镁合金表面纳米二氧化铈/磷酸盐复合转化膜的制备及其防护性能

添加纳米颗粒可改善金属表面膜层的性能,但目前添加纳米颗粒改善镁合金表面磷化膜性能的报道较少。通过向磷化处理液中添加纳米二氧化铈(nano-CeO_2)颗粒在镁合金表面制备了一层纳米二氧化铈/磷酸盐复合转化膜,采用X射线衍射仪(XRD)、X射线光电子能谱(XPS)、电化学阻抗谱(EIS)和极化曲线等手段研究了添加nano-CeO_2颗粒对膜层成分和防护性能的影响,讨论了nano-CeO_2颗粒的作用机制。结果表明:复合转化膜的相成分为Zn_3(PO_4)_2·4H_2O、Zn_2Mg(PO_4)_2和CeO_2,在单组分磷化膜成分的基础上多出了CeO_2相。在硼酸缓冲溶液中,单组分磷化膜的膜层电阻(R_c)和低频阻抗值(R_(0.01 Hz))分别为561.74 kΩ·cm~2和938.11 kΩ·cm~2,而复合转化膜的R_c和R_(0.01 Hz)分别为2 428.98 kΩ·cm~2和3 985.61 kΩ·cm~2;与此同时,覆盖复合转化膜镁合金的腐蚀电流密度为4.05×10~(-7)A/cm~2,而覆盖单组分磷化膜镁合金的为8.38×10~(-6)A/cm~2,R_c和R_(0.01 Hz)的增大以及J_(corr)的减小说明复合转化膜的防护作用明显优于单组分磷化膜的防护作用。nano-CeO_2颗粒的作用机制主要归因于两个方面:第一,nano-CeO_2颗粒在处理液中的添加有利于磷酸盐晶核的形成;第二,nano-CeO_2颗粒作为一种不溶性固体粒子在膜层中的存在可以强化膜层的物理屏蔽效应。     

PANI/CeO_2纳米复合纤维材料的合成和表征

用水热法制备了纳米CeO2,并利用其氧化性通过原位聚合法制备出PANI/CeO2复合纳米纤维。采用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(FT-IR)等检测技术对复合材料的结构进行了表征。结果表明:复合材料两相间存在化学键合作用;酸浓度和无机纳米相影响了聚苯胺纤维结晶。当CPANI0.1mol/L,随着酸浓度的升高,PANI/CeO2的结构形态从球状逐渐发展成纤维状,CeO2粒子的粒径会影响聚苯胺结晶状态,粒径越小,越易形成结晶规整的纤维结构。     

Fabrication characterization and activity of a solar light driven photocatalyst: cerium doped TiO2 magnetic nanofibers

A novel magnetic separable composite photocatalytic nanofiber consisting of TiO2 as the major phase, CeO(2-y) and CoFe2O4 as the dopant phase was prepared by sol-gel method and electrospinning technique, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectrum (UV-vis DRS) and vibrating sample magnetometer (VSM). The photocatalytic activity of the resultant CoFe2O4-TiO2 and CeO(2-y)/CoFe2O4-TiO2 nanofibers was evaluated by photodegradation of methylene blue (MB) in an aqueous solution under xenon lamp (the irradiation spectrum energy distribution is similar to sunlight) irradiation in a photochemical reactor. The results showed that the dopant of Ce could affect the absorbance ability and photo-response range. The sample containing 1.0 wt% CeO(2-y) exhibited the highest degradation with 35% for MB under simulate solar light irradiation. Furthermore, the as-synthesized composite photocatalytic nanofibers could be separated easily by an external magnetic field, thus it might hold potential for application in wastewater treatment.     

S、RE共掺杂TiO2的制备及其可见光分解水制氢性能

采用溶胶-凝胶法制备了系列稀土(La、Eu、Nd、Tb、Er)和硫共掺杂TiO2光催化剂RE/S/TiO2。通过紫外-可见(UV-Vis)漫反射、X射线衍射(XRD)对催化剂进行了表征。以EDTA为电子给体,考察了光催化剂在可见光照射下的制氢活性。研究结果表明,S/TiO2具有可见光活性,稀土掺杂进一步提高了S/TiO2可见光活性,其活性顺序依次为Eu/S/TiO2>La/S/TiO2>Nd/S/TiO2>Tb/S/TiO2>Er/S/TiO2。与纯TiO2和S/TiO2光催化剂相比,稀土掺杂使催化剂的粒径减小,晶格畸变应力增大,从而提高了催化剂可见光制氢活性。     

Preparation and characterization of visible-light-driven TiO2 photocatalyst Co-doped with nitrogen and erbium

A series of nitrogen and erbium co-doped TiO2 photocatalyst was prepared by sol-hydrothermal method. The structure and properties of the photocatalyst were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), and UV-vis diffuse reflectance spectra (DRS). The XRD and BET results showed that co-doping inhibited the increase of crystallite size and enlarged specific surface areas. XPS spectroscopy indicated nitrogen atoms were incorporated into TiO2 lattice, and erbium atoms mostly existed in the forms of Er2O3. A shift of the absorption edge to the lower energy and four absorption bands located at 654, 544, 524 and 489 nm attributed to the 4f transitions of 4I15/2 --> 4F2/9, 4I15/2 --> 4S3/2, 4I15/2 --> 2H11/2, 4I15/2 --> 4F7/2 of Er3+ were observed using DRS spectroscopy. The catalytic efficency was evaluated by the photocatalytic degradation of methyl orange (MO) under visible light irradiation. The results showed that the photocatalytic performance of the co-doped TiO2 was related with the hydrothermal temperature and the molar ratio of N/Ti, and they showed higher acitivites than pure TiO2. Results determined by fluorescence technique revealed that irradiation (lambda > 400 nm) of TiO2 photocatalyst dispersed in MO solution induces the generation of the highly active hydroxyl radicals (OH). It indicated the photocatalytic activities of TiO2 photocatalyst were correlation with the formation rate of hydroxyl radicals (OH) and other active oxygen species.     

溶胶-凝胶法涂覆氧化铈对铬表面氧化膜生长机制的影响

采用溶胶-凝胶法在纯铬表面涂覆纳米氧化铈，并对其在1000℃空气中的氧化行为进行了研究，对于了解稀土元素改善合金抗氧化机理及开发新型稀土掺杂陶瓷防护涂层具有重要意义．采用扫描电子显微镜（SEM）和透射电子显微镜（TEM）对铬表面氧化膜的微观形貌与结构进行观测，用激光拉曼（Raman）和X射线衍射（XRD）对铬及其涂覆纳米氧化铈样品表面氧化膜的应力水平进行测试；并用二次离子质谱（SIMS）对氧化膜内元素Cr、O及Ce的深度分布情况进行了测试．结果表明，纳米氧化铈涂层降低了铬的氧化速率，其抛物线速率常数由涂覆前的2．6×10^-6mg^2／（cm^4·s）下降为涂覆后的7．4×10^-7mg^2／（cm^4·s），并且显著细化了表面Cr2O3膜的晶粒尺寸．这种细晶氧化膜可以通过高温蠕变的方式释放掉部分膜内压应力，并呈现出褶皱特征纳米氧化铈的存在使Cr2O3膜的生长机制由原来的Cr^3＋向外扩散控制转变为O^2-向内扩散控制．X射线衍射和激光拉曼测量均反映出表面涂覆氧化铈所引起的Cr2O3膜内应力降低；此外，结合氧化膜生长机制的转变对两种应力测量结果之间的偏差进行了分析．     

Effect of morphology of dispersed nano-CeO2 on far infrared emission property of natural tourmaline

Dispersed nano-CeO2 successfully grew on the surface of natural tourmaline powders by a precipitation method. The results of Fourier transform infrared spectroscopy (FTIR) showed that CeO2 (111) nanospots could apparently enhance the far infrared emission property of tourmaline in relation to CeO2 nanoparticles. This is the first report regarding the effect of the morphology of nano-CeO2 on the far infrared emission property of natural tourmaline. The results of the characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) showed that CeO2 (111) nanospots have much more chemisorbed oxygen than CeO2 nanoparticles, which is beneficial to the unit cell volume shrinkage of tourmaline, thus increasing its far infrared emissivity.     

纳米CeO2对激光熔覆Fe/Cr3C2复合涂层组织与磨损性能的影响

采用扫描电镜(SEM)、能谱分析仪(EDS)、X射线衍射仪(XRD)、显微硬度仪及滑动磨损试验,研究了1%纳米CeO_2(质量分数)对低碳钢表面激光熔覆Fe/Cr_3C_2复合涂层的组织结构和耐磨性能的影响。结果表明,Fe+Cr_3C_2+1%CeO_2复合涂层的主要组成相是α-Fe、γ-Fe、Cr_3C_2、Cr_(23)C_6及Cr_7C_3等化合物相;加入1%纳米CeO_2后,复合涂层组织明显细化,未熔Cr_3C_2数量显著减少,初生碳化物由粗大杆状向块状转变,数量增加,分布均匀,有效抑制和消除了裂纹的形成;复合涂层硬度和耐磨性能显著提高,Fe+30%Cr_3C_2+1%CeO_2涂层截面显微硬度提高105HV,增幅达到15.4%,且涂层沿深度方向硬度分布均匀性得到明显改善。     

铁氮共掺杂TiO2光催化剂的制备及光催化性能

采用溶胶-凝胶法与微波合成法相结合制备铁氮共掺杂的TiO2光催化剂。通过XRD、FT-IR、UV-Vis、PL等对Fe-N-TiO2样品进行表征和分析,并以亚甲基蓝（MB）作为目标降解物,考察经不同温度热处理及不同掺铁量的样品对MB的降解效果。结果表明所制备的样品在700℃热处理5h后为锐钛矿相与金红石相混晶,样品的吸收阈值波长向可见光红移约45nm。铁氮共掺杂抑制了样品从锐钛矿相向金红石相的转变,提高了TiO2的光催化活性。在普通日光灯下,热处理温度为600℃、掺铁量与TiO2摩尔比为1︰200条件下制备的样品,其光催化活性明显高于Degussa P25。     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: preparation and photocatalytic behavior of TiO2/Sr2CeO4

The paper demonstrates that the photocatalytic activity of TiO(2) towards the decomposition of gaseous benzene in a batch reactor can be greatly improved by loading TiO(2) on the surface of Sr(2)CeO(4). The research investigates the optimum loading amount of TiO(2) on Sr(2)CeO(4) in enhancing the photocatalytic activity of TiO(2). The prepared photocatalyst was characterized by XRD, UV-vis diffuse reflectance and XPS analyses. TiO(2) is loaded on Sr(2)CeO(4) at 773K. TiO(2)/Sr(2)CeO(4) absorbs much more visible light than TiO(2). The XPS spectrum shows that there are Ti, O, C, Sr elements on the surface of the TiO(2)/Sr(2)CeO(4), and that the binding energy value of Ti2p transfers to a lower value. TiO(2)/Sr(2)CeO(4) demonstrates 2.0 times the photocatalytic activity of pure TiO(2). Based upon these observations, the mechanistic role of Sr(2)CeO(4) in the photocatalytic oxidation reaction has been suggested.     

表面包覆CeO2制备高耐候性钛白的研究

在金红石TiO2水性分散体浆料中,保持温度为70℃,PH值为9.5,分别加入TiO2基料的1%、0.2%、0.05%的硝酸铈溶液(w,以CeO2计)进行CeO2包膜,获得了光催化活性分别为0、0.13、0.47的高耐候性TiO2颜料.ξ电位测定表明,TiO2单分散的最佳条件是pH=9.5～10.5.热力学分析表明,CeO2在TiO2颗粒表面形核时的自由能ΔGh较小,CeO2可以顺利包覆于TiO2颗粒表面.     

Oxidative decomposition of azo dye C.I. Acid Orange 7 (AO7) under microwave electrodeless lamp irradiation in the presence of H2O2

A novel microwave electrodeless lamp (MWL) rather than traditional electrode lamp (TEL) was used in a H(2)O(2)/MWL system as light source. This technique provided a new way to study the simultaneous effect of both UV-vis light and microwave irradiations. This study showed that H(2)O(2)/MWL process was 32% more effective than H(2)O(2)/TEL process in degrading azo dye Acid Orange 7 (AO7). Further study found that the degradation of AO7 by the H(2)O(2)/MWL process was initiated by the attack of HO* radicals generated by the photolysis of H(2)O(2). However, the direct photolysis of AO7 by MWL irradiation was not negligible. Effect of operation parameters, such as the initial concentrations of AO7 and H(2)O(2) and pH, were investigated. A kinetic model of degradation of AO7 by H(2)O(2)/MWL process was found, in which not only the HO* oxidation but also direct photolysis were considered. The kinetic model was consistent with the experiment results. The degradation of AO7 by H(2)O(2)/MWL corresponded to a pseudo-first order reaction. The apparent reaction constant (k(ap)) was a function of initial concentrations of H(2)O(2) and AO7 and pH of the solution.     

Photocatalytic oxidation of 2,4,6-trichlorophenol in water using a cocurrent downflow contactor reactor (CDCR)

The heterogeneous photocatalytic oxidation of aqueous solutions of 2,4,6-trichlorophenol (2,4,6-TCP) as a model pollutant in industrial wastewater has been carried out in a pilot scale cocurrent downflow contactor reactor (CDCR). The reactions were carried out in the presence of Ultra-Violet radiation, O(2) and TiO(2) photocatalyst (VP Aeroperl P25/20). The TiO(2) was characterized by Dynamic Vapour Sorption (DVS) technique giving specific surface area and surface energy of 46.06 m(2)g(-1) and 80.12 mJ m(-2), respectively. The CDC reactor was fitted with an internally and vertically mounted 1.0 kW or 2.0 kW UV lamp. The reactions were carried out at 50 degrees C and 1 bar, with the reactor being operated in closed loop recycle mode and suspended photocatalyst being re-circulated. The CDC reactor, a device of very high mass transfer efficiency giving unusually large gas hold-up of approximately 50%, was operated with oxygen mass transfer and dissolution in the zone above the UV lamp (high mass transfer zone) and along and around the UV lamp housing (reaction zone). Under optimized reaction conditions, 100% conversion of 2,4,6-TCP was achieved in 180 min using 15 dm(3) solutions with initial concentration of 120 mg dm(-3). A combination of TiO(2) photocatalyst, UV irradiation and oxidant was observed to give the most rapid photodegradation and photomineralization of the 2,4,6-TCP in comparison with irradiation only. Using the 1 kW or 2 kW UV lamps, conversion of 100 mg dm(-3) of 2,4,6-TCP after 30 min was 62.51% and 90.71%, respectively, with initial reaction rates of 1.33 x 10(-5) and 4.22 x 10(-5) mol min(-1), respectively, and rate constants 0.0046 and 0.29 min(-1), respectively.     

纳米二氧化铈制备和应用研究进展

目的 通过比较各类纳米二氧化铈制备方法的优缺点,总结纳米二氧化铈在食品生物化学检测、催化与燃料电池等领域的应用研究,以促进纳米CeO2的发展,并为其应用提供参考.方法 对比分析纳米二氧化铈的制备方法,包括水热合成法、沉淀法、溶剂热法、溶胶-凝胶法、微乳液法和电化学沉积法.阐述纳米CeO2在催化(催化甲苯、CO和NOx、光催化)、食品生物化学检测(抗坏血酸、葡萄糖、黄嘌呤检测等)、燃料电池、食品包装等领域中的应用.结果 通常采用水热合成法制备纳米CeO2.纳米CeO2负载贵金属可制备生物检测催化剂及燃料电池阳极催化剂;纳米CeO2复合金属氧化物可用于制备抗紫外功能的食品包装.结论 纳米CeO2在食品生物化学检测、催化与燃料电池等领域有广阔的研究空间.     

磷石膏/粉煤灰/CaO复合材料对氧化石蜡皂的光催化吸附

利用磷石膏、粉煤灰、氧化钙作为吸附剂原料,CeO₂分析纯作为吸附过程的光催化助剂,试验使用紫外线除菌灯为试验提供光催化环境,试验证明:在磷石膏\\粉煤灰\\CaO掺比为1∶1∶2的前提条件下,加入10 mg的CeO₂助剂,并在紫外线除菌灯1 h的照射下对氧化石蜡皂的吸附率达到了88.10%。试验使用FT IR、SEM对吸附前后的样品进行表征,并研究了pH值、温度、CeO₂助剂的添加量、吸附质浓度、吸附时间对吸附过程的影响;结果表明:吸附较优的条件为pH在7～12,CeO₂助剂添加量为20 mg;吸附平衡时间为2 h;平衡吸附量为119.51 mg/g;平衡时的吸附率达94%;等温吸附线符合Langmuir等温吸附模型,吸附动力学遵循准二级吸附动力学方程。     

The decolorization and mineralization of acid orange 6 azo dye in aqueous solution by advanced oxidation processes: a comparative study

The comparison of different advanced oxidation processes (AOPs), i.e. ultraviolet (UV)/TiO(2), O(3), O(3)/UV, O(3)/UV/TiO(2), Fenton and electrocoagulation (EC), is of interest to determine the best removal performance for the destruction of the target compound in an Acid Orange 6 (AO6) solution, exploring the most efficient experimental conditions as well; on the other hand, the results may provide baseline information of the combination of different AOPs in treating industrial wastewater. The following conclusions can be drawn: (1) in the effects of individual and combined ozonation and photocatalytic UV irradiation, both O(3)/UV and O(3)/UV/TiO(2) processes exhibit remarkable TOC removal capability that can achieve a 65% removal efficiency at pH 7 and O(3) dose=45mg/L; (2) the optimum pH and ratio of [H(2)O(2)]/[Fe(2+)] found for the Fenton process, are pH 4 and [H(2)O(2)]/[Fe(2+)]=6.58. The optimum [H(2)O(2)] and [Fe(2+)] under the same HF value are 58.82 and 8.93mM, respectively; (3) the optimum applied voltage found in the EC experiment is 80V, and the initial pH will affect the AO6 and TOC removal rates in that acidic conditions may be favorable for a higher removal rate; (4) the AO6 decolorization rate ranking was obtained in the order of O(3)相似文献   

Catalytic combustion of ethyl acetate on supported copper oxide catalysts

Total oxidation of ethyl acetate on supported copper oxide catalysts was investigated. The catalysts have been prepared by wet impregnation method and characterized by XRD, TEM and XPS. Among the catalysts with the supports of TiO2, CeO2/TiO2 and CeO2-ZrO2/TiO2, CeO2-ZrO2 solid solutions doped TiO2 supported catalyst gives the highest catalytic activity. Catalyst with the composition of 5 wt.% CuO/10 wt.% CeO2-ZrO2-TiO2 shows the total oxidation of ethyl acetate at about 270 degrees C with the 100% CO2 selectivity. The characterization studies of supported copper oxide catalysts showed that the highly dispersed CuO is one of the active phase which contacts intimately with the support, the action of the interface between the components was not be ignored.     

Effect of metal doping into Ce0.5Zr0.5O2 on photocatalytic activity of TiO2/Ce0.45Zr0.45M0.1OX (M=Y, La, Mn)

The paper demonstrates that the photocatalytic activity of TiO2 towards the decomposition of gaseous benzene in a batch reactor can be greatly improved by loading TiO2 on the surface of CeO(2)-ZrO(2). The research investigates the effects of three metals doping into Ce(0.5)Zr(0.5)O(2) on photocatalytic activity of TiO2/Ce(0.45)Zr(0.45)M(0.1)O(X) (M=Y, La, Mn). The prepared photocatalysts were characterized by BET, XRD, UV-vis diffuse reflectance and XPS analyses. BET surface area of TiO2/Ce(0.45)Zr(0.45)M(0.1)O(X) (M=Y, La, Mn) is smaller than that of Ce(0.5)Zr(0.5)O(2). XRD results reveal that the deposited titania is highly dispersed as in the CeO(2)-ZrO(2) matrix, doping M in the CeO(2)-ZrO(2) lattice causes the changing of lattice space and the diffraction peaks shift to higher 2theta position. Among these four catalysts, the band gap value of TiO(2)/Ce(0.45)Zr(0.45)La(0.1)O(X) is the lowest. The binding energy value of Ti 2p(3/2) of four catalysts transfers to a lower value. The order of photocatalytic activity is TiO2/Ce(0.45)Zr(0.45)La(0.1)O(X)>TiO2/Ce(0.45)Zr(0.45)Y(0.1)O(X)>TiO2/Ce(0.45)Zr(0.45)Mn(0.1)O(X)>TiO2/Ce(0.5)Zr(0.5)O(2)>TiO2. The proposed mechanism is of electron transfer and the stronger absorption in the region 210-400 nm.     

基于一锅法制备的Ag/AgCl/CeO2复合纳米材料及其光催化有机物降解性能

采用一锅法制备Ag/CeO2光催化剂,并通过原位氧化法进一步制备Ag/AgCl/CeO2复合材料,使用XRD、SEM对Ag/AgCl/CeO2复合纳米材料的结构、形貌进行表征,采用橙黄II、罗丹明6G、诱惑红等有机染料测试复合材料的光催化性能。结果表明：AgCl在Ag/AgCl中占比80%时,Ag/AgCl/CeO2复合材料的光催化性能最佳,在模拟太阳光辐照6 min后能降解93%的橙黄II,且在4次循环8 min内能降解90%以上的橙黄II,在紫外-可见混合光照60 min后,能降解约90%的罗丹明6G和诱惑红。Ag/AgCl/CeO2复合材料具有优异的光催化活性的主要原因是贵金属Ag的局域表面等离子共振效应以及金属/半导体异质结结构。     

Enhanced TiO2 photocatalytic degradation of bisphenol E by beta-cyclodextrin in suspended solutions

Enhancement of beta-cyclodextrin (beta-CD) on TiO(2) photocatalytic degradation of bisphenol E (BPE, bis(4-hydroxyphenyl)ethane) was investigated under a 250 W metal halide lamp (lambda> or =365 nm) in this work. In the system of photocatalytic degradation of BPE, the photodegradation rate of BPE in aqueous solutions containing beta-CD and TiO(2) was obviously faster than that in aqueous solutions containing only TiO(2). After 40 min of irradiation, beta-CD could increase the photodegradation efficiency by about 26% for 10 mg l(-1) BPE in the UV-vis/TiO(2) system and the photodegradation of 2.5-20.0 mg l(-1) BPE in aqueous solutions was found to follow pseudo-first-order law and the adsorption constant and the reaction rate constant of BPE in the system containing beta-CD and TiO(2) are obviously higher than those in the system containing only TiO(2), the influence factors on photodegradation of BPE were studied and described in details, such as beta-CD concentration, pH, BPE initial concentration and gas medium. The formation of CO(2) as a result of mineralization of BPE was observed during the photodegradation process. After 120 min of irradiation, the mineralization efficiency of BPE reached 61% in the presence of beta-CD, whereas mineralization efficiency was only 23% in the absence of beta-CD. The enhancement of photodegradation of BPE could be dependent on the enhancement of adsorption of BPE on TiO(2) surface and moderate inclusion-depth of BPE in the beta-CD cavity.