双极性半导体钝化膜空间电荷电容分析(II)

将双极性半导体钝化膜空间电荷电容等效为钝化膜/溶液界面处电容和内层钝化膜/外层钝化膜界面处的np结电容的串联, 根据前期研究建立的半导体富集态、耗尽态以及反型态空间电荷电容的统一计算公式, 给出了双极性钝化膜Mott-Schottky(M-S)曲线的非线性拟合方法. 并将这一方法应用于镍基合金G3高温高压H2S/CO2腐蚀后的钝化膜半导体特征研究. M-S曲线非线性拟合结果显示, 温度升高外层p型半导体钝化膜多数载流子浓度明显增高, 而内层n型半导体钝化膜的多数载流子浓度基本未变. 通过非线性拟合, 证明本文所给出的M-S曲线非线性拟合方法能够同时给出钝化膜内外层多个半导体性质参数,为揭示钝化膜形成及破坏机制提供更多信息. 结合X射线光电子能谱(XPS)分析, 讨论了钝化膜结构变化机制及np结在抑制腐蚀过程中的作用.     

Effect of temperature on intrinsic permeation properties of 6FDA-Durene/1,3-phenylenediamine (mPDA) copolyimide and fabrication of its hollow fiber membranes for CO2/CH4 separation

We have determined the effect of temperature on intrinsic permeation properties of 6FDA-Durene/1,3-phenylenediamine (mPDA) 50/50 copolyimide dense film and fabricated high performance hollow fiber membranes of the copolyimide for CO₂/CH₄ separation. The hollow fiber membranes were wet-spun from a tertiary solution containing 6FDA-Durene/mPDA (PI), N-methyl-pyrrolidone (NMP) and tetrahydrofuran (THF) with a weight ratio of 20:50:30 at different shear rates within the spinneret. We observed the following facts: (1) the CO₂/CH₄ selectivity of the copolyimide dense film decreased significantly with an increase in temperature; (2) the performance of as-spun fibers was obviously influenced by the shear rate during spinning. For uncoated fibers, permeances of CH₄ and CO₂ decreased with increasing shear rate, while selectivity of CO₂/CH₄ sharply increased with shear rate until the shear rate reached 2169 s⁻¹ and then the selectivity leveled off; (3) After silicone rubber coating, permeances of CH₄ and CO₂ decreased, the selectivity of CO₂/CH₄ was recovered to the inherent selectivity of its dense film. Both the permeances and selectivity with increasing shear rate followed their same trends as that before the coating; (4) there was an optimal shear rate at which a defect-free fiber with a selectivity of CO₂/CH₄ at 42.9 and permeance of CO₂ at 53.3 GPU could be obtained after the coating; and (5) the pressure durability of the resultant hollow fiber membranes could reach 1000 psia at room temperature.     

690合金在300 ℃含硫模拟碱性水化学中的腐蚀行为

690 合金作为压水堆核电站蒸汽发生器传热管的一种关键材料, 其在碱性环境下还原态硫导致的钝化膜的腐蚀退化是引发应力腐蚀开裂的关键原因之一. 本文采用动电位极化曲线, 结合扫描电镜(SEM)、俄歇能谱(AES)、二次离子飞行时间质谱(ToF-SIMS)研究了690合金在300 ℃模拟碱性水化学中的腐蚀行为, 并分析了硫代硫酸根与硫酸根对钝化膜特性的影响. 实验结果表明: 300 ℃碱性溶液中690合金表面钝化膜为外层的多孔层与内层的紧密层组成的双层结构, 所加入的硫酸盐种类对690合金的耐蚀性有较大影响; 硫代硫酸根使690合金钝化电流密度增加, 过钝化电位降低, 即钝化膜的耐蚀性降低; 此外, 硫代硫酸根使钝化膜中的Cr含量降低而Ni 含量提高, 硫代硫酸根会在合金表面电化学还原成为更低价态的硫进入钝化膜, 使钝化膜中的硫化物增多也是导致钝化膜防护性能变差的原因; 而硫酸根与钝化膜的作用较弱, 对钝化膜的影响较小.     

Synthesis of spherical nanoparticles of Cu2L2O5 (L=Ho, Er) from W/O microemulsions

Nanoparticles of Cu₂L₂O₅ (L=Ho, Er) (15–25 nm in size) were synthesised by the intermediate use of W/O microemulsions. In this process the aqueous cores of water/cetyltrimethylammonium bromide/n-octane/1-butanol microemulsions were used as microreactors for the precipitation of Cu₂Ho₂(CO₃)₄(OH)₂ (25–30 nm) and Cu₂Er₂(CO₃)₄(OH)₂ (10–40 nm) as precursors. These mixed salts were separated and further decomposed to the corresponding mixed oxides at 900°C for 16 h. All solids were characterised by scanning and transmission electron microscopy, IR, XRPD, ICP-OES, TGA, XPS measurements and elemental analyses.     

Influence of Cr on the Electronic Properties of Passive Film on B30 Alloy in NaOH Solution

The influence of Cr on the electronic properties of the passive film on B30 alloy in NaOH solution was studied via electrochemical impedance spectra(EIS), potentiodynamic curve and Mott-Schottky plot. The Cr doped in the passive film on B30 alloy was detected by X-ray photoelectron spectroscopy(XPS). XPS results show that Cr₂O₃ appeared on the passive film, which implied the enhanced anti-corrosion of B30 alloy. The passive film showed a p-type semi-conductive character. The acceptor density(N_A) was in an order of magnitude of 10²² cm^-3, and N_A decreased with the increment of Cr. EIS results show that the film resistance(R_f) increased with increasing the amount of Cr. The diffusion coefficient(D₀) was calculated to be in a range of 10^-16-10^-17 cm^-2/s on the basement of point defect model(PDM).     

射频放电等离子体中CO2及CO2-H2混合气转化反应的原位研究

Currently, worldwide attention is focused on controlling the continually increasing emissions of greenhouse gases, especially carbon dioxide. To this end, a number of investigations have been carried out to convert the carbon dioxide molecules into value-added chemicals. As carbon dioxide is thermodynamically stable, it is necessary to develop an efficient carbon dioxide utilization method for future scaled-up applications. Recently, several approaches, such as electrocatalysis, thermolysis, and non-thermal plasma, have been utilized to achieve carbon dioxide conversion. Among them, non-thermal plasma, which contains chemically active species such as high-energy electrons, ions, atoms, and excited gas molecules, has the potential to achieve high energy efficiency without catalysts near room temperature. Here, we used radio-frequency (RF) discharge plasma, which exhibits the non-thermal feature, to explore the decomposition behavior of carbon dioxide in non-thermal plasma. We studied the ionization and decomposition behaviors of CO₂ and CO₂-H₂ mixtures in plasma at low gas pressure. The non-thermal plasma was realized by our custom-made inductively coupled RF plasma research system. The reaction products were analyzed by on-line quadrupole mass spectrometry (differentially pumped), while the plasma status was monitored using an in situ real-time optical emission spectrometer. Plasma parameters (such as the electron temperature and ion density), which can be tuned by utilizing different discharge conditions, played significant roles in the carbon dioxide dissociation process in non-thermal plasma. In this study, the conversion ratio and energy efficiency of pure carbon dioxide plasma were investigated at different values of power supply and gas flow. Subsequently, the effect of H₂ on CO₂ decomposition was studied with varying H₂ contents. Results showed that the carbon dioxide molecules were rapidly ionized and partially decomposed into CO and oxygen in the RF field. With increasing RF power, the conversion ratio of carbon dioxide increased, while the energy efficiency decreased. A maximum conversion ratio of 77.6% was achieved. It was found that the addition of hydrogen could substantially reduce the time required to attain the equilibrium of the carbon dioxide decomposition reaction. With increasing H₂ content, the conversion ratio of CO₂ decreased initially and then increased. The ionization state of H₂ and the consumption of oxygen owing to CO₂ decomposition were the main reasons for the V-shape plot of the CO₂ conversion ratio. In summary, this study investigates the influence of power supply, feed gas flow, and added hydrogen gas content, on the carbon dioxide decomposition behavior in non-thermal RF discharge plasma.     

富氢气氛下CeO_2-NiO纳米棒催化剂的CO选择性氧化性能研究

采用水热法制备了一系列不同Ce/Ni物质的量比的纳米棒CeO_2(x)-NiO催化剂。运用低温N_2吸附-脱附、XRD、TEM、拉曼光谱、H_2-TPR及XPS等技术对催化剂的形貌、结构进行了表征。考察了Ce/Ni物质的量比对CeO_2(x)-NiO催化剂形貌及富氢气氛下CO选择性氧化(CO PROX)反应性能的影响。TEM测试结果表明,调变Ce/Ni物质的量比可制得不同粒径的CeO_2(x)-NiO纳米棒催化剂。H_2-TPR测试结果表明,将NiO掺入CeO_2可提升Ce O_2(x)-NiO催化剂的氧化还原能力。拉曼光谱及XPS测试结果表明,镍含量较低时,CeO_2(x)-NiO催化剂表面活性氧物种及氧空位含量均较多,利于提升其催化性能。CO PROX催化性能测试结果显示,镍含量较低的CeO_2(0.89)-NiO纳米棒催化剂的活性和选择性最好,在170-220℃的反应条件下,CO转化率为100%,CO_2选择性为52%。     

增压O_2/CO_2气氛下煤燃烧特性实验研究

增压O2/CO2燃烧是一种可高效分离回收CO2的新兴燃烧技术,其燃烧机理与常压空气、常压O2/CO2燃烧存在较大差异。在加压热重分析仪上研究了增压条件下总压、氧浓度、气氛及粒径等反应参数对美国烟煤和淮北无烟煤燃烧特性的影响,确定了煤的着火温度,并对其进行燃烧动力学分析。结果表明,增压O2/CO2气氛下,随着压力或氧浓度的增加,DTG曲线向低温区移动,煤样整体燃烧速率加快。压力提升、氧浓度增加及煤粉细化均可改善O2/CO2气氛下煤样的着火特性。常压O2/CO2气氛下煤粉燃烧基本属于一级反应;增压O2/CO2气氛下,低温区属于0.5级反应,而高温区属于1.5级反应。     

基于金属氧化物材料的二氧化碳电催化还原

The CO₂ level in the atmosphere has been increasing since the industrial revolution owing to anthropogenic activities. The increased CO₂ level has led to global warming and also has detrimental effects on human beings. Reducing the CO₂ level in the atmosphere is urgent for balancing the carbon cycle. In this regard, reduction in CO₂ emission and CO₂ storage and usage are the main strategies. Among these, CO₂ usage has been extensively explored, because it can reduce the CO₂ level and simultaneously provide opportunities for the development in catalysts and industries to convert CO₂ as a carbon source for preparing valuable products. However, transformation of CO₂ to other chemicals is challenging owing to its thermodynamic and kinetic stabilities. Among the CO₂ utilization techniques, electrochemical CO₂ reduction (ECR) is a promising alternative because it is generally conducted under ambient conditions, and water is used as the economical hydrogen source. Moreover, ECR offers a potential route to store electrical energy from renewable sources in the form of chemical energy, through generation of CO₂ reduction products. To improve the energy efficiency and viability of ECR, it is important to decrease the operational overpotential and maintain large current densities and high product selectivities; the development of efficient electrocatalysts is a critical aspect in this regard. To date, many kinds of materials have been designed and studied for application in ECR. Among these materials, metal oxide-based materials exhibit excellent performance as electrocatalysts for ECR and are attracting increasing attention in recent years. Investigation of the mechanism of reactions that involve metallic electrocatalysts has revealed the function of trace amount of oxidized metal species—it has been suggested that the presence of metal oxides and metal-oxygen bonds facilitates the activation of CO₂ and the subsequent formation and stabilization of the reaction intermediates, thereby resulting in high efficiency and selectivity of the ECR. Although the stability of metal oxides is a concern as they are prone to reduction under a cathodic potential, the catalytic performance of metal oxide-based catalysts can be maintained through careful designing of the morphology and structure of the materials. In addition, introducing other metal species to metal oxides and fabricating composites of metal oxides and other materials are effective strategies to achieve enhanced performance in ECR. In this review, we summarize the recent progress in the use of metal oxide-based materials as electrocatalysts and their application in ECR. The critical role, stability, and structure-performance relationship of the metal oxide-based materials for ECR are highlighted in the discussion. In the final part, we propose the future prospects for the development of metal oxide-based electrocatalysts for ECR.     

Reversible Adsorption of NOx on ZrO2-supported CeO2 Prepared in Water-in-oil Microemulsion

Nitric oxides (NOx) storage catalyst^[1] provides an alternative route for abatement of NO in presence of oxygen by first adsorbing NOx and then desorbing it by temperature swing or pressure swing. YBa₂Cu₃Oy^[2] and Mn-Zr mixed oxides^[3] were reported to have large NOx adsorption capacity, but the former suffered from a great amount of coexisting CO₂ gases. The author previously reported that high NOx adsorption capacity could be obtained on Ce modified TiO₂-pillared montmorillonite without deactivation by CO₂^[1]. Microemulsion method was reported to be effective to control particle sizes and microstructures of the metal oxides^[4]. In this paper, a thermal stable ZrO₂ with high surface area was prepared in water-in-oil microemulsion, and NOx adsorption capacity was tested on the above ZrO₂ sample after impregnating with manganese nitrate and cerium nitrate.     

Systematic investigation of the effects of temperature and pressure on gas transport through polyurethane/poly(methylmethacrylate) phase-separated blends

Polyurethane (PU) and polyurethane–poly(methylmethacrylate) (PMMA) blend membranes were used in gas separation studies. The effects of blend composition, temperature, and pressure on the permeability, diffusivity, and solubility of CO₂, H₂, O₂, CH₄, and N₂ were investigated. The separation factors of some gas pairs were also evaluated. Positron annihilation lifetime spectroscopy was applied to assess free volume changes as a function of blend composition and temperature. Free volume size increases by approximately 30% with increasing temperature from 10 to 40 °C for all blends studied. The permeability of all gases decreases by approximately 55% with the addition of 30 wt% of PMMA. The permeation process is governed by diffusion, except that of CO₂. In relation to the behavior of gas transport as a function of temperature, some important observations are (i) CO₂ presents the lowest permeation activation energy value (28 kJ/mol), and (ii) gas pair selectivity increases at low temperatures and is high for gas pairs that present differences in permeation activation energies as high as 15 kJ/mol for the CO₂/CH₄ gas pair. Furthermore, the study with pressure variations shows that: (i) at elevated pressure, the PU and the blend membrane permeability to CO₂ and H₂ increases by approximately 35%, and (ii) oxygen-to-nitrogen selectivity increases with pressure as a consequence of the decrease in the permeability to nitrogen in the case of the 30%-PMMA blend.     

Separation of CO_2–N_2 using zeolite NaKA with high selectivity

The adsorption method based on solid adsorbents is one of feasible ways to capture and store CO_2. Using the ion exchange method, different zeolites Na KA varying in K+content were produced. The adsorption isotherms and kinetic uptakes were measured. The experimental results show that the optimal NaKA could adsorb significant quantities of CO_2 and little N_2. On the zeolite Na KA with 14.7 at.% K+, the adsorption capacity for pure CO_2 is over 3.10 mmol g~(-1) and the CO_2–N_2 selectivity is about 149 at ambient pressure and temperature. The kinetic CO_2–N_2 selectivity could also achieved 200 within 3 min according to the uptake data. To demonstrate the separation effectiveness, breakthrough curves of pure components and binary mixtures were investigated experimentally and theoretically in a fixed bed. It is found that the breakthrough points of CO_2 and N_2 are almost at the same time under the atmospheric pressure at 348 K with the raw gas composition CO_2/N_2(20:80, v/v). If the pressure has been increased higher than 0.1 MPa, CO_2 would break through the bed much slower than N_2. Therefore, the pressure may become the limiting factor for the separation performance of zeolites NaKA.     

Ca-P Conversion Coating on AZ60 Magnesium Alloy for Biomedical Application

To improve the anti-corrosion behaviors of magnesium alloy in the inner environment of human body,a bioactive Ca-P coating was deposited on the AZ60 magnesium alloy by a novel simple method.The morphologies of the Ca-P coatings formed under different treatment time were studied by scanning electron microscopy（SEM）.The corrosion behaviors of Ca-P coating were investigated by electrochemical polarization test and electrochemical impedance spectroscopy in both 3％（mass fraction） NaCl solution and simulated body fluid（SBF）.Immersion test in SBF was performed to evaluate the corrosion rate of Ca-P coated magnesium alloy.X-Ray diffraction（XRD） analysis result shows that the coating mentioned above mainly consists of dicalcium phosphate dehydrate（CaHPO4·2H2O,DCPD） and β-tricalcium phosphate dehydrate[β-TCP,Ca3（PO4）2],which exhibits good corrosion resistance.After magnesium alloy was immersed in 1 mol/L NaOH solution at 80 ℃ for 2 h,hydroxyapatite [Ca10（PO4）6（OH）2,HA]appeared on the magnesium alloy substrate,which can further decrease the corrosion rate of AZ60 magnesium alloy in SBF.     

Study of near resonant energy transfer from laser excited CO2 to SO2

Collisional energy transfer from CO₂ to SO₂ was studied subsequent to pumping of CO₂ (ν₃) by a Q-switched laser. The measurements were made in the temperature range 300–800 K and in the pressure range 1–30 Torr. The fluorescence from the ν₃ level of CO₂ was monitored with the help of a Ge:Au detector at 77 K with an estimated response time of ≈2 μs. The probability of the energy transfer was found to be increasing with increasing temperature. The probable kinetic models for the V---V relaxation pathways were discussed and the experimentally measured energy transfer rate is related to the cross-over transfer processes. Theoretical calculations using both a simple SSH-breathing sphere model and the Sharma-Brau theory were carried out to evaluate the probabilities of the involved cross-over energy transfer processes and the results were compared with the experimental rates.     

CO_2在三聚氰胺酚醛纤维上的吸附分离

以三聚氰胺、间苯三酚和甲醛为原料,通过水热缩聚反应合成了三聚氰胺酚醛纤维(PMF),考察了温度对PMF合成的影响。以扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N_2吸脱附和傅里叶变换红外(FT-IR)光谱等表征了PMF的形貌和结构,并采用体积法测定不同温度下CO_2和N_2在PMF上的单组分吸附平衡等温线。结果表明,在393 K下合成的PMF具有较大的比表面积(64 m2/g)和较高的CO_2吸附量(1.83 mmol/g,298 K、118 k Pa)。穿透柱实验表明,在298 K、200-600 k Pa,CO_2-N_2混合气在PMF上均可实现有效分离。将PMF在873 K下,N_2、H2及水蒸气等多种气氛中进行后处理,其比表面积和微孔孔容均显著增加,其中,在15%H_2O气氛中处理后,样品CO_2吸附量提高至2.83 mmol/g(298 K、118 k Pa)。     

催化剂表面Cu0含量对二氧化碳加氢合成C2+醇性能的影响

通过在空气气氛下焙烧Cu@Fe-MIL-88B MOF材料制备了CuFe组分均匀分散的催化剂前驱物, 该前驱物经过不同温度下的预还原制得表面具有不同Cu和Fe价态分布的系列催化剂. 将所制备的催化剂用于固定床反应器上CO₂加氢合成C₂₊醇的性能研究, 并结合催化剂的X射线衍射(XRD)、 X射线光电子能谱(XPS)、 氢气程序升温还原(H₂-TPR)、 氮气吸附-脱附、 扫描电子显微镜(SEM) 和高分辨率透射电子显微镜(HRTEM)等表征结果发现, 较高的还原温度增加了催化剂表面低价态的Cu和Fe的含量; 当还原温度为350 ℃时, 催化剂表面Cu⁰/(Cu⁺+Cu⁰)摩尔比为73.9%, 单质Fe摩尔分数为0.40%, 催化效果最好, CO₂转化率达到6.82%, 总醇选择性为39.4%, 其中C₂₊醇的摩尔比达到95.1%.     

在负载铼催化剂上由CO2/H2合成甲醇的研究

CO加H₂合成甲醇的工作已应用于工业化生产,其中多采用锌、铬、铜基催化剂。而CO₂加H₂合成甲醇研究工作尚不很多,其催化剂多数是在CO/H₂制甲醇催化剂基础上发展而来。     

Corrosion behavior of AZ91D magnesium alloy in distilled water

The corrosion of AZ91D magnesium alloy has received extensive attention due to the continuous expansion of its application field in recent years. However, the corrosion of AZ91D magnesium alloy in distilled water is relatively few. In this paper, the corrosion behavior of AZ91D magnesium alloy was studied in distilled water by electrochemical tests in combination with weight loss and surface analysis methods. The results indicated that the corrosion rate of AZ91D magnesium alloy increased with the increase of temperature and immersion time. The increase of the corrosion rate of AZ91D magnesium alloy with the increase of immersion time might be attributed to the damage of the structure of corrosion product film by hydrogen evolution, significantly accelerating the anodic process of AZ91D magnesium alloy. It was interesting that, in distilled water, the EIS of AZ91D magnesium alloy excluded an inductive arc in the low frequency region, which indicated that there was no the adsorption and desorption of aggressive ions or the damage and repair of film. The corrosion product film of AZ91D magnesium alloy in distilled water was composed of a compact inner corrosion product film and a loose outer corrosion product film.     

ALD-Al2O3涂层保护的高抗湿5-氨基戊酸铰链甲胺铅溴钙钛矿薄膜

近年来,混合铅卤钙钛矿材料在光电领域引发的研究热潮引人注目。然而,钙钛矿材料对水和氧气的敏感性严重的阻碍了其实用化进程。在众多的稳定钙钛矿的方法中,利用简单的原子层沉积方法(Atomic layer deposition,ALD)在钙钛矿表面沉积一层保护层的技术具有极大的潜力。而ALD应用的困难在于,在常规的ALD过程中,做为氧源的H2O和O3对铅卤钙钛矿有着腐蚀作用。在本文,我们提出将双官能团的5-氨基戊酸(5-Aminovaleric acid,AVA)引入到CH₃NH₃PbBr₃(MAPbBr₃)钙钛矿晶格层中,形成稳定的铰链结构的2D/3D钙钛矿AVA(MAPbBr₃)2。AVA的引入可以钝化并防止ALD过程中水对钙钛矿的侵蚀,从而成功地直接在钙钛矿表面沉积了Al₂O₃保护层。覆盖了保护层的AVA(MAPbBr₃)2钙钛矿薄膜获得了优异的热稳定性和抗水性。     

新型类沸石金属-有机骨架材料用于天然气中CO2的分离

研究了在usf型类沸石金属-有机骨架材料(usf-ZMOF)中不同金属离子(Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Al³⁺)对天然气分离(以CO₂/CH₄, CO₂/H₂, CO₂/N₂为研究对象)的不同影响. 结果表明, 此类材料对于3种体系的分离选择性均高于现有材料. 其中性能最好的是Al-usf-ZMOF, 其对CO₂/CH₄, CO₂/N₂和CO₂/H₂的分离选择性分别为290, 1700和16800. 同时, 对于经不同的离子交换后的usf-ZMOF, 吸附选择性随着离子电荷值的增加而增大; 对于同一主族的离子, 选择性随着原子序数的增加而减小. 而上述现象的产生是由阳离子和CO₂间的强静电作用所致.