Highly stable Fe/γ‐Al2O3 catalyst for catalytic wet peroxide oxidation

BACKGROUND: A highly stable Fe/γ‐Al₂O₃ catalyst for catalytic wet peroxide oxidation has been studied using phenol as target pollutant. The catalyst was prepared by incipient wetness impregnation of γ‐Al₂O₃ with an aqueous solution of Fe(NO₃)₃· 9H₂O. The influence of pH, temperature, catalyst and H₂O₂ doses, as well as the initial phenol concentration has been analyzed. RESULTS: The reaction temperature and initial pH significantly affect both phenol conversion and total organic carbon removal. Working at 50 °C, an initial pH of 3, 100 mg L^?1 of phenol, a dose of H₂O₂ corresponding to the stoichiometric amount and 1250 mg L^?1 of catalyst, complete phenol conversion and a total organic carbon removal efficiency close to 80% were achieved. When the initial phenol concentration was increased to 1500 mg L^?1, a decreased efficiency in total organic carbon removal was observed with increased leaching of iron that can be related to a higher concentration of oxalic acid, as by‐product from catalytic wet peroxide oxidation of phenol. CONCLUSION: A laboratory synthesized γ‐Al₂O₃ supported Fe has shown potential application in catalytic wet peroxide oxidation of phenolic wastewaters. The catalyst showed remarkable stability in long‐term continuous experiments with limited Fe leaching, < 3% of the initial loading. Copyright © 2010 Society of Chemical Industry     

钼添加对CrN涂层抗氧化性能的影响

研究钼添加对CrN涂层微观结构和抗氧化性能的影响,采用反应磁控溅射法在硅片和高速钢片上制备不同Mo含量的Cr-Mo-N涂层,并在500~800 ℃的高温空气中退火1 h,用X射线衍射（XRD）、拉曼光谱和扫描电子显微镜（SEM）对涂层退火前后的微观形貌进行表征。沉积的CrN和Cr-Mo-N涂层均表现出基于CrN晶格的B1面心立方相（fcc）。Mo离子取代Cr-N晶格中的Cr离子,形成Cr-Mo-N固溶体。在600 ℃时,XRD和拉曼光谱表明,Mo含量较高的Cr-Mo-N涂层中形成MoO₃相,表面较粗糙,含氧量较高。在700 ℃时,CrN涂层由于内应力的作用,其横截面形貌为疏松的柱状晶,并有一定的多孔区,而Cr-Mo-N涂层则为致密的柱状晶结构。低Mo含量（<17at%）的Cr-Mo-N涂层比CrN涂层具有更好的抗氧化性。     

改性TiO2纳米管阵列电极的光电化学性能研究

近年来,掺杂改性的TiO₂纳米管作为光催化材料的研究受到广泛关注。本实验采用阳极氧化法在Ti板表面制备规则有序的TiO₂纳米管,通过在电解液中直接添加含Fe、N元素的化学试剂对其进行掺杂改性。利用扫描电子显微镜、X射线衍射仪和X射线光电子能谱对TiO2纳米管进行表征,确定TiO₂纳米管的最佳制备条件。最后利用瞬态光电流曲线、开路电位曲线、线性伏安扫描曲线对其光电化学性能进行比较。研究发现,1%的Fe元素掺杂材料具有更好的光电响应,光照时开路电位可达0.345 V;9%的N元素掺杂材料具有最好的光电活性,光照时开路电位可达0.3 V。     

钛表面改性Al/NiCu组合涂层反应机理及抗氧化性能

采用等离子结合电弧喷涂的工艺方法在工业纯钛表面制备了Al/Ni Cu组合涂层,在700℃的大气环境下对Al/Ni Cu/Ti试件进行加热处理,使得Al、Ni Cu复合涂层之间发生扩散反应并原位生成具有一定抗高温氧化性能的Ni-Al金属间化合物涂层。对加热改性处理前后涂层的微观组织及Ni-Al金属间化合物的形成机理进行了研究,并对经加热和打磨处理后的Al/Ni Cu/Ti试件及无防护涂层的Ti块进行了800℃/100 h的高温氧化试验。研究结果显示,Ti基体表面Al/Ni Cu涂层经700℃炉中加热改性处理后,Al、Ni Cu涂层间可发生扩散反应并原位生成Ni Al3、Cu Al2、Ni2Al3及含有一定Cu元素的Ni Al金属间化合物,但只有高熔点的Ni Al金属间化合物能够始终稳定地存在,且此金属间化合物对Ti基体起到了较好的高温防护作用。     

Effect of NaOH on plasma electrolytic oxidation of A356 aluminium alloy in moderately concentrated aluminate electrolyte

Plasma electrolytic oxidation(PEO) of cast A356 aluminum alloy was carried out in 32 g/L NaAlO₂ with the addition of different concentrations of NaOH. The stability of the aluminate solution is greatly enhanced by increasing the concentration of NaOH. However, corresponding changes in the PEO behaviour occur due to the increment of NaOH concentration. Thicker precursor coatings are required for the PEO treatment in a more concentrated NaOH electrolyte. The results show that the optimal NaOH concentration is 5 g/L, which improves the stability of storage electrolyte to about 35 days, and leads to dense coatings with high wear performance (wear rate: 4.1×10⁻⁷ mm³·N⁻¹·m⁻¹).     

镁锂合金低能耗等离子电解氧化膜层的制备与耐蚀性研究

目的 在保证膜层耐蚀性能的前提下,降低镁锂合金等离子电解氧化过程中的能量消耗.方法 分别使用常规NaOH-Na2SiO3电解体系与自研的NaOH-Na2SiO3-Na2B4O7-Na3C6H5O7·2H2O(柠檬酸钠)低能耗电解体系,对LA91型镁锂合金进行等离子电解氧化,并探究其放电过程.采用扫描电子显微镜(SEM)、能谱仪(EDS)、掠入射X射线衍射仪(GIXRD),表征等离子电解氧化膜层的表面形貌、元素组成、物相组成.通过电化学极化曲线、盐雾试验,测试膜层的耐蚀性.结果 使用低能耗体系对镁锂合金进行等离子电解氧化处理,可将膜层的单位体积能耗降低至12.87 kJ/(dm2·μm),节约能耗约50.34％.在两个体系中制备的膜层表面均产生等离子电解氧化的特征性孔洞.低能耗体系膜层孔洞数量较少,但孔洞直径差异较大,孔隙率为14.21％;常规体系膜层孔洞大小均匀,但数量较多,孔隙率为13.93％.两个膜层表面的主要元素均为O、Mg、Na和Si.在低能耗体系中制备的膜层,主要物相为方镁石型MgO,而在常规体系中制备的膜层,物相组成较为复杂.盐雾试验和电化学极化曲线结果显示,在两种体系中进行等离子电解氧化,均能提升镁锂合金的耐蚀性.低能耗等离子氧化处理后,镁锂合金的腐蚀电流密度降低约3个数量级,腐蚀速率降低约2个数量级,自腐蚀电位正移0.261 V,有效地提升了镁锂合金的耐蚀性,并且耐蚀性的提升程度要优于常规体系.结论 使用低能耗体系电解液进行等离子电解氧化,能够形成孔洞特征不同于常规体系的等离子电解氧化膜层.与常规体系下制备的膜层相比,其厚度、孔隙率并无较大差异,但能够在节约较多能耗的情况下制备出耐蚀性能更好的等离子电解氧化膜层.     

磷酸盐后处理对Mg-Gd-Y合金微弧氧化涂层耐蚀性能的影响

目的 为进一步提高镁稀土合金微弧氧化涂层的耐蚀性能.方法 首先在镁稀土合金表面制备了微弧氧化涂层,随后用磷酸盐后处理溶液,对Mg-Gd-Y合金硅酸盐微弧氧化涂层进行了封孔后处理,并在此过程中添加了缓蚀剂.利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对涂层表面形貌和成分进行分析,利用极化曲线和电化学阻抗(EIS)测试了涂层的耐蚀性能.结果 后处理能够在微弧氧化涂层表面形成MgHPO4沉积层,沉积层的产生有效地封闭了微弧氧化涂层表面的微孔、裂纹等缺陷.缓蚀剂的添加显著增加了沉积物的量,使涂层的磷元素原子数分数由5.37％增加至14.90％,沉积效果显著.极化实验证明,封孔后处理涂层的腐蚀电流密度由1.51×10–7 A/cm2降至4.91×10–8 A/cm2,负载缓蚀剂后,涂层的腐蚀电流密度进一步降低至5.76×10–9 A/cm2,表明其耐蚀性能显著提高.微弧氧化涂层在3.5％NaCl溶液中浸泡384 h后,含缓蚀剂的涂层的总阻抗值可达7825.3?·cm2,明显高于未封孔处理的微弧氧化涂层(403?·cm2),这证明,后处理可有效提高微弧氧化涂层的耐蚀性能.结论 磷酸盐后处理能够在微弧氧化涂层表面生成MgHPO4沉积层,有效地对微弧氧化涂层表面的微孔和微裂纹进行了封闭.缓蚀剂的添加能够显著增强磷酸盐的沉积效果,使涂层的耐蚀性能在后处理的基础上进一步提高.     

Novel Co‐Mn‐O nanosheet catalyst for CO preferential oxidation toward hydrogen purification

Co‐Mn‐O composite oxide nanosheet catalyst was successfully prepared using a facile urea‐assisted one‐step hydrothermal method in the absence of organic or organic templating reagent. Co‐Mn‐O nanosheet catalyst was optimized by varying hydrothermal process parameters such as molar ratio of Co‐Mn to urea, hydrothermal temperature, and hydrothermal time. Various characterization techniques including scanning electron microscopy, X‐ray diffraction, nitrogen adsorption, X‐ray photoelectron spectroscopy, Raman spectroscopy, and H₂ temperature‐programmed reduction were used to reveal the relationship between catalyst nature and catalytic performance in CO preferential oxidation (CO PROX) in excess H₂. The developed Co‐Mn‐O nanosheet catalyst have demonstrated much superior catalytic performance to Co‐Mn‐O nanoparticle, particularly in the low temperature range, and 100% CO conversion over the developed Co‐Mn‐O nanosheet can be achieved in temperature range of 50 to 150°C at 10,000 mL g^?1 h^?1 of gas hourly space velocity in the standard feed. Furthermore, the almost complete CO removal over Co‐Mn‐O nanosheet at 125°C of low temperature with 94.9% selectivity can be achieved even in the simulated reformed gas. The excellent catalytic performance is ascribed to nanosheet morphology, more surface Co³⁺, smaller average crystallite size, higher reducibility, and strong Co‐Mn interaction. Catalytic stability investigation indicates the developed nanostructured catalyst exhibits high catalytic stability for CO PROX reaction in simulated gas. The developed Co‐Mn‐O nanosheet catalyst can be a potential candidate for catalytic elimination of trace CO from H₂‐rich gas for Proton exchange membrane fuel cell applications. © 2014 American Institute of Chemical Engineers AIChE J, 61: 239–252, 2015     

双氧水对自呼吸式燃料电池性能的影响

将双氧水加入到阳极燃料甲醇溶液中来研究其对DMFC性能的影响。双氧水作为阳极助氧化剂将甲醇催化氧化产生的中间体CO氧化成气体CO2排出,从而减少中间体在催化层表面的吸附,增强催化剂的催化性能,从而提高电池的输出性能。通过探讨不同双氧水浓度和不同温度情况下,甲醇催化氧化的氧化峰电流密度及自呼吸式燃料电池的极限功率密度,阻抗等性能来分析双氧水在其中的作用。结果表明低浓度的双氧水确实能提高DMFC的输出性能,并且在双氧水的浓度为0.05 mol/L,温度为55℃时DMFC性能最佳。