Magnesium incorporation activates perovskite cobaltites toward efficient and stable electrocatalytic oxygen evolution

Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability.In response to the defects,herein,the Mg-incorporated perovskite cobaltite SrCo_(0.6)Fe_(0.3M)g_(0.1)O_(3-δ)(SCFM-0.1)is proposed as a novel earth-abundant and durable OER electrocatalyst.A well-consolidated cubic-symmetry structure and more active oxygen intermediates are enabled upon Mg substitution.Hence,the optimized SCFM-0.1 perovskite oxide achieves prominent OER electrocatalytic performance,that is,a low overpotential of only 320 mV at 10 mA cm^(-2),a small Tafel slope of 65 mV dec^(-1),as well as an outstanding durability within 20 h,substantially outperforming that of the pristine SrCo_(0.7)Fe_(0.3)O_(3-δ)and benchmark Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)and IrO_(2) catalysts.The strong pHdependent behavior associated with lattice oxygen activation mechanism for SCFM-0.1 catalyst is also confirmed.This work paves a unique avenue to develop cost-effective and robust perovskite cobaltites for efficient OER electrocatalysis.

Layer-Contacted Graphene-Like BN/Ultrathin Bi_(3)O_(4)Br Stacking for Boosting Photocatalytic Molecular Oxygen Activation

Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrathin Bi_(3)O_(4)Br was achieved with strong interaction. Dehalogenation is designed to harvest more visible light, and the ultrathin structure of Bi_(3)O_(4)Br is designed to accelerate charge transfer from inside to the surface. After graphene-like BN was engineered, photocatalytic performance greatly improved under visible light irradiation. Graphene-like BN can act as a surface electron-withdrawing center and adsorption center, facilitating molecular oxygen activation. O_(2)^(·-)was determined to be the main active species during the degradation process through analyses of electron spin resonance and XPS valence band spectra.

Changes of Reactive Oxygen Species and Related Enzymes in Mitochondrial Respiration During Storage of Harvested Peach Fruits

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.

The Maturation and Senescence in Relation to Ca^2+,CaMContent and Ca^2+-ATPase Activity and Active OxygenMetabolism in Strawberry Fruits

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.

Active oxygen center in oxidative coupling of methane on La_(2)O_(3) catalyst

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.

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.

Effects of salt-alkali stress on active oxygen metabolism in roots of Spiraea × bumalda 'Gold Mound' and Spiraea × bumalda 'Gold Flame'

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.

Low temperature surface oxygen activation in crystalline MnO_(2) triggered by lattice confined Pd single atoms

Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as support. Compared with the Pd clusters anchored on the surface, the lattice confined Pd single atoms allows spontaneous exaction of surrounding lattice oxygen at room temperature when employed in CO oxidation. The MnO_(2) supported Pd SAC exhibited a high turnover frequency of 0.203 s^(−1) at low reaction temperature, which is higher than that of recently reported Pd SACs. Theoretical calculations also confirmed the confined monatomic Pd activate lattice oxygen with an ultralow energy barrier. Our results illustrate that the unique coordination environment of single atom provided by lattice confinement is promising to boost the activity of SACs.

Simulation of oxygen transfer in liquid lead under influence of nanoparticles by using lattice Boltzmann method

Oxygen transfer presents a serious challenge in the application of liquid lead as a nuclear coolant in advanced reactors. To mitigate corrosion by liquid lead in contact with steel, carefully controlling the oxygen concentration has been used as an effective way. Oxygen needs to mix in liquid lead uniformly and quickly. To enhance oxygen transport in liquid lead, nanoparticles are added to the liquid metal. In the current study, a lattice Boltzmann method is applied to investigate natural convection of copper/lead and aluminum oxide/lead in two-dimensional simplified container. Two thermal boundary cases are evaluated in order to check the effect of different natural convection flow patterns on oxygen transport. Some useful information are obtained such as improvement in natural convection and reduction in oxygen equilibrium time.

The Effect of Oxygen Partial Pressure during Active Layer Deposition on Bias Stability of a-InGaZnO TFTs

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.

Effects of Exogenous NO on Active Oxygen Metabolism in Cucumber Seedlings under NaCl Stress

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.

STUDY ON NODULE RATIO AND COMPACTED GRAPHITE RATIO OF IRON FLUID TREATED BY RARE EARTH MAGNESIUM ALLOY QUICKLY EXAMINED BY CONCENTRATED DIFFERENCE FIXING OXYGEN

The article uses the method of regression statistics to obtain the regression formula of iron fluid nodule ratio Q and compacted graphite ratio R, through rare earth magnesium treatment. At the same time it has given thejudging figure of Q and R, considering oxygen activity and temperature. When using oxygen activity to judgenodule ratio and compacted graphite ratio of the ironfluid treated by rare earth magnesium alloy, its limit value changes with the change of temperature.

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.

Oxygen Molecule Activation on Single-Atom Catalysts with Cu, Ag, and Au: A Cluster Model Study

(M = Au, Ag, Cu;n= 1, 2, 3) clusters were used as a cluster model to study the activation of oxygen molecules on single-atom catalysts. Structures of clusters were studied by density functional calculations with global optimization. For each n, the most stable structures are quite similar for different metal types, and the oxygen molecule prefers to be adsorbed onto M atoms. It is found that the activation degree of oxygen is higher on clusters with non-noble metal Cu than that of Ag or Au containing clusters, by comparing the changes of O-O bond length and vibrational frequency, natural charge population analysis, Fuzzy bond order analysis, and energy barriers of O2 dissociation. CO oxidation was used as a probe reaction to study the reactivity of Cu-containing clusters, and it is found that the reactivity decreases with the increase of the size of silicon-oxygen clusters. Our results give a new aspect to understand the reaction mechanism of non-precious metal single-atom catalyst for oxygen activation with high efficiency.

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.

THE ELECTROCATALYTIC ACTIVITY OF NiCo2O4 FOR THE OXYGEN EVOLUTION REACTION

A spinel oxide NiCo204 prepared by thermal decomposition is of very high activity for the oxygen evolution reaction(OER)in alkaline solution.The oxygen evolution overpotential on NiCo204 is 0.252-0.262V in 10 M NaOH solution at 343K and current density 100 mAcm^(-2).

Effects of treatment time and temperature on the DC corona pretreatment performance of waste activated sludge

In order to improve the anaerobic digestion efficiency of waste activated sludge（WAS）,a pretreatment procedure should be carried out so as to disrupt the microbial cell structure,thus releasing intracellular organic matters.In this paper,a corona discharge triggered by a DC voltage was employed to pre-treat WAS for various time periods under different temperatures.The magnitude of the DC voltage was 4 k V at both negative and positive polarities.The changes in the soluble chemical oxygen demand,phosphorus and nitrogen content,and p H value within the WAS were utilized to estimate the pretreatment performance of the DC corona.It was found that with increasing treatment time,the pretreatment efficiency tends to be reduced.With increased temperature,the pretreatment efficiency appears to be better.It is suggested that the oxidative species and the active particles generated in the corona discharge play an important role in disrupting the microbial cell structure,which is dependent upon the treatment time and the temperature.

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.

Selective photocatalytic oxidation of methane to C1 oxygenates by regulating sizes and facets over Au/ZnO

Photocatalytic oxidation of methane to value-added chemicals is a promising process under mild conditions,nevertheless confronting great challenges in efficiently activating C-H bonds and inhibiting over-oxidation.Herein,we propose a comprehensive strategy for the selective generation of reactive oxygen species(ROS)by regulating the sizes and facets of Au nanoparticles loaded on ZnO.For photocatalytic methane oxidation at ambient temperature,a high oxygenates yield of 36.4 mmol·g^(-1)·h^(-1) with a nearly 100%selectivity has been achieved over the optimized 1.0%Au/ZnO-9.6(1%Au with(111)facet and 9.6 nm size on ZnO)photocatalyst,exceeding most reported literatures.Mechanism investigations reveal that 1.0%Au/ZnO-9.6 with the medium size and Au(111)facet guarantees the favourable formation of superoxide radicals(·OOH)through mild oxygen reduction,ultimately leading to excellent photocatalytic methane oxidation performance.This work provides some guidance for the delicate design of photocatalysts for efficient photocatalytic methane oxidation and oxygen utilization.