TiO2-yNx纳米光催化剂的制备及其可见光响应机理

利用溶胶-凝胶技术,以尿素为氮源,采用原位掺杂方式制备了TiO2-yNx纳米粉体;以亚甲基蓝(MB)溶液在可见光下的光催化降解评价其可见光催化活性;考察了体系初始pH值、N的掺杂量和焙烧温度对样品可见光催化活性的影响。 结合XRD、XPS、ESR和DRS测试技术,研究了N掺杂纳米TiO2的可见光响应机理。 研究结果表明,TiO2-yNx纳米粉体的优化制备工艺条件为：体系初始pH=0.52,掺杂比n(N)∶n(Ti)=1∶6,焙烧温度为440 ℃。 此条件下制备的样品N含量为0.77%,为单一的锐钛矿相,平均粒径为19.0 nm,具有良好的可见光催化活性。 N掺杂导致TiO2纳米粉体的表面羟基含量增加,形成了大量束缚单电子的氧空位;N取代晶格O形成了N-Ti-O和O-N-Ti键合结构。 N掺杂导致TiO2纳米粒子的吸收带边红移,对可见光的吸收能力明显增强,这表明N掺杂改变TiO2电子结构,使带隙窄化,降低光响应阈值。 N掺杂TiO2纳米粒子的可见光响应归因于N取代掺杂形成的掺杂能级与氧空位形成的缺陷能级共同作用所致。     

The Vital Role of Buffer Anions in the Antioxidant Activity of CeO(2) Nanoparticles

Cerium oxide (CeO(2) ) nanoparticles display excellent antioxidant properties by scavenging free radicals. However, some studies have indicated that they can cause an adverse response by generating reactive oxygen species (ROS). Hence, it is important to clarify the factors that affect the oxidant/antioxidant activities of CeO(2) nanoparticles. In this work, we report the effects of different buffer anions on the antioxidant activity of CeO(2) nanoparticles. Considering the main anions present in the body, Tris-HCl, sulfate, and phosphate buffer solutions have been used to evaluate the antioxidant activity of CeO(2) nanoparticles by studying their DNA protective effect. The results show that CeO(2) nanoparticles can protect DNA from damage in Tris-HCl and sulfate systems, but not in phosphate buffer solution (PBS) systems. The mechanism of action has been explored: cerium phosphate is formed on the surface of the nanoparticles, which interferes with the redox cycling between Ce(3+) and Ce(4+) . As a result, the antioxidant activity of CeO(2) nanoparticles is greatly affected by the external environment, especially the anions. These results may provide guidance for the further practical application of CeO(2) nanoparticles.     

Synthesis of CeO2@SiO2 core-shell nanoparticles by water-in-oil microemulsion. Preparation of functional thin film

Synthesis of nanoparticles under restricted environment offered by water-in-oil (W/O) microemulsions provides excellent control over particle size and shape, and inter-particle spacing. Such an environment has been involved to synthesize silica nanoparticles with a CeO2 core, so-called CeO2@SiO2. Aqueous fluids made up of ceria nanoparticles with a size close to 5 nm have been used as the water phase component. The starting CeO2 sols and obtained CeO2@SiO2 nanoparticles have been characterized by dynamic light scattering (DLS), X-ray diffraction, scanning and transmission electron microscopy, and specific surface area measurements. The microemulsion process has been characterized by DLS. Preliminary results on CeO2@SiO2 thin films are presented.     

二氧化铈纳米微粒过氧化物酶活性及其在葡萄糖检测中的应用

合成了一种稳定和水溶性的聚丙烯酸修饰CeO2 NPs,利用动态光散射(DLS)、傅里叶变换红外光谱(FT-IR)和X射线光电子能谱(XPS)进行表征.结果表明,CeO2 NPs能够催化H2O2氧化3,3′,5,5′-四甲基联苯胺(TMB)发生显色反应,表现出过氧化物模拟酶催化活性.利用Raman和顺磁共振(EPR)光谱技术研究了其催化机理.基于CeO2 NPs催化TMB变色反应对H2O2浓度的依赖性和葡萄糖氧化酶能够催化溶解氧氧化葡萄糖产生H2O2的原理,构建了一种简单、灵敏、选择性高的测定血清中葡萄糖的检测方法.在优化条件下,测定葡萄糖的线性范围为0.5~10 mmol/L,检出限(3σ)为0.1 mmol/L.对1.0 mmol/L葡萄糖进行11次平行测定,其相对标准偏差为2.4%.该方法已成功用于血清样品中葡萄糖的测定.     

A new type of strong metal-support interaction and the production of H2 through the transformation of water on Pt/CeO2(111) and Pt/CeO(x)/TiO2(110) catalysts

The electronic properties of Pt nanoparticles deposited on CeO(2)(111) and CeO(x)/TiO(2)(110) model catalysts have been examined using valence photoemission experiments and density functional theory (DFT) calculations. The valence photoemission and DFT results point to a new type of "strong metal-support interaction" that produces large electronic perturbations for small Pt particles in contact with ceria and significantly enhances the ability of the admetal to dissociate the O-H bonds in water. When going from Pt(111) to Pt(8)/CeO(2)(111), the dissociation of water becomes a very exothermic process. The ceria-supported Pt(8) appears as a fluxional system that can change geometry and charge distribution to accommodate adsorbates better. In comparison with other water-gas shift (WGS) catalysts [Cu(111), Pt(111), Cu/CeO(2)(111), and Au/CeO(2)(111)], the Pt/CeO(2)(111) surface has the unique property that the admetal is able to dissociate water in an efficient way. Furthermore, for the codeposition of Pt and CeO(x) nanoparticles on TiO(2)(110), we have found a transfer of O from the ceria to Pt that opens new paths for the WGS process and makes the mixed-metal oxide an extremely active catalyst for the production of hydrogen.     

透明纳米CeO2的合成与表征

采用胶溶法合成了表面修饰十二烷基苯磺酸钠（DBS）的CeO2纳米粒子有机溶胶，探讨了制轩CeO2纳米有机溶胶的最佳实验条件TEM分析表明，CeO2（DBS）纳米粒子呈球形，约3nm，粒径分布均匀，无团聚现象。ED分析表明，CeO2（DBS）纳米粒子为多晶结构。     

棒状CeO_2负载Pt催化剂的合成及其电化学性能研究

通过水热法合成棒状纳米Ce O2(Ce O2-R),并将Pt纳米颗粒负载于Ce O2表面,制得甲醇燃料电池的阳极催化剂Pt/Ce O2-R.通过结构与形貌表征,结果表明,Pt/Ce O2-R中Ce O2的暴露晶面为(111)和(002)晶面,改变了Pt周围的电子结构,进而降低了Pt-COads的键能,释放出更多的活性位.另外,Pt纳米颗粒在Ce O2-R表面分散更均匀.利用电化学工作站测试阳极催化剂Pt/Ce O2-R在酸性溶液中的电化学性能,证明Pt/Ce O2-R催化剂的甲醇电氧化性能与抗CO毒害能力较颗粒状Ce O2负载Pt催化剂(Pt/Ce O2-P)都有很大的提高,证明Ce O2-R作为Pt纳米颗粒的载体用于直接甲醇燃料电池的阳极反应具有发展潜力.     

Density functional studies of model cerium oxide nanoparticles

Density functional plane-wave calculations have been performed to investigate a series of ceria nanoparticles (CeO2-x)(n), n Ce3+ reduction have been accounted for through the use of an effective on-site Coulomb repulsive interaction within the so-called DFT+U approach. Twelve nanoparticles of up to 2 nm in diameter and of both cuboctahedral and octahedral forms are chosen as representative model systems. Energetic and structural effects of oxygen vacancy formation in these nanoparticles are discussed with respect to those in the bulk and on extended surfaces. We show that the average interatomic distances of the nanoparticles are most significantly affected by the creation of oxygen vacancies. The formation energies of non-stoichiometric nanoparticles (CeO2-x)(n) are found to scale linearly with the average coordination number of Ce atoms; where x < 0 species, containing partially reduced O atoms, are less stable. The stability of octahedral ceria particles at small sizes, and the predicted strong propensity of Ce cations to acquire a reduced state at lower coordinated sites, is supported by interatomic potential-based global optimisations probing the low energy isomers of the Ce19O32 nanoparticle.     

氮掺杂TiO_2纳米线阵列优越的可见光光电性能(英文)

成功制备了氮掺杂锐钛矿TiO2纳米线,并研究了它的光电化学性质.结果表明,与商用P25 TiO2纳米粒子和未掺杂TiO2纳米线相比,氮掺杂TiO2纳米线作为光阳极明显地提高了光电转换效率(IPCE%),在可见光区有明显光吸收;在100 mW/cm2可见光光照下,氮掺杂TiO2纳米线具有最大的光电流密度和能量转换效率.例如,当电压为0.09 V(vs.Ag/AgC l)时最大能量转换效率为0.52%,均高于未掺杂TiO2纳米线和商用P25 TiO2纳米粒子的,充分表现出它优越的光响应和光电化学性能,在光电化学池、太阳能制氢等方面具有广泛的应用前景.     

硝酸盐制备三维有序大孔金属氧化物材料研究

用硝酸盐、柠檬酸和乙醇/水按一定摩尔比配置成前驱物溶液, 采用胶晶模板法, 制备了三维有序大孔金属氧化物材料: Al₂O₃, CeO₂, Cr₂O₃, NiO, MgO, In₂O₃, CeO₂/Al₂O₃, Cr₂O₃/Al₂O₃和NiO/Al₂O₃. SEM观察表明, 材料中大孔有序排列, 大孔间由小孔相连, 形成三维规则的笼状网络结构. XRD和TEM测试表明, 大孔孔壁由具有纳米尺寸的金属氧化物粒子组成. 实验表明, 加入乙醇、柠檬酸, 提高溶液对胶球润湿性, 改善溶液渗透能力, 避免粒子团聚, 有利于有序大孔结构的形成. 这一研究表明, 根据硝酸盐的物理化学性质, 调整溶液组成, 选择合适的热处理温度, 能得到大孔排列有序、三维规整性好的大孔结构材料. 此法具有原料易得, 操作简单的特点, 是3DOM材料的一种新型高效制备路线.     

Stabilization of miniemulsion droplets by cerium oxide nanoparticles: a step toward the elaboration of armored composite latexes

Stable methyl methacrylate (MMA) miniemulsions were successfully prepared using for the first time cerium oxide (CeO(2)) nanoparticles as solid stabilizers in the absence of any molecular surfactant. The interaction between MMA droplets and CeO(2) nanoparticles was induced by the use of methacrylic acid (MAA) as a comonomer. Both MAA and CeO(2) contents played a key role on the diameter and the stability of the droplets formed during the emulsification step. Cryo-transmission electron microscopy (TEM) images of the suspensions formed with 35 wt % of CeO(2) showed the presence of polydisperse 50-150 nm spherical droplets. More surprisingly, some nonspherical (likely discoidal) objects that could be the result of the sonication step were also observed. The subsequent polymerization of these Pickering miniemulsion droplets led to the formation of composite PMMA latex particles armored with CeO(2). In all cases, the conversion was limited to ca. 85%, concomitant with a loss of stability of the latex for CeO(2) contents lower than 35 wt %. This stability issues were likely related to the screening of the cationic charges present on CeO(2) nanoparticles upon polymerization. TEM images showed mostly spherical particles with a diameter ranging from 100 to 400 nm and homogeneously covered with CeO(2). Besides, for particles typically larger than 200 nm, a buckled morphology was observed supporting the presence of residual monomer at the end of the polymerization and consistent with the limited conversion. The versatility of these systems was further demonstrated using 35 wt % of CeO(2) and replacing MMA by n-butyl acrylate (BA) either alone or in combination with MMA. Stable monomer emulsions were always obtained, with the droplet size increasing with the hydrophobicity of the oil phase, pointing out the key influence of the wettability of the solid stabilizer. The polymerization of Pickering miniemulsion stabilized by CeO(2) nanoparticles proved to be an efficient strategy to form armored composite latex particles which may find applications in coating technology.     

Interrelated functionalities of hierarchically CNT/CeO2/Pt nanostructured layers: synthesis, characterization, and electroactivity

We present a free-standing catalyst layer comprising current collector/CNTs (catalyst support)/CeO(2)/Pt (catalyst) nanostructured layers, each layer constructed upon the one below it. FESEM and TEM showed that a CeO(2) layer has a fluffy morphology recalling the texture of cotton, whereas Pt nanoparticles assemble into cauliflower or broccoli-like arrangement. New insights have been gained into the effect of CeO(2) on the structural properties of the beneath CNTs layer and on the above Pt layer. First, by means of Raman analysis, it was found that interaction of CeO(2) with CNTs induced a decrease in the crystallinity of the latter. Second, by TEM and XPS analyses, it was observed that the size of Pt nanoparticles in the CNT/CeO(2)/Pt structure was inferior to that in the CNT/Pt, implying that CeO(2) influenced the dispersion quality of Pt nanoparticles. For the first time, it is observed that CeO(2) supported CNTs undergo oxidation/reduction reactions at low potentials in the ethanol electrolyte. The electrochemical analysis showed that entities produced from those redox processes are surface adsorbed/desorbed species most likely hydroxides. This unexpected electroactivity is due to the beneath CNTs that boosted the conductivity of CeO(2). Such improved conductivity of CeO(2) has fostered the electron-transfer kinetics of ethanol at Pt as demonstrated by the decreased overpotential required to oxidize ethanol and by the specific mass activity, which was greater than that of CNT/Pt.     

CeO2@Au核壳结构纳米粒子的合成与性质研究

采用沉淀法制备了球形CeO2纳米粒子,将其作为核粒子溶液,然后向其中滴加四氯合金酸溶液,在CeO2胶体表面利用柠檬酸钠还原[AuCl4]-离子,得到了CeO2@Au核壳结构纳米粒子。TEM分析表明,CeO2纳米粒子分散效果好,粒径为5 nm;CeO2@Au核壳粒子为球形,无团聚,平均粒径为15 nm。XRD分析表明,CeO2@Au核壳粒子为晶型结构,属于立方晶系,CeO2空间群为O5H-FM3M,Au的空间群为Fm-3m。UV-vis分析发现,CeO2@Au核壳粒子在300和520 nm处呈现出两个比较强的吸收峰,分别对应于CeO2胶体溶液的吸收峰和金粒子的表面等离子共振吸收峰。EDS分析了核壳结构CeO2@Au纳米粒子中存在Ce,O和Au 3种元素。XPS分析表明,Ce3d3/2和Au4f电子结合能与标准结合能相比发生了变化,说明CeO2与Au之间存在着相互作用。     

CeO2/BiVO4复合可见光催化剂的制备及其催化性能的研究

通过水热法制备了CeO2/BiVO4复合可见光催化剂,并采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、能量色散X射线光谱(EDX)和紫外-可见漫反射光谱对其晶体结构、表面形貌、化学组成以及光谱特性等进行了表征。此外还研究了光照时间、催化剂用量、不同染料、光照强度和重复使用次数对CeO2/BiVO4复合可见光催化剂和BiVO4在可见光照射下催化降解次甲基蓝活性的影响。结果表明:当光照时间为120 min,催化剂用量为1.00 g·L^-1及光照强度为1.00 mW·cm^-2时, CeO2/BiVO4复合可见光催化剂对次甲基蓝的催化降解效果最佳,并且有较高的稳定性。     

氧化铈纳米微粒的制备及其在金属钒钝化中的应用

用表面修饰法制备了氧化铈纳米微粒 ,并作为抗钒钝化剂的研究结果表明 ,纳米微粒浸渍到钒污染催化剂上可以钝化钒对催化剂的污染 ,改善裂化反应的产品分布。     

粒径可控纳米CeO_2的微乳液法合成

以十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/硝酸铈(Ce(NO3)3)水溶液(氨水)所形成的反相微乳液体系合成CeO2前驱体,利用热重(TG)和X射线衍射(XRD)分析方法确定了得到纳米CeO2的适宜焙烧温度为550℃,CeO2前驱体经550℃焙烧后得到纳米CeO2.采用XRD、透射电镜(TEM)、紫外-可见(UV-Vis)分光光度计等表征手段分别对纳米CeO2的晶形、形貌、粒径及紫外吸收性质进行了表征,该纳米CeO2粒子具有立方晶型结构,分散性较好、粒径范围为5-18nm.考察了微乳液中正辛烷与正丁醇质量比、Ce(NO3)3浓度对纳米CeO2粒径的影响,结果表明:利用微乳液法,通过改变微乳液中正辛烷与正丁醇质量比、Ce(NO3)3浓度能够对纳米CeO2粒径进行有效控制;纳米CeO2的粒径均随着正辛烷与正丁醇质量比和Ce(NO3)3浓度的增大而减小.同时,对不同条件下制得的纳米CeO2的紫外吸收性质进行了考察.     

氧化铈的结构对其热稳定性及催化丙烷氧化脱氢反应性能的影响

采用湿化学法制备了低维氧化铈的纳米棒和纳米颗粒,通过原位X射线粉末衍射、透射电镜和N2物理吸附等技术研究了氧化铈纳米结构对其热稳定性的影响.结果表明,氧化铈纳米棒的稳定性更高.采用浸渍法制备了氧化铈负载的氧化钒催化剂,并用于丙烷氧化脱氢反应中,发现以氧化铈纳米棒为载体的催化剂表现出更高的丙烯选择性,这可能是由于棒状结构的开放性有利于产物丙烯的直接扩散.     

CeO_2/Pt复合电极及其电催化特性

应用恒电位沉积(psd)和电位脉冲沉积(ppd)法在Pt基底制备CeO2/Pt复合电极,用能量色散X射线光谱(EDX)和X射线衍射(XRD)检测CeO2纳米粒子的成分和结构,场发射扫描电子显微镜(FESEM)观察样品形貌.结果表明:CeO2颗粒细小、致密.在KOH溶液中,CeO2/Pt对甲醇氧化和氧还原有电催化作用;若在稀硫酸中溶除CeO2/Pt电极(ppd)的部分CeO2,则电极的电催化作用进一步增强.     

纳米CeO2的制备及其在PMMA中的分散

制备得到一Ce-三乙醇胺(TEA)配合物,以该配合物作为制备纳米CeO2的前驱体.将甲基丙烯酸甲酯(MMA)分散于配合物水溶液中,然后在同一反应器中依次进行水解、乳液聚合反应,得到纳米CeO2分散于聚甲基丙烯酸甲酯(PMMA)基质中的复合物粉末.分别运用XRD,TEM,TGA和DSC对复合物进行了表征.结果表明,纳米CeO2粒径为3～5nm,其均匀分散于聚合物基质中且单分散性良好.聚合物的热稳定性和玻璃化温度得到提高.     

Sonochemical synthesis of cerium oxide nanoparticles-effect of additives and quantum size effect

Cerium oxide (CeO(2)) nanoparticles were prepared sonochemically, by using cerium nitrate and azodicarbonamide as starting materials, and ethylenediamine or tetraalkylammonium hydroxide as additives. The additives have a strong effect on the particle size and particle size distribution. CeO(2) nanoparticles with small particle size and narrow particle size distribution are obtained with the addition of additives; while highly agglomerated CeO(2) nanoparticles are obtained in the absence of additives. Monodispersed CeO(2) nanoparticles with a mean particle size of ca. 3.3 nm are obtained when tetramethylammonium hydroxide (TMAOH) is used as the additive and the molar ratio of cerium nitrate/azodicarbonamine/TMAOH is 1/1/1. Blue shifts of the absorption peak and the absorption edges of the products are observed in the UV-Vis absorption spectra as a result of the quantum size effect. The samples have been characterized using powder XRD, TEM, DLS, and absorption spectra.