of China(2017YFC0212606,2017YFC0211503,2016YFC0204102)the National Natural Science Foundation of China(51608500)。
文摘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.
基金the Key Projects of Shanghai Science and Technology Commission (18JC1412100)the National Natural Science Foundation of China (No. 91745105, 22072092, 92045301)+2 种基金the startup funding provided by Shanghai Tech University for funding their participation in this workfunding provided through The Shell Foundation Grants (No. PT66201)the support from Analytical Instrumentation Center (contract no. SPSTAIC10112914), SPST, Shanghai Tech University。
文摘La_(2)O_(3) catalyzed oxidative coupling of methane(OCM) is a promising process that converts methane directly to valuable C_(2)(ethylene and ethane) products. Our online MS transient study results indicate that pristine surface without carbonate species demonstrates a higher selectivity to C_(2) products, and a lower light-off temperature as well. Further study is focused on carbonate-free La_(2)O_(3) catalyst surface for identification of active oxygen species associated with such products behavior. XPS reveals unique oxygen species with O 1 s binding energy of 531.5 e V correlated with OCM catalytic activity and carbonates removal. However, indicated thermal stability of this species is much higher than the surface peroxide or superoxide structures proposed by earlier computation models. Motivated by experimental results,DFT calculations reveal a new more stable peroxide structure, formed at the subsurface hexacoordinate lattice oxygen sites, with energy 2.18 e V lower than the previous models. The new model of subsurface peroxide provides a perspective for understanding of methyl radicals formation and C_(2) products selectivity in OCM over La_(2)O_(3) catalyst.
基金the National Natural Science Foundation of China ( No.30270933).
文摘The changes in content of Ca2 + and CaM, Ca2 + -ATPase activity and active oxygen metabolism during strawberry (Fragaria ananassa Duch. cv. Chunxing) fruits maturation and senescence were investigated in this study. The results showed that the soluble Ca2+ content and SOD activity in fruits tended to decline and O2 production rate to increase, the Ca2 + -ATPase activity peaked at first and then declined during fruits maturation and senescence. There were the highest CaM content at white stage in preharvest fruits and at marked senescence stage in postharvest ones. The above biochemical changes in fruits stored at low temperature (4℃)were slower than those stored at normal temperature(25℃). Thus, it indicated that the stimulation of calcium messenger system and accumulation of active oxygen free radical were closely related to fruits maturation and senescence.
基金support of State Key Laboratory of Chemical Engineering (No.SKL-ChE-20A02)the support of International Clean Energy Talent Program by China Scholarship Council.
文摘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.
基金supported by Innovation Team Project of Northeast Agricultural University of P. R. China (CXZ004-3)Science Foundation of Heilongjiang Province (C2007-16)
文摘Under artificially-simulated complex salt-alkali stress, the levels of active oxygen metabolism in roots were studied using three-year-old cutting seedlings of Spiraea × bumalda ‘Gold Mound＇ and Spiraea × bumalda ‘Gold Flame＇. The present study aimed at exploring the antioxidant capacity in roots of spiraeas and revealing their adaptability to salt-alkali stress. Results indicate that the oxygen free radicals contents, electrolyte leakage rates and MDA contents in roots of Spiraea × bumalda ＇Gold Mound＇ and Spiraea × bumalda ＇Gold Flame＇ show an increasing tendency with the increases of the salinity and pH value, whereas the activities of superoxide dismutase （SOD）, peroxidase （POD） and catalase （CAT） all increased firstly and then decreased. With the increase in intensity of salt-alkali stress, the CAT activity in roots of Spiraea × bumalda ‘Gold Flame＇ is higher and the increasing extents in the oxygen free radicals contents, electrolyte leakage rates as well as MDA contents are lower compared with Spiraea × bumalda ‘Gold Mound＇, indicating that Spiraea × bumalda ‘Gold Flame＇ has a stronger antioxidant capacity.
基金Project supported by the National key research and development program(2016YFC0204901)the National Natural Science Foundation of China(21576207)+1 种基金the Introduction Of Talent and Technology Cooperation Plan Of Tianjin(14RCGFGX00849)GM Global Research&Development(GAC 1539)
文摘This study was focused on the influence of active oxygen on the performance of Pt/CeO2 catalysts for CO oxidation. A series of CeO2 supports with different contents of active oxygen were obtained by adding surfactant at different synthesis steps. 0.25 wt% Pt was loaded on these CeO2 supports by incipientwetness impregnation methods. The catalysts were characterized by N2 adsorption, X-ray diffraction（XRD）, high-resolution transmission electron microscopy（HRTEM）, H2 temperature-programmed reduction（H2-TPR）, dynamic oxygen storage capacity（DOSC） and in-situ DRIFTS technologies. For S-f supports, the surfactant was added into the solution before spray-drying in the synthesis process, which facilitates more active oxygen formation on the surface of CeO2. After loading Pt, the more active oxygen on CeO2 contributes to dispersing Pt species and enhancing the CO oxidation activity. As for the aged samples,Pt-R-h shows the highest activity above 190 ℃ because of the presence of more partly oxidized Pt^（δ＋） species. Thus the activity is also influenced by the states of Pt and the Pt^（δ＋） species may contribute to the high activity at elevated temperature.
基金Supported by the National Basic Research Program of China under Grant Nos 2010CB327504,2011CB922100 and2011CB301900the National Natural Science Foundation of China under Grant Nos 11104130 and 61322112+2 种基金the Natural Science Foundation of Jiangsu Province under Grant Nos BK2011556 and BK2011050the Priority Academic Program Development of Jiangsu Higher Education Institutionsand the NUPTSF Grant Nos NY213069 and NY214028
文摘The effect of oxygen partial pressure （Po2） during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide （a-IGZO） thin film transistors （TFTs） is investigated. As Po2 increases from 10% to 30%, it is found that the device shows enhanced bias stress stability with significantly reduced threshold voltage drift under positive gate bias stress. Based on the x-ray photoelectron spectroscopy measurement, the concentration of oxygen vacancies （Or） within the a-IGZO layer is suppressed by increasing Po2. Meanwhile, the low-frequency noise analysis indicates that the average trap density near the channel/dielectric interface continuously drops with increasing Po2. Therefore, the improved interface quality with increasing Po2 during the channel layer deposition can be attributed to the reduction of interface Ov-related defects, which agrees with the enhanced bias stress stability of the a-IGZO TFTs.
文摘Applying quantitative temporal analysis of products reactor measurements, we studied the reactive removal of active oxygen present on Au/TiO2 catalysts after calcination at elevated temperatures （400 ＆#176;C） by CO pulses and its replenishment by O2 pulses at 80 ＆#176;C, focusing on the nature of the active oxygen species. In contrast to previous studies, which mainly focused on and clarified the nature of the active oxygen species for the catalytic CO oxidation, which is reversibly formed and replenished under typical reaction conditions, this study demonstrates that directly after calcina‐tion an additional oxygen species is present. This species is also active for the CO oxidation, but it is not or only very little formed under typical reaction conditions. Implications of these results on the mechanistic understanding of the CO oxidation on Au/TiO2, in particular on the role of different active oxygen species, will be discussed.
文摘Two series of layered mixed oxides La4BaCu5-xMxO13+(M=Mn, Co, x=05) were prepared and characterized by means of XRD, XPS, O2TPD and chemical analysis. The results show that their structures are 5layered ABO3 perovskite, and the XPS and O2TPD investigation confirms that there exists synergistic effect between Cu ion and M when M ion is doped into the lattice of La4BaCu5O13+, and the synergistic effect between Mn and Cu is stronger than that of CuCo.
基金Supported by Independent Innovation Project of Jiangsu Province[CX(11)1005]Nanjing Science and Technology Development Project(2011ZD006)
文摘Employing nutrient solution hydroponic method,the effects of exogenous nitric oxide（NO）on the growth and active oxygen metabolism in cucumber（Cucumis sativus L.）seedlings under NaCl stress were investigated.The results indicated that NaCl treatment significantly inhibited the growth of cucumber seedlings,while exogenous NO could significantly alleviate the inhibitory effects of NaCl stress on seedling growth.Especially,0.1 mmol/L SNP treatment exhibited better effects than 0.5 mmol/L SNP treatment on alleviating NaCl stress.Under 0.1 mmol/L NaCl stress,adding 0.1 mmol/L exogenous NO could significantly decrease the generation rate of O·-2and MDA content,significantly improve soluble protein content and enhance the activities of SOD,POD and CAT,thus reducing the damage of salt stress to cucumber seedlings.
基金supported by the National Natural Science Foundation of China (Nos.51868030,52070090,52100122,22266019,and 21876071)the Science and Technology Planning Project of Yunnan Province (Nos.202001AU070031,202101BE070001-030,and 202101BC070001-009)Applied Basic Research Program of Yunnan Province (No.2019FD043)。
文摘To investigate the enhancing effect of Mn on the performance of simultaneous catalytic oxidation of AsH_(3)and PH_(3)by CuO-Al_(2)O_(3)in a reducing atmosphere under micro-oxygen conditions,Cu-Mn modifiedγ-Al_(2)O_(3)catalysts were prepared.The characteristics of the catalysts showed that Mn reduced the crystallinity of the active CuO component,increased the number of oxygen vacancies and acidic sites on the catalyst surface,enhanced the mobility of surface oxygen,and the interaction between copper and manganese promoted the redox cycling ability of the catalysts and improved their oxidation performance,which increased the conversion frequency(TOF)by 2.54×10^(-2)to 3.07×10^(-2)sec^(-1).On the other hand,the introduction of Mn reduced the production of phosphate and As_(2)O_(3)on the catalyst surface by30.96%and 44.9%,which reduced the coverage and inerting of the active sites by phosphate and As_(2)O_(3),resulting in an 8 hr(6 hr)improvement in the stability of PH_(3)(AsH_(3))removal.
文摘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.
基金financially supported by the National Natural Science Foundation of China (52474338,22109084 and 52304338)the Hunan Provincial Key Research and Development Program (2024JK2093,2023GK2016)supported in part by the High Performance Computing Center of Central South University.
文摘Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy density.However,the all-solid-state batteries with nickel-rich oxide cathodes suffer from performance degradation due to the reactions between the highly reactive surface oxygen of the cathode and the electrolyte,as well as the instability of the bulk oxygen structure in the cathode.Herein,we propose a synergistic modification design scheme to adjust the oxygen activity from surface to bulk.The LiBO_(2)coating inhibits the reactivity of surface lattice oxygen ions.Meanwhile,Zr doping in the bulk phase forms strong Zr-O covalent bonds that stabilize the bulk lattice oxygen structure.The synergistic effect of these modifications prevents the release of oxygen,thus avoiding the degradation of the cathode/SE interface.Additionally,the regulation of surface-to-bulk oxygen activity establishes a highly stable interface,thereby enhancing the lithium ion diffusion kinetics and mechanical stability of the cathode.Consequently,cathodes modified with this synergistic strategy exhibit outstanding performance in sulfide-based ASSLBs,including an ultra-long cycle life of 100,000 cycles,ultra-high rate capability at 45C,and 85% high active material content in the composite cathode.Additionally,ASSLB exhibits stable cycling under high loading conditions of 82.82 mg cm^(-2),achieving an areal capacity of 17.90 mA h cm^(-2).These encouraging results pave the way for practical applications of ASSLBs in fast charging,long cycle life,and high energy density in the future.
基金Advanced Materials-National Science and Technology Major Project(2024ZD0606500)National Natural Science Foundation of China(21902110)Sichuan Provincial Science Foundation(2023NSFSC0093)。
文摘Gasoline soot particles pose a severe threat to the ecological environment and human health,but they can be potentially filtered out by using catalytic gasoline particulate filter(cGPF),whose core component is a catalyst coating.To develop more effective catalyst coatings with excellent activity,stability,and water resistance,a kind of composite oxide MnO_(x)/CeO_(2)-ZrO_(2) was synthesized using different methods,and its soot oxidation performance was evaluated under low O_(2) concentrations.Herein,MnO_(x)/CeO_(2)-ZrO_(2) prepared by impregnation(abbreviated as MCZ-IM)exhibits a T_(50)(temperature required for 50% soot conversion)of 329℃in 1%O_(2) and 370℃ in 0.5%O_(2),displaying better comprehensive performance when compared to catalysts prepared by high-energy ball milling(abbreviated as MCZ-HB)and co-precipitation(abbreviated as MCZ-CP).Structure-activity relationship reveals that soot oxidation under low O_(2) concentrations is weakly correlated with textural and structural properties,but strongly depends on the generation and migration of active oxygen species(AOS),especially superoxide(O_(2)^(-))and peroxide(O_(2)^(2-))anions,which are linked to redox properties,oxygen storage and release capacity,as well as amount of oxygen vacancies.The impregnation method enhances oxygen species adsorption,activation and desorption more effectively,endowing it with a more effective approach to enhancing AOS generation and mobility.Therefore,this study not only provides a preparation strategy for particulate matter oxidation catalysts applicable to actual operating conditions,but also offers insights into the migration of AOS at low O_(2) concentrations.
基金supported by National Natural Science Foundation of China(52204376)Open Project of Yunnan Precious Metals Laboratory Co.(YPML-2023050266)Youth Foundation of Hebei Province(E2022103007)。
文摘NO catalytic oxidation is the key performance of the diesel oxidation catalyst(DOC).We present a facile deposition method for the core-shell rare-earth manganese-zirconium composite oxide that shows the Mn mullite phase uniform loading on the surface of zirconium-based composite(YMO/CYZO),which demonstrates a superior NO oxidation catalytic performance in simulated diesel combustion conditions and better thermal stability than mullite phase YMn_(2)O_(5)oxide.The NO oxidation at 250℃over YMO/CYZO-a approaches 25.2%in contrast to 13.52%over YMn_(2)O_(5)-a.Then the catalytic performance of YMO/CYZO,YMO and commercial 1 wt%Pt/Al_(2)O_(3)in a NO+O_(2)atmosphere was compared.The maximum conversion rate of YMO/CYZO to NO oxidation is 89.6%at 274℃with a GHSV of 50000 h^(-1),and the performance is superior to that of YMO(82.8%at 293℃)and 1 wt%Pt/Al_(2)O_(3)(68.6%,335℃).The NO-temperature programmed desorption(NO-TPD)and diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)results reveal that YMO/CYZO has multiple NO adsorption sites and high storage capacity.Furthermore,density functional theory(DFT)calculation indicates that YMO/CYZO has lower oxygen vacancy formation energies(E_(v)=0.93 eV)and favorable NO adsorption energies(E_(ads)=2.1 eV).Moreover,in situ X-ray photoelectron spectroscopy(XPS)characterization shows that the core-shell structure of YMO/CYZO has the potential to transmit active oxygen species to help realize Mn3+to Mn4+during the reaction process to enhance the conversion of NO*molecules,while NO oxidation reactions follow the MvK mechanism.
