Ca and Sr co-doping induced oxygen vacancies in 3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts for boosting low-temperature oxidative coupling of methane

It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.

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.

粗糙金属电极的原位电化学拉曼光谱法在固-液界面分析中的进展

原位电化学拉曼光谱利用入射光诱导物质分子的散射现象,通过测定拉曼光谱信号与电极电位或电流强度的变化关系,来表征电极表面(界面)的分子微观结构。该技术能够获取电化学界面上的分子振动信息以及与化学反应相关的结构信息,并进行实时监测,因此在物质界面表征领域得到了广泛应用。本文从原位电化学拉曼光谱的原理出发,综合叙述了基于粗糙金属电极的原位电化学拉曼光谱在固-液界面分析的进展,包括分子吸附、析氧反应、析氢反应和氧还原反应;同时,探讨了界面结构、反应过程以及催化中间体与拉曼信号强度的关系,介绍了催化过程反应机理和催化物质的催化机理,最后,对下一阶段原位电化学拉曼光谱法在固-液界面分析中存在的科学问题进行展望。

铅精矿侧吹熔炼气-液多相流动过程数值模拟

铅精矿富氧侧吹熔池熔炼技术具备原料适用范围广、炉体使用寿命长、废热废料利用率高、热量有效利用率高等诸多特点,在炼铅工艺中占有重要地位。基于VOF多相流模型与Realizable k-ε湍流模型建立了侧吹炉内的多相湍流流动过程数值仿真模型,并利用物理模型对仿真可靠性进行了验证。模拟研究了喷枪喷气速度、喷嘴排布方式以及渣液位高度对熔池搅拌效果的影响,确定了喷枪结构不变的情况下,最佳的工艺条件为喷枪喷气速度100~150 m/s、渣液位高度1.6~1.7 m。

Ionic liquid derived electrocatalysts for electrochemical water splitting

Hydrogen production from electrochemical water splitting is a promising strategy to generate green energy,which requires the development of efficient and stable electrocatalysts for the hydrogen evolution reaction and the oxygen evolution reaction(HER and OER).Ionic liquids(ILs)or poly(ionic liquids)(PILs),containing heteroatoms,metal-based anions,and various structures,have been frequently involved as precursors to prepare electrocatalysts for water splitting.Moreover,ILs/PILs possess high conductivity,wide electrochemical windows,and high thermal and chemical stability,which can be directly applied in the electrocatalysis process with high durability.In this review,we focus on the studies of ILs/PILs-derived electrocatalysts for HER and OER,where ILs/PILs are applied as heteroatom dopants and metal precursors to prepare catalysts or are directly utilized as the electrocatalysts.Due to those attractive properties,IL/PIL-derived electrocatalysts exhibit excellent performance for electrochemical water splitting.All these accomplishments and developments are systematically summarized and thoughtfully discussed.Then,the overall perspectives for the current challenges and future developments of ILs/PILs-derived electrocatalysts are provided.

针-水结构纳秒脉冲气液放电降解四环素

过度使用抗生素导致的水污染,对自然环境和人类健康造成了重大威胁。低温等离子体作为一种绿色环保的高级氧化技术,被认为是一种最具前景的抗生素降解方法之一,然而在降解效率和能量效率方面还有待进一步提高。利用纳秒脉冲放电激励针-水结构气液放电,获得了一种能产生高活性等离子体的瞬态火花模式放电,并应用于水中四环素降解,研究了脉冲电压、频率、初始浓度、初始pH值等参数对四环素降解的影响,结果表明初始浓度50 mg/L,脉冲电压9 kV、频率2 kHz,初始pH值为中性的条件下四环素的降解率最高,处理时间10 min时降解率达到了91.6%,能量效率和每阶电能分别为0.165 g·kW^(-1)·h^(-1)和0.78 kW·h·m^(-3)。自由基淬灭实验表明羟基自由基(·OH)在四环素降解过程中起主要作用,而H_(2)O_(2)和O_(3)的作用稍弱。细胞毒性实验也表明气液放电处理10 min后的溶液毒性显著下降。

Study on fluid-structure interaction in liquid oxygen feeding pipe systems using finite volume method

The fluid-structure interaction may occur in space launch vehicles,which would lead to bad performance of vehicles,damage equipments on vehicles,or even affect astronauts＇ health.In this paper,analysis on dynamic behavior of liquid oxygen （LOX） feeding pipe system in a large scale launch vehicle is performed,with the effect of fluid-structure interaction （FSI） taken into consideration.The pipe system is simplified as a planar FSI model with Poisson coupling and junction coupling.Numerical tests on pipes between the tank and the pump are solved by the finite volume method.Results show that restrictions weaken the interaction between axial and lateral vibrations.The reasonable results regarding frequencies and modes indicate that the FSI affects substantially the dynamic analysis,and thus highlight the usefulness of the proposed model.This study would provide a reference to the pipe test,as well as facilitate further studies on oscillation suppression.

The effect of temperature on ionic liquid modified Fe-N-C catalysts for alkaline oxygen reduction reaction

Modifying solid catalysts with an ionic liquid layer is an effective approach for boosting the performance of both Pt-based and non-precious metal catalysts toward the oxygen reduction reaction. While most studies operated at room temperature it remains unclear whether the IL-associated boosting effect can be maintained at elevated temperature, which is of high relevance for practical applications in low temperature fuel cells. Herein, Fe-N-C catalysts were modified by introducing small amounts of hydrophobic ionic liquid, resulting in boosted electrocatalytic activity towards the alkaline oxygen reduction reaction at room temperature. It is demonstrated that the boosting effect can be maintained and even strengthened when increasing the electrolyte temperature up to 70℃. These findings show for the first time that the incorporation of ionic liquid is a suited method to obtain advanced noble metal-free electrocatalysts that can be applied at operating temperature condition.

液氧-甲烷发动机点火器接口过度烧蚀问题研究

针对某液氧-甲烷发动机试车中出现的点火器与管路接口过度烧蚀问题,进行了原因分析及试验验证,提出改进措施并对其进行试验验证。结果表明:接口倒台阶和缝隙过大是造成过度烧蚀的原因。采用“突变式”变径结构代替“斜面过度”变径结构,可避免点火器与管路内径公差设计不合理及装配不对位造成的倒台阶问题;并且,将石墨垫圈厚度由4.0~4.5 mm调整为2.6~3.0 mm,可使压紧后接口缝隙小于0.1 mm。试验表明改进措施有效。

Effect of Molybdenum Doping on Oxygen Permeation Properties and Chemical Stability of SrCo0.8Fe0.2O3-δ

The phase composition, microstructure, thermal expansion coefficients, oxygen permeation properties and chemical stability of SrCo0.8Fe0.2O3-δ （SCFM） were investigated and compared with those of SrCo0.8Fe0.2O3-δ（SCF）. Single phase SCFM was successfully prepared by a combined EDTA-citric method. SCFM shows a lower thermal expansion coefficient （24× 10^-6-29× 10^-6/K） than SCF between 500 and 1050 ℃, indicating a more stable structure. SCFM shows a high oxygen permeation flux, although the oxygen flux of SCFM decreases slightly because of Mo dopant. Furthermore, it was demonstrated that the doping of Mo in SCF can prevent the order-disorder transition and improves the chemical stability to CO2.

2002—Emergence of the Gas-to-Liquids Industry:a Review of Global GTL Developments

This paper reviews the status of the gas-to-liquids (GTL) industry-including current commercial plants, announced projects and the technologies that are likely to be implemented in these future projects. Today, only 35,000 B/D of GTL products (0.1% of market) are manufactured from commercial gas-based plants. Advances in technology have lowered the cost of plants to the point where GTL plants can be profitable at crude oil prices of ＄16/B. The advanced stage of development of several proposed GTL projects and attractive integrated economics, for both the gas field and plant, show that GTL can be a significant alternative for monetizing natural gas in the 21st century. GTL technologies includes more than Fischer-Tropsch technology and extends to other liquid fuels, especially in the oxygenate family (methanol, dimethyl ether, etc.).

Methane Oxidation to Synthesis Gas Using Lattice Oxygen of La_(1-x)Sr_xMO_(3-λ)(M =Fe,Mn) Perovskite Oxides Instead of Molecular Oxygen

In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.

Oxygen ionic conductivity of a composite electrolyte SDC-LSGM prepared via glycine-nitrate process

Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ（SDC-LSGM）is prepared by the glycine-nitrate process（GNP）.SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so as to obtain homogeneous nano-sized precursor powders. The X-ray diffraction （XRD） and the scan electron microscope （SEM） are used to investigate the phases and microstructures. The measurements and analyses of oxygen ionic conductivity of SDC-LSGM are carried out through the four-terminal direct current （DC） method and the electrochemical impendence spectroscopy, respectively. The optimum weight ratio of SDC-LSGM is 8∶2, of which the ionic conductivity is 0.113 S/cm at 800℃ and the conductivity activation energy is 0.620 eV. The impendence spectra shows that the grain boundary resistance becomes the main barrier for the ionic conductivity of electrolyte at lower temperatures. The appropriate introduction of LSGM to the electrolyte SDC can not only decrease the electronic conductivity but also improve the conditions of the grain and grain boundary, which is advantageous to cause an increase in oxygen ionic conductivity.

Preparation and oxygen permeability of Bi_(26)Mo_(10)O_(69) porous layer modified ionic-electronic mixed conductor on air side

Bi26MO10O69 nanopowder was prepared by hydrothermal method and used as a surface modification material for oxygen separation membrane to enhance oxygen permeability. Thermal decomposition behavior and phase variation of the precursor were investigated by thermal analyzer （TG-DSC） and high-temperature X-ray diffraction （HT-XRD）. Bi26MO10O69 porous layer was coated on the air side of BaCo0.7Fe0.2Nb0.1O3-δ （BCFN） oxygen permeable membrane by dipping method. In the partial oxidation experiment of coke oven gas （COG）, the Bi26Mo10O69-coated BCFN membrane exhibits higher oxygen permeability and CH4 conversion than the uncoated BCFN membrane. When the thickness of BCFN membrane was 1 mm and the COG and air fluxes were 120 and 100 mL/min, the oxygen permeation flux reached 16.48 mL/（min.cm^2） at 875℃, which was 16.96% higher than the uncoated BCFN membrane. Therefore, Bi26MoloO69 porous layer on the air side will be promising modification coating on the oxygen permeability of BCFN membrane.

Novel cobalt-free tantalum-doped perovskite Ba Fe_(1-y)Ta_yO_(3-δ)with high oxygen permeation

Cobalt-free perovskite-type oxides BaFel_yTayO3-6 （0 _〈 y -〈 0.2） were synthesized via a simple solid state reac- tion. The cubic perovskite structure can be obtained when y is over 0.1. BaFeo.Ta0.lO3-6 （BFT0.1） membrane shows the highest oxygen permeation flux, which can reach 1.6 ml. min- 1. cm-2 at 950 ℃ under the gradient of air/He. The O2-TPD results reveal that BaFe0.9Ta0.lO3-a material shows an excellent reversibility and phase structure stability in air. The oxygen permeation flux is limited by the bulk diffusion when the membrane thick- ness is over 0.8 mm, and it is limited by both the bulk diffusion and the surface exchange when the membrane thickness is below 0.5 mm. Stable oxygen permeation fluxes are obtained during 180 h operation.

Oxygen Isotope Records of Core 8KL of the South China Sea and Sea - level Change

Based on a comparison between the oxygen isotope records of benthic and plank tonic foraminifers from core 8KL of the South China Sea and sea-level change records derived from the Huon Peninsula, New Guinea, it is found that both records are very similar from 72 K a B.P. to the present, especially for the benthic oxygen isotope record. The linear regression shows that δ18O changes (0.9995‰ for benthic foraminifers and 1.022‰ for planktonic foraminifers) are equal to 100 m in sea-level fluctuation. After making temperature correction in the δ18O record of benthic foraminifers from 72 to 120 Ka B.P., the curve of sea-level oscillation of the South China Sea since 186 Ka B.P. has been reconstructed. The lowermost sea - level that occurred in the last glacial maximum and oxygen isotope stage 6 is approximately - 130 m.

SrCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ) perovskite stabilized by niobium for oxygen permeation

The effect of Nb doping on the oxygen permeation and stability of SrCo_(0.8)Fe_(0.2)O_(3-δ)(SCFO) was investigated comprehensively.Cubic perovskite phase was formed in SrCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ)(SCFNO).The SCFNO with a thickness of 1 mm had a high level of oxygen permeation flux of 1.4 ml.min^(-1).cm^(-2) at 850 ℃ under air/He gradient.The bulk diffusion is the rate-limiting step in overall oxygen permeation mechanism for SCFNO when the thickness is higher than 1.0 mm.The partial substitution of Nb for Co suppresses the transition of oxygen vacancies order/disorder proven by DSC measurement and enhances the phase stability under low oxygen partial pressure.During long-term tests under low oxygen pressure,the SCFNO exhibites structural stability and stable oxygen permeation.It is proved that substitution of Nb for Co is an effective way to improve the properties of SCFO.

THERMODYNAMICS OF Fe-Nb-Ce LIQUID SOLUTIONS CONTAINING TRACE O,S AND C

The solid oxide electrolyte galvanic cell represented by Mo/Cr,Cr_2O_3//ZrO_2(MgO)//[O], Ce_2O_2S/Mo+ZrO_2 ceramic-metal,Mo have been used to study the thermodynamic proper- ties of Fe-Nb-Ce solution containing trace carbon at 1600℃.The equilibrium constant for the reaction Ce_2O_2S=2[Ce]+2[O]+[S] and the standard free energy of formation of Ce_2O_2S have been determined in liquid iron at 1600℃ as K=4.395×10^(-15).ΔG_(Ce_2)O_2S=-514.786 kJ·mol^(-1).The interaction coefficients between cerium and niobium are found to he e_(Nd)^(Ce)=-2.306,e_(Nd)^(Ce)=-3.481. The equilibrium products began to contain the compound NbC with the increase of Nh concentration in the condition of trace carbon.The formation of NbC is discussed in this work.The standard free energy of formation of NbC in liquid iron at 1600℃ have been de- termined as ΔG_(NbC)=-87.111 kJ·mol^(-1).

Promoting surface reconstruction of NiFe layered double hydroxides via intercalating[Cr(C_(2)O_(4))_(3)]^(3-)for enhanced oxygen evolution

Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(C_(2)O_(4))_(3)]^(3-)into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction(OER)activity.In view of the weak electronegativity of Cr^(3+) in[Cr(C_(2)O_(4))_(3)]^(3-),the intercalation of[Cr(C_(2)O_(4))_(3)]^(3-)is expected to result in an electron-rich structure of Fe sites in NiFe LDHs,and higher valence state of Ni can be formed with the charge transfer between Fe and Ni.The optimized electronic structure of NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs with more active Ni^(3+) species and the expedited dynamic generation of Ni^(3+) (Fe)OOH phase during the OER process contributed to its excellent catalytic property,revealed by in situ X-ray absorption spectroscopy,Raman spectroscopy,and quasi-in situ X-ray photoelectron spectroscopy.With the modulated electronic structure of metal sites,NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm^(-2).This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni^(3+) sites with the optimal electronic environment for improved OER electrocatalysis.

Oxygen vacancy-rich amorphous FeNi hydroxide nanoclusters as an efficient electrocatalyst for water oxidation

In this work,a one-pot strategy is presented to directly synthesize amorphous Fe_(x)Ni_(y) hydroxide nanoclusters(denoted as ANC-Fe_(x)Ni_(y),<2 nm)with oxygen vacancies induced by ionic liquids.The ANC-Fe_(x)Ni_(y) catalyst presents abundant catalytic sites and high intrinsic conductivity.As such,the optimized ANC-Fe_(1)Ni_(2) exhibits high activity in oxygen evolution reaction(OER)with a Tafel slope of 39 m V dec^(–1) and an overpotential of 266 m V at 10 m A cm^(-2).Notably,the optimized ANC-Fe_(1)Ni_(2) shows an extraordinarily large mass activity of 3028 Ag_(FeNi)^(–1) at the overpotential of 300 m V,which is~24-fold of commercial RuO_(2) catalyst.The superior activity of these Fe_(x)Ni_(y) hydroxide nanoclusters is ascribed to(i)the amorphous and distorted structure with abundant oxygen vacancies,and(ii)enhanced active site density by downsizing the ANC-FexNiyclusters.This strategy provides a novel route for enhancing OER electrocatalytic performance and highly encouraging for the future application of amorphous metal hydroxides in catalysis.