Effect of Calcination Temperature on Surface Oxygen Vacancies and Catalytic Performance Towards CO Oxidation of Co3O4 Nanoparticles Supported on SiO2

Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction （XRD）, laser Raman spectroscopy, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR） and X-ray absorption fine structure （XAFS） spectroscopy. Both XRD and Raman spectroscopy only detect the existence of Co3O4 crystallites in all catalysts. However, XPS results indicate that excess Co2＋ ions are present on the surface of Co3O4 in Co3O4（200）/Si02 as compared with bulk Co3O4. Meanwhile, TPR results suggest the presence of surface oxygen vacancies on Co3O4 in Co3O4（200）/SiO2, and XAFS results demonstrate that Co3O4 in Co3O4（200）/SIO2 contains excess Co2＋. Increasing calcination temperature results in oxidation of excess Co2＋ and the decrease of the concentration of surface oxygen vacancies, consequently the for- mation of stoichiometric Co3O4 on supported catalysts. Among all Co3O4/SiO2 catalysts, Co3O4（200）/SiO2 exhibits the best catalytic performance towards CO oxidation, demonstrating that excess Co2＋ and surface oxygen vacancies can enhance the catalytic activity of Co3O4 towards CO oxidation. These results nicely demonstrate the effect of calcination temperature on the structure and catalytic performance towards CO oxidation of silicasupported Co3O4 catalysts and highlight the important role of surface oxygen vacancies on Co3O4.

Rearrangement on surface structures by boride to enhanced cycle stability for LiNi0.80Co0.15Al0.05O2 cathode in lithium ion batteries

The side reaction between the active material and liquid-electrolyte cause structural damage and particle pulverization is one of the important factors leading to the capacity decay of LiNi0.80Co0.15Al0.05O2(NCA)materials in Li ion batteries(LIBs).Surface modification is an effective strategy for NCA cathodes,which could alleviate the degradation associated with surface processes.Herein,a surface structure rearrangement of NCA cathode secondary particles was reported by in-situ forming a solid electrolyte LiBO2.The LiBO2 is beneficial for alleviating the stress during charge/discharge process,thereby slowing down the rate of cracks formation in the secondary particles,which facilitates the Li+de-intercalation as well as prevents penetration of the liquid-electrolyte into the interior of the particles.As a result,the surface structure rearrangement NCA(RS-NCA)delivers a high discharge capacity of 202.5 m Ah g^-1 at 0.1 C,and exhibits excellent cycle stability with discharge capacity retaining 148 m Ah g^-1 after 200 cycles at 2 C.This surface structure rearrangement approach provides a new viewpoint in designing high-performance high-voltage LIBs.

Simulation and Experiment for Oxygen-enriched Combustion Engine Using Liquid Oxygen to Solidify CO2

For capturing and recycling of CO2 in the internal combustion engine, Rankle cycle engine can reduce the exhaust pollutants effectively under the condition of ensuring the engine thermal efficiency by using the techniques of spraying water in the cylinder and optimizing the ignition advance angle. However, due to the water spray nozzle need to be installed on the cylinder, which increases the cylinder head design difficulty and makes the combustion conditions become more complicated. In this paper, a new method is presented to carry out the closing inlet and exhaust system for internal combustion engines. The proposed new method uses liquid oxygen to solidify part of cooled CO2 from exhaust system into dry ice and the liquid oxygen turns into gas oxygen which is sent to inlet system. The other part of CO2 is sent to inlet system and mixed with oxygen, which can reduce the oxygen-enriched combustion detonation tendency and make combustion stable. Computing grid of the IP52FMI single-cylinder four-stroke gasoline-engine is established according to the actual shape of the combustion chamber using KIVA-3V program. The effects of exhaust gas recirculation （EGR） rate are analyzed on the temperatures, the pressures and the instantaneous heat release rates when the EGR rate is more than 8%. The possibility of enclosing intake and exhaust system for engine is verified. The carbon dioxide trapping device is designed and the IP52FMI engine is transformed and the CO2 capture experiment is carried out. The experimental results show that when the EGR rate is 36% for the optimum EGR rate. When the liquid oxygen of 35.80-437.40 g is imported into the device and last 1-20 min, respectively, 21.50-701.30 g dry ice is obtained. This research proposes a new design method which can capture CO2 for vehicular internal combustion engine.

Effect of rich R-TiO2 on the rate and cycle properties of Li4Ti5O12 as anode for lithium ion batteries

Li4Ti5012 (LTO) with rich R-TiO2 (17.06, 23.69, and 34.42 wt%), namely, R-TiO2@Li4Ti5O12 composites, were synthesized using the hydrothermal method and tetrabutyl titanate (TBT) as the precursor. Rietveld refinement of X-ray diffraction (XRD) results show that the proportion of Li occupying 16d sites is extraordinary low and the lattice constants of LTO and R-TiO2 change with the ritanium dioxide content. EIS measurements showed that with in creasing R-TiO2 content, both its charge transfer impedance (Rct) and lithium ion diffusion coefficient (DLi) decreased. The changes of Rct and DLi caused by the increase of titanium dioxide content have synergic-antagonistic effects on the rate and cycle properties of Li4Ti5012. The rate performance is positively related to DLi, while the cycle property is negatively correlated with Rct, indicati ng that the rate performs nee is mainly related to DLi, while Rct more significantly affects the cycle performance. LTO-RT-17.06% exhibited excellent rate properties, especially under a high current density (5.0 C, 132.5 mAh/g) and LTO-RT-34.42% showed superior long-term cycle performance (0.012% capacity loss per cycle) compared to that of LTO-RT-17.06% and LTO-RT-23.69%.

Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry

P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.

Phase Transition and Oxygen Ion Diffusion in （La1-xLnx）2Mo2O9 （Ln=Nd, Gd, x=0.05-0.25） Using Dielectric Relaxation Method

Dielectric relaxation method was employed to study the properties of oxygen ion diffusion and phase transition in the oxide-ion conductors （Lal-xLnx）2Mo209 （Ln=Nd, Gd, x=0.05-0.25）. Two dielectric loss peaks were observed： peak Pd at about 600 K and peak P5 around 720 K. Peak Pd is a relaxational peak and associated with the short-range diffusion of oxygen ions, while peak P5 hardly changes its position and dramatically decreases in height with increasing frequency, exhibiting non-relaxational nature. With increasing Ln^3＋ concentration, the heights of peak Ph and Pd increase at first and then decrease after passing a maximum at 15% doping. It is suggested that peak P5 is related to the phase transition of a static disordered state to a dynamic disordered state in oxygen ions/vacancies distribution. It is found that the 15%Gd or 15%Nd doped La2Mo209 samples exhibit the highest conductivity in accordance with the highest height of peak Pd at this doping content.

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).

RBaCo2O(5＋δ)陶瓷的氧阻性能研究(英文)

用固相反应法制备了RBaCo2O5+δ(R=Y、Dy、Gd、Pr、Nd、Sm和Eu)系列陶瓷.用标准四探针法测量了它们从室温到600℃之间的电阻率变化.在温度较低时,它们的电阻率都随着温度的升高而减小,显示为半导体特征.当电阻率在某一温度达到最大值后,电阻率开始随着温度升高而缓慢增加,显示为半金属特征.进一步研究了RBaCo2O5+δ系列陶瓷在高温恒温时的电阻率随着环境气氛的变化情况.结果表明RBaCo2O5+δ陶瓷是一类潜在的氧阻传感器材料,并且它们的响应速率从快到慢顺序是YBaCo2O5+δ>DyBaCo2O5+δ>GdBaCo2O5+δ>PrBaCo2O5+δ>NdBaCo2O5+δ>SmBaCo2O5+δ>EuBaCo2O5+δ.以YBaCo2O5+δ陶瓷为例,在700℃恒温时,当从氧气氛切换到氮气氛时,由于晶格中氧的脱附导致电阻率先是快速上升,然后缓慢上升,并在90 s内达到最大平衡值.反之,当从氮气氛切换为氧气氛时,由于氧的吸附,电阻率迅速降低,约30 s内达到最小平衡值.

Effects of Atomic Oxygen Irradiation on Transparent Conductive Oxide Thin Films

Transparent conductive oxide （TCO） thin film is a kind of functional material which has potential applications in solar cells and atomic oxygen （AO） resisting systems in spacecrafts. Of TCO, ZnO：Al （ZAO） and In2O3：Sn （ITO） thin films have been widely used and investigated. In this study, ZAO and ITO thin films were irradiated by AO with different amounts of fluence. The as-deposited samples and irradiated ones were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and Hall-effect measurement to investigate the dependence of the structure, morphology and electrical properties of ZAO or ITO on the amount of fluence of AO irradiation. It is noticed that AO has erosion effects on the surface of ZAO without evident influences upon its structure and conductive properties. Moreover, as the amount of AO fluence rises, the carrier concentration of ITO decreases causing the resistivity to increase by at most 21.7%.

Selective hydrogenation of CO2 to methanol over Ni/In2O3 catalyst

An In2O3 supported nickel catalyst has been prepared by wet chemical reduction with sodium borohydride(NaBH4) as a reducing agent for selective hydrogenation of carbon dioxide to methanol. Highly dispersed Ni species with intense Ni-In2O3 interaction and enhanced oxygen vacancies have been achieved.The highly dispersed Ni species serve as the active sites for hydrogen activation and hydrogen spillover.Abundant H adatoms are thereby generated for the oxygen vacancy creation on the In2O3 surface. The enhanced surface oxygen vacancies further lead to improved CO2 conversion. As a result, an effective synergy between the active Ni sites and surface oxygen vacancies on In2O3 causes a superior catalytic performance for CO2 hydrogenation with high methanol selectivity. Carbon monoxide is the only by product detected. The formation of methane can be ignored. When the reaction temperature is lower than 225 ℃,the selectivity of methanol is 100%. It is higher than 64% at the temperature range between 225 ℃ and 275 ℃. The methanol selectivity is still higher than 54% at 300 ℃ with a CO2 conversion of 18.47% and a methanol yield of 0.55 gMeOHg-1cath-1(at 5 MPa). The activity of Ni/In2O3 is higher than most of the reported In2O3-based catalysts.

N Cycle, N Flow Trends in Japan, and Strategies for Reducing N_2O Emission and NO_3^- Pollution

To feed an increasing population, large amounts of chemical nitrogen fertilizer have been used to produce much of our food, feed and fiber thereby increasing nitrogen levels in soils, natural waters, crop residues, livestock wastes,and municipal and agricultural wastes, with national and international concern about its potential adverse effects on environmental quality and public health. To understand these phenomena and problems, first the nitrogen cycle and the environment are described. Then recent trends for nitrogen cycling through the food and feed system, N2O emissions from fertilized upland and paddy soils, and NO-3 pollution in ground water in Japan are reported. Finally, mitigation strategies in Japan for reducing N2O emission and NO-3 pollution are proposed, including nitrification inhibitors, controlled release fertilizers, utilization of plant species that could suppress nitrification, utilizing the toposequence, government policy, and appropriate agricultural practices. Of all the technologies presented, use of nitrification inhibitors and controlled release fertilizers are deemed the most important with further development of these aspects of technologies being expected. These practices, if employed worldwide, could help reduce the load, or environmental deterioration, on the Earth's biosphere.

Ent-11α-Hydroxy-15-oxo-kaur-16-en-19-oic-acid Inhibits Growth of Human Lung Cancer A549 Cells by Arresting Cell Cycle and Triggering Apoptosis

Objective： To examine the apoptotic effect of ent-llα-hydroxy-15-oxo-kaur-16-en-19-oic-acid （5F）, a compound isolated from Pteris semipinnata L （PsL）, in human lung cancer A549 cells. Methods： A549 cells were treated with 5F （0-80 lag/ml） for different time periods. Cytotoxicity was examined using a Ml-I- method. Cell cycle was examined using propidium iodide staining. Apoptosis was examined using Hoechst 33258 staining, enzyme-linked immunosorbent assay （ELISA） and caspase-3 activity analysis. Expression of representative apoptosis-related proteins was evaluated by Western blot analysis. Reactive oxygen species （ROS） level was measured using standard protocols. Potential interaction of 5F with cisplatin was also examined. Results： 5F inhibited the proliferation of A549 cells in a concentration- and time-dependent manner. 5F increased the accumulation of cells in sub-G1 phase and arrested the cells in the G2 phase. Exposure to 5F induced morphological changes and DNA fragmentation that are characteristic of apoptosis. The expression of p21 was increased. 5F exposure also increased Bax expression, release of cytochrome c and apoptosis inducing factor （AIF）, and activation of caspase-3. 5F significantly sensitized the cells to cisplatin toxicity. Interestingly, treatment with 5F did not increase ROS, but reduced ROS production induced by cisplatin. Conclusion： 5F could inhibit the proliferation of A549 cells by arresting the cells in G2 phase and by inducing mitochondrial-mediated apoptosis.

Oxygen vacancies engineering by coordinating oxygen-buffering CeO_(2) with CoO_(x) nanorods as efficient bifunctional oxygen electrode electrocatalyst

CeO_(2)decorated CoOx rod-like hybrid,supported onto holey reduced graphene(CoOx/CeO_(2)/RGO)composite,was fabricated via a surfactant-assisted route.Its corresponding electrocatalytic performance towards oxygen reduction/evolution reactions(ORR and OER)was systematically investigated in alkaline electrolyte.Structural,morphological and compositional studies revealed changes in electronic and surface properties when CeO_(2)was introduced as an oxygen buffer material.The oxygen vacancies effectively enhanced the electrocatalytic activity,while the synergistic effect of co-catalyst CeO_(2),CoOx activecenters,and defective graphene with many voids facilitate the charge/mass transfer,making CoOx/CeO_(2)/RGO an efficient and stable bifunctional electrocatalyst for OER/ORR with△E=0.76 V(△E=E10mAcm.-2OER-E_(1/2).ORR).This parameter is 70 mV and 270 mV lower than CoOx/RGO and the benchmark Pt/C,respectively.In addition,the OER/ORR bifunctionality of CoOx/CeO_(2)/RGO composite outperforms that of Pt/C catalyst in a H2-O_(2)micro fuel cell platform.

Effects of freeze–thaw cycles on soil N_2O concentration and flux in the permafrost regions of the Qinghai–Tibetan Plateau

Nitrous oxide(N_2 O) is one of the most important greenhouse gases in the atmosphere; freeze–thaw cycles(FTCs) might strongly influence the emission of soil N_2 O on the Qinghai–Tibetan Plateau(QTP). However, there is a lack of in situ research on the characteristics of soil N_2 O concentration and flux in response to variations in soil properties caused by FTCs.Here, we report the effect of FTC-induced changes in soil properties on the soil N_2 O concentration and flux in the permafrost region of the higher reaches of the Shule River Basin on the northeastern margin of the QTP. We measured chemical properties of the topsoil, activities of soil microorganisms, and air temperature(AT), as well as soil N_2 O concentration and flux, over an annual cycle from July 31, 2011, to July 30, 2012. The results showed that soil N_2 O concentration was significantly affected by soil temperature(ST), soil moisture(SM), soil salinity(SS), soil polyphenol oxidase(SPO), soil alkaline phosphatase(SAP), and soil culturable actinomycetes(SCA), ranked as SM>SS>ST>SPO>SAP>SCA, whereas ST significantly increased soil N_2 O flux, compared with SS. Overall, our study indicated that the soil N_2 O concentration and flux in permafrost zone FTCs were strongly affected by soil properties, especially soil moisture, soil salinity, and soil temperature.

Electrochemical Cycled Structure of MnV_2O_6 Nanoribbons Synthesized via Hydrothermal Route

1 Introduction Low-dimensional nanostructures, such as nanorods, nanowires, and nanotubes, have received much attention for their superior optical, electrical, catalytic and magnetic properties. Owing to their low dimensionality and quantum continement effect, low-dimensional nanoscale materials can be exploited as fundamental building blocks for nanoscience and nanodevices^[1-3]. In recent years, efforts have been devoted to develop new approaches to synthesize one-dimensional（lD） nanostructrued vanadium oxides or vanadates materials, such as V205, NaV2Os, and CuV206, which have been widely investigated in catalytic or electrochemical fields due to their outstanding structural flexibility^[4-6].

Investigation on pumping oxygen characteristics of (Bi_2O_3)_(0.73)(Y_2O_3)_(0.27) solid electrolyte

（Bi2O3）0.73（Y2O3）0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 （Y2O3 stabilized） oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10^-2-1×10^-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10^-37-1×10^-27 Pa at 1.0 V and 1×10^-53-1×10^47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.

Design of hierarchical, three-dimensional free-standing single-atom electrode for H2O2 production in acidic media

Electrochemical reduction of molecular O2 to hydrogen peroxide(H2O2)offers a promising solution for water purification and environmental remediation.Here,we design a hierarchical free-standing single-Co-atom(with Co-N4 coordination)electrode for oxygen reduction reaction(ORR)via a two-electron pathway to make H2O2 in acidic media.The current density of the single-Co-atom electrode reached 51 mA/cm2 at 0.1 V vs reversible hydrogen electrode,lasting for more than 10 hours of continuous operation with H2O2 selectivity greater than 80%.Toward practical application,the single-Co-atom electrode was directly used to assemble an electrochemical cell to produce H2O2 at a rate of 676 mol/kgcat/h with a cell voltage of about 1.6 V.

Effect of nano-sized Al2O3 reinforcing particles on uniaxial and high cycle fatigue behaviors of hot-forged AZ31B magnesium alloy

The effect of hot-forging process was investigated on microstructural and mechanical properties of AZ31 B alloy and AZ31 B/1.5 vol.%Al2 O3 nanocomposite under static and cycling loading. The as-cast alloy and composite were firstly subjected to a homogenization heat treatment at 450 ℃ and then an open-die forging at 450 ℃. The results indicated that the presence of reinforcing particles led to grain refinement and improvement of dynamic recrystallization. The forging process was more effective to eliminate the porosity in the cast alloy workpiece. Microhardness of the forged composite was increased by up to 80% and 16%, in comparison with those of the cast and forged alloy samples, respectively. Ultimate tensile strength and maximum tensile strain of the composite were improved by up to 45% and 23%, compared with those of the forged alloy in similar regions. These enhancements were respectively 50% and 37% in the compression test. The composite exhibited a fatigue life improvement in the region with low applied strain;however, a degradation was observed in the high applied strain region. Unlike AZ31 B samples, tensile, compressive and high cycle fatigue behaviors of the composite showed less sensitivity to the applied strain, which can be attributed to the amount of porosity in the samples before and after the hot-forging.

Facile Fabrication of Fe3O4@TiO2@C Yolk–Shell Spheres as Anode Material for Lithium Ion Batteries

Transition metal oxides have been actively exploited for application in lithium ion batteries due to their facile synthesis,high specific capacity,and environmental-friendly.In this paper,Fe3O4@TiO2@C yolk-shell(Y-S)spheres,used as anode material for lithium ion batteries,were successfully fabricated by Stober method.XRD patterns reveal that Fe3O4@TiO2@C Y-S spheres possess a good crystallinity.But the diffraction peaks’intensity of Fe3O4 crystals in the composites is much weaker than that of bare Fe3O4 spheres,indicating that the outer anatase TiO2@C layer can cover up the diffraction peaks of inner Fe3O4 spheres.The yolk-shell structure of Fe3O4@TiO2@C spheres is further characterized by TEM,HAADFSTEM,and EDS mapping.The yolk-shell structure is good for improving the cycling stability of the inner Fe3O4 spheres during lithium ions insertion-extraction processes.When tested at 200 mA/g,the Fe3O4@TiO2@C Y-S spheres can provide a stable discharge capacity of 450 mAh/g over 100 cycles,which is much better than that of bare Fe3O4 spheres and TiO2@C spheres.Furthermore,cyclic voltammetry curves show that the composites have a good cycling stability compared to bare Fe3O4 spheres.

Potential methane and nitrous oxide production and respiration rates from penguin and seal colony tundra soils during freezing–thawing cycles under different water contents in coastal Antarctica

In coastal Antarctica, frequent freezing-thawing cycles （FTCs） and changes to the hydrological conditions may affect methane （CH4） and nitrous oxide （N2O） production and respiration rates in tundra soils, which are difficult to observe in situ. Tundra soils including omithogenic tundra soil （OAS）, seal colony soil （SCS） and emperor penguin colony soil （EPS） were collected. In laboratory, we investigated the effects of FTCs and water addition on potential N2O and CH4 production and respiration rates in the soils. The CH4 fluxes from OAS and SCS were much less than that from EPS. Meanwhile, the N2O fluxes from OAS and EPS were much less than that from SCS. The N2O production rates from all soils were extremely low during freezing, but rapidly increased following thawing. In all cases, FTC also induced considerably enhanced soil respiration, indicating that soil respiration response was sensitive to the FTCs. The highest cumulative rates of CH4, N2O and CO2 were 59.5 mg CH4-C·kg-1 in EPS, 6268.8μg N2O-N·kg-1 in SCS and 3522.1mg CO2-C·kg-1 in OAS. Soil water addition had no significant effects on CH4 production and respiration rates, but it could reduce N2O production in OAS and EPS, and it stimulated N2O production in SCS. Overall, CH4 and N2O production rates showed a trade-off relationship during the three FTCs. Our results indicated that FTCs greatly stimulated soil N2O and CO2 production, and water increase has an important effect on soil N2O production in coastal Antarctic tundra.