化学气相沉积法低温合成纳米洋葱状富勒烯

以Al（OH）3担载铁作催化剂,乙炔为碳源、氩气为载气分别在400℃和460℃下利用化学气相沉积法进行了催化反应,采用高分辨透射电镜对产物进行了结构表征。同时,还探讨了化学气相沉积法催化合成内包金属纳米洋葱状富勒烯的生长机理,从理论上分析了低温合成纳米洋葱状富勒烯的合理性。     

The synthesis and characterization of a Co-N/C composite catalyst for the oxygen reduction reaction in acidic solution

A non-precious metal Co-N/C catalyst for the oxygen reduction reaction (ORR) was synthesized by heating a mechanical mixture of cobalt chloride, urea and acetylene black under a nitrogen atmosphere. The catalyst was characterized by XRD and XPS. The electrocatalytic activity in the ORR was evaluated by linear sweep voltammetry in 0.5 mol L⁻¹ H₂SO₄ solution. The results show that the Co-N/C catalyst aids the reduction of oxygen. The presence of elemental cobalt in the precursor allows nitrogen atoms to embed themselves in the graphite matrix to form pyridinic and graphitic type C-N structures as the ORR active sites. The effect of heat-treating temperature on the catalytic activity was also investigated. The results also show that the Co-N/C catalyst is most active when pyrolyzed at 600°C. The obtained Co-N/C catalyst loses some activity after initial exposure to the H₂SO₄ solution because of leaching, but is then stable for up to 20 h immersion. The catalyst is also stable when charged, which is supported by the cyclic voltammetry results.     

静态再结晶处理对Co36Fe36Cr18Ni8Ti2合金力学性能与耐腐蚀性的影响

对冷变形后的Co₃₆Fe₃₆Cr₁₈Ni₈Ti₂合金在700 ℃和800 ℃下再结晶退火,制备成具有高强度及良好耐蚀性的多主元合金。采用电子背散射衍射（electron back-scattered diffraction, EBSD）表征了合金的相分布、再结晶组织以及晶界分布等微观结构特征,采用静态拉伸试验测试了合金的力学性能。结果表明,700 ℃退火的合金断后伸长率较低,但其抗拉强度与屈服强度分别达到了1 038和956 MPa。采用电化学工作站与扫描电子显微镜（scanning electron microscope, SEM）表征了合金在模拟体液中的耐蚀性。结果表明,700 ℃退火的样品具有较好的耐蚀性,腐蚀后的样品表面较为均匀。结合力学性能可知,700 ℃退火的样品具有作为新型医用金属材料的潜力。     

Synthesis mechanism of LiNiVO4 by wet chemical method and mixed valence of nickel and vanadium

The single phase LiNiVO₄ has been successfully synthesized by adopting a new mild liquid route with oxalic acid as both complexant and precipitant, and this method is named the CPG method. The products were obtained by sintering the dry gel precursor which was prepared by the CPG method at 200—850℃ for 2—10 h in air. The products were tested by XRD, XPS, ESR and TGA-DTA, and the results indicate that the single phase LiNiVO₄ could be obtained at 450℃ for 2—3 h in air and LiNiVO₄ was still steady at 850℃ for 10 h. The valence analyses show that in LiNiVO₄ the valence of lithium is +1, both nickel and vanadium have the mixed valence, namely +2, +3 for nickel and +4, +5 for vanadium respectively. The LiNiVO₄ can be expressed as LiNi³⁺_xNi²⁺_1-xV⁴⁺_xV⁵⁺_1-xO₄ (0≤x<1). The pyrolysis mechanism of the dry gel is also discussed.     

Synthesis, characterization and magnetic properties of near monodisperse Fe3O4 sub-microspheres

Near monodisperse Fe3O4 sub-microspheres with an average diameter of 170 nm have been synthesized by a solvothermal reduction method, using K3[Fe（CN）6] as the raw material in the absence of any surfactants at 200~C℃ for 24 h. The products were detected by XRD, FESEM, TEM, and XPS. The investigation of the reaction parameters indicates that ethylene glycol plays a key role both as reducing agent and solvent. In addition, the reaction time and temperature also have important influences on the final product. The hysteresis loop of the near monodisperse Fe3O4 sub-microspheres shows a ferromagnetic behavior with saturation magnetization of 60.8 emu/g and coercivity of 124.7Oe.     

Systematically controlled synthesis of rGO/nano-MnO_x materials for supercapacitors

The effects of hydrothermal production conditions on crystal forms,morphology and electrochemical performance of in situ reduced graphene oxide/manganese oxides(r GO/Mn O_x)hybrid electrode materials were studied.The XRD/SEM results show that the ratio of precursors,reaction temperature and type of solvent significantly affected the crystal form obtained and nano-structure of MnO_x.Varied precursor ratios of KMnO_4:GO(5:1,7:1,9:1 and 11:1)yielded the hybrids of rGO/Mn_7O_(13)5H_2O,rGO/β-MnO_2,rGO/Mn_(98)O_2,and rGO/K_(0.27)MnO_2(H_2O)_(0.54),respectively,having corresponding nano structures of nano-sheets composed petal-like shape,petal-like shape based nano-wire clusters,petal-like shape with backwardly arched top and bigger mesoporous petal-like nano structures.Hybrid prepared precursor with the ratio of 5:1 exhibited the highest specific capacitance of 320 F/g at 0.2 A/g and the smallest diffusion impedance.However,hybrid prepared precursor with the ratio of 7:1 presented the lowest electron transfer impedance.Varying hydrothermal treatment temperatures(140,160 and 200℃)yielded hybrids:rGO/MnO(OH),rGO/Mn_(0.91)O_(1,82)(H_2O)_(0.18),and rGO/Mn_7O_(13)5H_2O,respectively.The nano structures of the hybrids were nano-sheets having petal-like mesoporous structure,but having larger dimensions as temperature increase.The hybrid prepared at 160℃ showed the highest specific capacitance of 214 F/g at a current density of 0.2 A/g and the lowest solution resistance of1.61Ω,whiles,the hybrid prepared at 140℃ inferred the best cyclic reversibility.     

Properties improvement of SPEEK based proton exchange membranes by doping of ionic liquids and Y2O3

The membranes of sulfonated poly(etheretherketone) with 65％ sulfonation degree were prepared by doping of Y2O3 and ionic liquids,such as 1-ethyl-3-methylimidazole tetrafluoroborate (EB) or 1-butyl-3-me...     

养护温度对LiNO3抑制碱硅酸反应及其膨胀的影响

研究了38℃和60℃下石英玻璃在掺LiNO_3的Na OH溶液中碱硅酸反应过程,采用酸化处理法确定体系中SiO_2分布,采用等离子发射光谱(ICP)分析溶液中Na、Si和Li元素浓度变化,采用X射线衍射(XRD)和扫描电子显微镜(SEM)表征反应产物的组成和形貌;并检测了38℃和80℃湿气养护下掺LiNO_3的沸石化珍珠岩混凝土微柱的膨胀性。结果表明:加入LiNO_3降低了溶液中石英玻璃的溶蚀率和SiO_2的溶解度,减缓了ASR的反应速率;不同养护温度下形成的含锂产物不同,提高温度有利于Li_2SiO_3晶体的形成。对于混凝土微柱,掺锂试件早期抑制效果良好,后期仍膨胀;相同锂掺量下80℃湿气养护的试件膨胀率却明显低于38℃时的膨胀率。可见,高温养护下LiNO_3抑制ASR膨胀的效果不能很好地评价在低温下的作用效果。     

Ce掺杂的NiCo2O4催化氧化甲苯性能研究

NiCo₂O₄是一种很前景的甲苯氧化催化剂。本文以Ce为杂原子,利用水热法制备Ce/NiCo₂O₄催化剂,以提高NiCo₂O₄尖晶石表面活性氧生成速率。采用氢气程序升温还原(H₂-TPR)、X射线光电子能谱(XPS)、X射线衍射(XRD)、比表面积测定(BET)、以及透射电子显微镜(TEM)等表征催化剂。通过改变铈掺杂量,得到最佳掺杂比例。甲苯降解实验表明,在甲苯浓度为2538ppm,空速为10000h^_-1,催化剂体积为0.5mL 时,一次水热法制备得到的15%Ce/NiCo₂O₄催化剂降解性能最优(T₉₉=267℃),在267℃下进行催化反应72h后催化剂性能无显著变化。机理研究发现,掺杂铈可提升催化剂中高价金属含量,同时催化剂良好的氧化还原性能可加快表面活性氧生成速率,从而催化性能得以提升。     

杨晓智 郭建华* 于凯川 王树谦

为了探究重金属胁迫下生物炭对玉米幼苗生长的影响,采用盆栽水培玉米幼苗,在无Pb2+和含Pb2+对照下观察不同裂解温度制备的生物炭对玉米幼苗生长的影响。研究结果表明：生物炭滤出液对玉米种子的萌发影响不显著, WS300(300℃生物炭)促进玉米幼苗的干物质量增加了27%, WS500(500℃生物炭)促进玉米幼苗的干物质量增加了35%。在Pb2+胁迫下,不同裂解温度生物炭对培养液中的Pb2+去除率达到了25%-30%,其中PWS300(含Pb2+的300℃生物炭)促进玉米幼苗茎长增加了25%、干物质量增加了30%。由此可见,生物炭在Pb2+胁迫下对玉米幼苗生长的促进作用有虽所减弱,但依然能明显促进玉米幼苗的早期生长。     

一步法合成耐久性水基超疏水TiO2/DTMS涂层

为制备具有优异自清洁功能的耐久性水基超疏水涂层,以十二烷基三甲氧基硅烷(n-dodecyltrimethoxysilane, DTMS)为有机改性物,通过一步法在纳米TiO₂表面嫁接长链烷基官能团得到超疏水TiO₂/DTMS涂层。分析了TiO₂涂层及TiO₂/DTMS涂层的表面润湿性、形貌和化学组成,并对所得超疏水TiO₂/DTMS涂层的自清洁性能、机械及化学稳定性进行了测试。结果表明：超疏水TiO₂/DTMS涂层表面水接触角(water contact angle, WCA)达到159°;以亚甲基蓝粉末作模拟污染物,涂覆有超疏水TiO₂/DTMS涂层的玻璃具有优异的自清洁性能;经机械磨损(10 min)、酸碱液(pH=1、3、5、7、9、11、13)浸泡、高低温(−20、30、60、90、120、150 ℃)处理后超疏水TiO₂/DTMS涂层的WCA仍大于150°,表明其具有优异的机械和化学稳定性,可用于室外防污,如建筑物外墙、玻璃、太阳能电池板等。     

CuMn_2O_4/NiMn_2O_4近常温热催化降解亚甲基蓝研究

采用高温固相合成法制备Cu Mn2O4/Ni Mn2O4热敏催化剂,通过XRD、TEM、TGA、UV-vis和SEM等手段对样品进行了表征,研究了近常温热催化降解亚甲基蓝有机污染物。结果表明:亚甲基蓝底物质量浓度分别为30、40和50 mg/L时,随着温度从30、35到40℃的升高,去除率分别达到68.35%、79.64%和88.89%;在完全遮光、40℃、亚甲基蓝底物质量浓度为30 mg/L和热敏催化剂用量45 mg的条件下,经过48 h热催化降解过程,最佳降解率达到最优。此外,利用GC-MS对降解产物进行了分析,发现降解的主要产物为二氯甲烷和甲苯,由此证明亚甲基蓝确实发生了降解反应,且其降解程度也比较彻底。综上所述,近常温热催化降解途径将为未来工业废水处理提供潜在解决方案。     

Enhanced low-temperature performance of slight Mn-substituted LiFePO<Subscript>4</Subscript>/C cathode for lithium ion batteries

Low temperature performance of LiFePO₄/C cathode was remarkably improved by slight Mn-substitution. Electrochemical measurements showed that about 95% of the discharge capacity of LiFe_0.98Mn_0.02PO₄/C cathode at 20°C was obtained at 0°C, compared to 85% of that of LiFePO₄/C cathode. The LiFe_0.98Mn_0.02PO₄/C sample also presented enhanced rate performance at −20°C with the discharge capacities of 124.4 mA h/g (0.1C), 99.8 mA h/g (1C), 80.7mAh/g (2C) and 70 mA h/g (5C), respectively, while pristine LiFePO₄/C only delivered capacities of 120.5 mA h/g (0.1C), 90.7 mA h/g (1C), 70.4 mA h/g (2C) and 52.2 mA h/g (5C). Cyclic voltammetry measurements demonstrated an obvious improvement of the lithium insertion-extraction process of the LiFePO₄/C cathode by slight Mn-substitution. The results of FSEM observation and electrical conductivity measurement indicated that slight Mn-substitution minimized the particle size of LiFe_0.98Mn_0.02PO₄/C and also obviously improved the electrical conductivity of the compound, thus obviously enhances the interface reaction process on the cathode.     

Effect of sintering temperature on the preparation of Cu–Ti3SiC2 metal matrix composite

Ti3SiC2 has the potential to replace graphite as reinforcing particles in Cu matrix composites for applications in brush,electrical contacts and electrode materials.In this paper the fabrication of Cu-Ti3SiC2 metal matrix composites prepared by warm compaction powder metallurgy forming and spark plasma sintering(SPS) was studied.The stability of Ti3SiC2 at different sintering temperatures was also studied.The present experimental results indicate that the reinforcing particles in Cu-Ti3SiC2 composites are not stable at and above 800℃.The decomposition of Ti3SiC2 will lead to the formation of TiC and/or other carbides and TiSi2.If purity is the major concern,the processing and servicing temperatures of the Cu-Ti3SiC2 composite should be limited to 750℃ or lower.The composites prepared by warm compaction forming and SPS sintering at 750℃ have lower density when compared with the composites prepared by SPS sintering at 950℃,but their electrical resistivity values are very close to each other and even lower.     

Fe3O4@NiSiO3纳米催化剂制备及催化臭氧化降解对苯二甲酸性能研究

采用水热法和溶胶凝胶法制备Fe₃O₄@SiO₂纳米颗粒,经表面镍刻蚀得到Fe₃O₄@NiSiO₃磁性纳米催化剂。利用XRD、TEM和VSM等手段表征催化剂的晶体和表面结构。构建类均相催化臭氧化体系,考察其催化降解对苯二甲酸性能。结果表明：在臭氧通入量10.52 mg.min_-1、催化剂投加量40 mg.L_-1和初始溶液pH=9的条件下,催化臭氧化反应20 min时对苯二甲酸降解率为78.13%,TOC去除率27.25%;5次循环实验后,PTA降解率仅下降2.75%。     

ZrO_2-supported α-MnO_2:Improving low-temperature activity and stability for catalytic oxidation of methane

The single phaseα-Mn O_2and in-situ supportedα-Mn O_2/Zr O_2with different ratios of Mn/Zr were synthesized by one-pot hydrothermal method.They showed superior activity for catalytic oxidation of methane and even better than that of 1%Pt/Al_2O_3.The T_(50)of Mn O_2/Zr O_2catalysts with different ratios of Mn/Zr were located in the range of 315–335°C at a WHSV of 90 L g~(-1)h~(-1),whereas that of Pt/Al_2O_3was 380°C.After sulfur ageing,the Mn O_2/Zr O_2catalysts with Mn/Zr ratio of 2:1(2Mn O_2/1Zr O_2)and 1:1(1Mn O_2/1Zr O_2)exhibited satisfying sulfur resistance in comparison to the pure Mn O_2.The 2Mn O_2/1Zr O_2catalyst also showed acceptable catalytic stability,and the addition of 10 vol%CO_2had no obvious negative effect on its stability,whereas the addition of2.6 vol%H_2O caused slight but reversible decreasing methane oxidative activity.     

Bulk Al-Al3Zr composite prepared by mechanical alloying and hot extrusion for high-temperature applications

Bulk Al/Al₃Zr composite was prepared by a combination of mechanical alloying (MA) and hot extrusion processes. Elemental Al and Zr powders were milled for up to 10 h and heat treated at 600℃ for 1 h to form stable Al₃Zr. The prepared Al₃Zr powder was then mixed with the pure Al powder to produce an Al-Al₃Zr composite. The composite powder was finally consolidated by hot extrusion at 550℃. The mechanical properties of consolidated samples were evaluated by hardness and tension tests at room and elevated temperatures. The results show that annealing of the 10-h-milled powder at 600℃ for 1 h led to the formation of a stable Al₃Zr phase. Differential scanning calorimetry (DSC) results confirmed that the formation of Al₃Zr began with the nucleation of a metastable phase, which subsequently transformed to the stable tetragonal Al₃Zr structure. The tension yield strength of the Al-10wt%Al₃Zr composite was determined to be 103 MPa, which is approximately twice that for pure Al (53 MPa). The yield stress of the Al/Al₃Zr composite at 300℃ is just 10% lower than that at room temperature, which demonstrates the strong potential for the prepared composite to be used in high-temperature structural applications.     

Fabrication and Photocatalytic Characteristics of TiO2 Films on Silicon Substrates

Silicon ( 111 ) and Silicon (100) have been employed for fabrication of TiO2 films by metal organic chemical vapor deposition (MOCVD). Titanium (Ⅳ) isopropoxide (Ti[O (C3H7)4 ])was used as a precursor. The as-deposited TiO2 films have been characterized with Field emission scanning electron microscopy (FE-SEM), X ray diffraction (XRD) and atomic force microscopy (AFM). The photocatalytic properties were investigated by decomposition of aqueous orange Ⅱ. The crystalline and structural properties of TiO2 film had crucial influences on the photodegradation efficiency. For MOCVD in-situ deposited films on Si substrates, thephotoactivities varied following a shape of “M”: At lower (350 ℃ ) middle (500 ℃) and higher (800 ℃) temperature of deposition, relative lower photodegradation activities have been observed. At 400 ℃ and 700 ℃ of deposition, relative higher efficiencies of degradation have been obtained, because one predominant crystallite orientation could be obtained as deposition at those two temperatures, especially a single anatase crystalline TiO2 film could be obtained at 700 ℃ growth.     

Nitridation of chromium powder in ammonia atmosphere

CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were constructed for different temperatures. Chromium nitride formed at 7002-1200℃ under relatively higher nitrogen and lower oxygen partial pressures. Phases in the products were then investigated using X-ray diffraction (XRD), and the Cr₂N content varied with reaction temperature and holding time. The results indicate that the Cr metal powder nitridation process can be explained by a diffusion model. Further, Cr₂N formed as an intermediate product because of an incomplete reaction, which was observed by high-resolution transmission electron microscopy (HRTEM). After nitriding at 1000℃ for 20 h, CrN powder with an average grain size of 63 nm was obtained, and the obtained sample was analyzed by using a scanning electron microscope (SEM).     

Microstructure and growth kinetics of Ce and Y jointly modified silicide coatings for Nb–Ti–Si based ultrahigh temperature alloy

In order to protect Nb-Ti-Si based ultrahigh temperature alloy from oxidation, pack cementation processes were utilized to prepare Ce and Y jointly modified silicide coatings. The Ce and Y jointly modified silicide coating has a double-layer structure: a relatively thick (Nb, X)Si2 (X represents Ti, Cr and Hf elements) outer layer and a thin (Ti, Nb)5Si4 transitional layer. The pack cementation experiments at 1150 ℃ for 8 h proved that the addition of certain amounts of CeO2 and Y2O3 powders in the packs distinctly influenced the coating thickness, the contents of Si, Ce and Y in the (Nb, X)Si2 outer layers, and the density of cavities in the coatings. In order to study the effects of Ce and Y joint modification in the silicide coatings, both only Ce and only Y modified silicide coatings were also prepared for comparison. The mechanisms of the beneficial effects of Ce and Y are discussed. A pack mixture containing 1.5CeO2-0.75Y2O3 (wt%) powders was employed to investigate the growth kinetics of the Ce and Y jointly modified silicide coating at 1050, 1150 and 1250 ℃. It has been found that the growth kinetics obeyed parabolic laws and the parabolic rate constants were 109.20 mm2/h at 1050 ℃, 366.75 mm2/h at 1150 ℃ and 569.78 mm2/h at 1250 ℃, and the activation energy for the growth of the Ce and Y jointly modified silicide coating was 197.53 kJ/mol.