电解液体系对TiO_2纳米管阵列形貌及光催化性能的影响

采用阳极氧化法制备出TiO_2纳米管阵列,对比了3种电解液体系[(a)氢氟酸+硫酸+水、(b)氟化钠+甘油+水、(c)氟化铵+乙二醇]对纳米管阵列形貌及光催化性能的影响。结果表明:3种电解液体系中制备出了不同长径比的TiO_2纳米管阵列,样品经450℃热处理后,主要为锐钛矿相TiO_2,同时具有良好的紫外光吸收能力,并在可见光范围内产生不同程度的波动。其中电解液(b)制备出的纳米管因具有合适的长径比而表现出优异的光催化降解气相苯的性能。     

晶面调控和新型二氧化钛纳米结构的研究进展

太阳能光催化技术在缓解环境污染压力和能源危机方面有着重要的应用前景,纳米结构TiO_2以其催化活性高、稳定性好、环境友好等特点在光催化领域受到广泛关注。近期研究表明,锐钛矿TiO_2不同晶面能够有效地促进光激发载流子的空间分离转移。锐钛矿TiO_2中光激发产生的电子倾向于迁移至(101)表面,而空穴则移动至(001)表面,从而通过晶面调控即可实现光生载流子的定向转移。另外,锐钛矿TiO_2介晶是一类具有特殊结构和性质的纳米材料,其高的结晶性和大的比表面积有利于光催化反应的进行,多级TiO_2纳米结构和具有特殊活性的TiO_2也是目前研究的一个趋势-综述了几种高能量晶面暴露锐钛矿TiO_2纳米晶、锐钛矿TiO_2介晶以及多级复杂纳米结构TiO_2的合成,分析了光催化剂结构对光催化性能的影响,重点探讨了晶面调控TiO_2光催化的机理,总结了新兴发展的光还原活性TiO_2的合成及其在可逆光致变色体系和光打印可擦写纸张领域的新型应用。     

不同暴露比例(001)晶面锐钛矿相TiO2纳米方块的合成及气敏性能

在众多提高TiO_2气敏性能的尝试中,晶面调控的方法引起了极大的关注。主要通过调整水热反应的制备工艺,实现TiO_2的(001)晶面暴露不同比例,对其进行气敏性能的研究。通过改变反应物浓度完成了一系列不同晶面暴露比的TiO_2纳米方块的可控水热合成,实现了对TiO_2纳米方块形貌以及晶面的调控。合成TiO_2纳米方块暴露(001)晶面的比例从33.33%增加到83.33%。随(001)晶面暴露比例的提高,对于丙酮气体的灵敏度从14.3提高到了27.8。     

具有高活性(001)晶面的TiO2纳米方块的制备及光催化性能

采用水热法制备了尺寸为70~100 nm, 具有高活性(001)晶面的锐钛矿相TiO₂纳米方块, 利用FE-SEM、TEM、XRD和UV-Vis DRS等手段对催化剂结构和光吸收性能进行分析, 同时考察了水热反应温度和溶液pH对TiO₂形貌和(001)晶面暴露率的影响。以酸性红染料为目标污染物, 对催化剂的光催化活性进行研究。实验结果表明, 合成TiO₂纳米方块的最佳条件为水热温度180℃、溶液pH=4~5。(001)晶面的光催化活性优于(101)晶面, 具有33%(001)晶面暴露率的TiO₂纳米方块的光催化活性是普通TiO₂的1.6倍。     

载Pt-TiO2纳米管阵列制备及其光电催化性能

采用阳极氧化法在纯钛箔表面制备TiO2纳米管,再用直流电沉积法在纳米管内沉积Pt,制备出载Pt-TiO2纳米管电极.并采用场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)对其进行表征.研究载Pt-TiO2纳米管阵列与TiO2纳米管阵列对有机磷农药敌敌畏(DDVP)的光电催化降解效果,并与光催化、电降解做了简单对比.结果表明:所制Pt-TiO2纳米管存在锐钛矿晶型TiO2,其饱合光电流比TiO2纳米管大.与单独光催化、电降解相比,载Pt-TiO2纳米管电极光电催化降解效果更显著.     

改进的二次阳极氧化法制备表面平整的TiO_2纳米管阵列

在钛基体上采用改进的二次阳极氧化法制得了结构规整均匀有序的TiO_2纳米管阵列。利用FESEM、XRD等对产品的微观形貌和结构晶型进行了表征和分析,通过光催化降解甲基橙评价了TiO_2纳米管阵列的光催化活性。研究结果表明,改进的二次阳极氧化法制备的TiO_2纳米管阵列克服了常规二次阳极氧化法制备的纳米管两次氧化的纳米孔道不重合的缺陷,制备出大面积表面平整的TiO_2纳米管阵列。     

两步水热法制备还原氧化石墨烯/纳米TiO_2复合材料及其光催化性能

为研究由还原氧化石墨烯(RGO)和具有高活性晶面的TiO_2组成的复合材料的制备方法及其光催化性能,首先采用两步水热法制备了RGO/纳米TiO_2复合材料:第1步为合成暴露高活性晶面的纳米TiO_2;第2步为将合成的纳米TiO_2与氧化石墨烯(GO)复合,形成RGO/纳米TiO_2复合材料。然后,利用XRD、SEM、X射线光电子能谱仪和紫外-可见漫反射光谱等手段对制备的暴露不同晶面的纳米TiO_2和RGO/纳米TiO_2复合材料进行了表征,评价了其光催化性能。结果表明:在水热法的第1步中,通过调节HF的浓度能可控制备出具有高活性的(001)和(101)晶面的纳米TiO_2,氟原子在纳米TiO_2中以物理吸附态和化学结合态这2种形态存在;在第2步后,GO与纳米TiO_2复合形成RGO/纳米TiO_2复合材料,同时在此过程中GO被转化成RGO。在紫外光照射下,两步水热法合成的RGO/纳米TiO_2复合材料具有很好的光催化性能,明显优于商用TiO_2(P25)和纳米TiO_2的。RGO/纳米TiO_2复合材料的光催化性能有明显的提高,RGO和TiO_2暴露的晶面对光催化活性有影响。     

AgX(Cl,Br)-TiO_2复合材料光电化学研究

以阳极氧化法制备的高度有序TiO_2纳米管阵列作为基底,用沉积法在TiO_2纳米管上复合Ag Cl和Ag Br纳米颗粒形成Ag X-TiO_2异质结。采用XRD、FESEM等分析结果表征,结果表明:Ag Cl以厚度为50 nm、长度为1?m的片状结构堆叠分布,Ag Br的沉积过程较温和,沉积速度相对更慢,均匀分散在TiO_2纳米管表面;随着沉积次数增加,纳米管阵列表面形貌发生改变。光电化学研究表明:样品经过复合Ag Br后,可以有效提高TiO_2纳米管阵列的光电转化效率,当Ag Br沉积1次时,其光电转化效率达到2.67%,而复合的Ag Cl对于TiO_2纳米管阵列的光电效率改善效果欠佳。     

Ag/TiO2纳米管阵列等离子体光催化剂的制备及性能研究

以阳极氧化法制备的二氧化钛(TiO_2)纳米管阵列为基底,利用化学还原法制备了不同银(Ag)含量的Ag/TiO_2复合薄膜,并对其进行表征。结果表明,化学还原法有利于Ag纳米颗粒在TiO_2纳米管上的均匀分布,Ag能产生表面等离子体共振吸收,有效增强TiO_2纳米管阵列对可见光的吸收能力,Ag的修饰大幅度提高了TiO_2纳米管阵列对气相苯的光催化降解活性,在光催化反应80min条件下,Ag含量为2%(wt,质量分数)制得的Ag/TiO_2复合薄膜光催化活性最佳,对气相苯的降解率达到97%。     

TiO2纳米管晶型对钛生物活性的影响

利用阳极氧化法在HF电解液体系中制备了高有序TiO2纳米管。样品分别在400和600℃下热处理后,得到锐钛矿和金红石两种晶型的TiO2纳米管。对样品进行了表征,将样品浸泡于模拟体液中,观察表面HA沉积情况,并进行体外细胞毒性实验以探讨样品的生物相容性。结果发现,400和600℃退火处理的纳米管样品生物活性高于未退火处理样品,400℃退火处理纳米管活性高于600℃退火处理纳米管。由于不同后处理条件下制备的纳米管形貌相似,仅为晶型不同,故推断出锐钛矿型TiO2生物活性最好,金红石型TiO2次之,无定型TiO2生物活性相对最差。     

Enhanced photoelectrochemical cell property from alpha-Fe2O3 nanoparticle decoration on vertically grown TiO2 nanotubes arrays

TiO2 nanotube arrays decorated with alpha-Fe2O3 were prepared by forming a nanotube-like TiO2 film on a Ti sheet using an anodization process, followed by electrochemical deposition to decorate hematite (alpha-Fe2O3) nanoparticles on the TiO2 nanotube arrays. The SEM and XRD results revealed that the alpha-Fe2O3 nanoparticles were homogeneously embedded on the surface of the TiO2 nanotube arrays. The photoelectrochemical properties of the alpha-Fe2O3/TiO2 nanotube arrays as photoanode were studied by photocurrent-potential behavior in 1 M NaOH electrolyte under 100 mW/cm2 UV-Visible light irradiation. Also, the length dependence of TiO2 nanotubes and the amount dependence of alpha-Fe2O3 nanoparticles on the photocatalytic ability were studied and thus the optimum conditions were determined.     

Mesocrystalline TiO<Subscript>2</Subscript> nanosheet arrays with exposed {001} facets: Synthesis via topotactic transformation and applications in dye-sensitized solar cells

A facile,fluorine-free approach for synthesizing vertically aligned arrays of mesocrystalline anatase TiO2 nanosheets with highly exposed {001} facets was developed through topotactic transformation.Unique mesocrystalline {001}-faceted TiO2 nanosheet arrays vertically aligned on conductive fluorine-doped tin oxide glass were realized through topotactic conversion from single-crystalline precursor nanosheet arrays based on lattice matching between the precursor and the anatase crystals.The morphology and microstructure of the {001}-faceted TiO2 nanosheets could be readily modulated by changing the reactant concentration and annealing temperature.Owing to enhanced dye adsorption,reduced charge recombination,and enhanced light scattering arising from the exposed {001} facets,in addition to the advantageous features of low-dimensional structure arrays (e.g.,fast electron transport and efficient charge collection),the obtained TiO2 nanosheet arrays exhibited superior performance when they were used as anodes for dye-sensitized solar cells (DSSCs).Particularly,{001}-faceted TiO2 nanosheet arrays ～15 μm long annealed at 500 ℃ showed a power conversion efficiency of 7.51％.Furthermore,a remarkable efficiency of 8.85％ was achieved for a DSSC based on double-layered TiO2 nanosheet arrays ～35 μm long,which were prepared by conversion from the precursor nanoarrays produced via secondary hydrothermal growth.     

电解液组分对阳极氧化法制备TiO_2纳米管的影响

在不同电解液组分中采用阳极氧化法制备了不同结构参数的TiO2纳米管,考察了不同电解液组分对TiO2纳米管形貌和尺寸参数的影响.采用场发射扫描电子显微镜(SEM)和X射线衍射仪(XRD)对纳米管的形貌和结构进行了表征,并分析了电解液组分对纳米管生长的影响机制.结果表明,降低电解液中H+浓度以及减少电解液中H2O的含量可有效提高纳米管的长度.     

Synthesis of Fe(2)O(3)/TiO(2) nanorod-nanotube arrays by filling TiO(2) nanotubes with Fe

Synthesis of hematite (α-Fe(2)O(3)) nanostructures on a titania (TiO(2)) nanotubular template is carried out using a pulsed electrodeposition technique. The TiO(2) nanotubes are prepared by the sonoelectrochemical anodization method and are filled with iron (Fe) by pulsed electrodeposition. The Fe/TiO(2) composite is then annealed in an O(2) atmosphere to convert it to Fe(2)O(3)/TiO(2) nanorod-nanotube arrays. The length of the Fe(2)O(3) inside the TiO(2) nanotubes can be tuned from 50 to 550?nm by changing the deposition time. The composite material is characterized by scanning electron microscopy, transmission electron microscopy and diffuse reflectance ultraviolet-visible studies to confirm the formation of one-dimensional Fe(2)O(3)/TiO(2) nanorod-nanotube arrays. The present approach can be used for designing variable one-dimensional metal oxide heterostructures.     

Fabrication of highly ordered TiO2 nanotube arrays via anodization of Ti-6Al-4V alloy sheet

Uniform and highly ordered TiO2 nanotube arrays were fabricated by the electrochemical anodic oxidation on Ti-6Al-4V surface, using graphite plate as cathode and ethylene glycol (EG) with addition of a certain amount of H2O and NH4F as electrolyte, and the anodization voltage went up to a presetting voltage by stepwise increment. The morphology, structure and composition of TiO2 nanotube arrays were characterized by SEM, EDS, XRD and XPS. The formation process of TiO2 nanotubes was introduced in brief. The experiments were arranged by an orthogonal experiment method and the experimental results showed that the formation of TiO2 nanotube arrays was influenced by not only each factor (F- content, H2O content, external voltage and duration), but also cross correlation among the four factors. The optimal condition was F- content 0.2 wt%, H2O content 4 vol%, external voltage 40 V and duration 1 h in the studied electrochemical system, and the length of obtained nanotubes was 1.5 microm, the outer diameter was approximately 100 nm and the aspect ratio was 15. As-formed nanotube arrays were amorphous and changed to anatase TiO2 after annealed at 500 degrees C for 2 h in air ambience. XPS survey spectra revealed the surface of as-formed nanotube arrays containing Ti, O, C, F and N. The nanotube arrays on Ti-6Al-4V surface with better thermo-stability and crystallinity would have great potential in biomaterials.     

不同阳极氧化条件下TiO_2纳米管阵列的制备及表征

分别在三种不同的电解液中,以钛为基体采用阳极氧化的方法制备了TiO2纳米管阵列薄膜,用SEM观察纳米管阵列薄膜的形貌、测量纳米管管径大小;用XRD、拉曼光谱检测TiO2纳米管阵列薄膜热处理前后的晶型.结果表明:不同的电解液体系和氧化电压下得到的纳米管形貌各不相同.在0.24wt%HF水溶液中得到的TiO2纳米管排列整齐,管径为110nm;在0.5wt%NaF+2.7wt%Na2SO4水溶液和0.88wt%NH4F的丙三醇-水(体积比1:1)混合溶液中得到的纳米管排列不规整,管径为100nm;在0.24wt%HF条件下生成的TiO2纳米管管径与氧化电压成线性关系:d=k×U+b,其中,系数k=5.2nm/V,b=2.2nm,0≤U≤25V.经450℃热处理2h后TiO2纳米管结构由无定形态转变为锐钛矿.     

An innovative approach to synthesize highly-ordered TiO2 nanotubes

An innovative route to prepare highly-ordered and dimensionally controlled TiO2 nanotubes has been proposed using a mild sonication method. The nanotube arrays were prepared by the anodization of titanium in an electrolyte containing 3% NH4F and 5% H2O in glycerol. It is demonstrated that the TiO2 nanostructures has two layers: the top layer is TiO2 nanowire and underneath is well-ordered TiO2 nanotubes. The top layer can easily fall off and form nanowires bundles by implementing a mild sonication after a short annealing time. We found that the dimensions of the TiO2 nanotubes were only dependent on the anodizing condition. The proposed technique may be extended to fabricate reproducible well-ordered TiO2 nanotubes with large area on other metals.     

Dye-sensitized solar cells based on thick highly ordered TiO(2) nanotubes produced by controlled anodic oxidation in non-aqueous electrolytic media

Dye-sensitized solar cells (DSSCs) were prepared using TiO(2) nanotubes, grown by controlled Ti anodic oxidation in non-aqueous media. Smooth, vertically oriented TiO(2) nanotube arrays, presenting a high degree of self-organization and a length of 20 μm, have been grown using ethylene glycol electrolyte containing HF. As-grown nanotubes exhibit an amorphous structure, which transforms to the anatase TiO(2) crystalline phase upon post-annealing in air at 450?°C. Atomic force microscopy (AFM) revealed the porous morphology together with high roughness and fractality of the surface. The annealed tubes were sensitized by the standard N719 ruthenium dye and the adsorption was characterized using resonance micro-Raman spectroscopy and adsorption-desorption measurements. The sensitized tubes were further used as active photoelectrodes after incorporation in sandwich-type DSSCs using both liquid and solidified electrolytes. The efficiencies obtained under air mass (AM) 1.5 conditions, using a back-side illumination geometry, were very promising: 0.85% using a composite polymer redox electrolyte, while the efficiency was further increased up to 1.65% using a liquid electrolyte.     

Anatase TiO₂ crystal facet growth: mechanistic role of hydrofluoric acid and photoelectrocatalytic activity

This work reports a facile hydrothermal approach to directly grow anatase TiO(2) crystals with exposed {001} facets on titanium foil substrate by controlling pH of HF solution. The mechanistic role of HF for control growth of the crystal facet of anatase TiO(2) crystals has been investigated. The results demonstrate that controlling solution pH controls the extent of surface fluorination of anatase TiO(2), hence the size, shape, morphology, and {001} faceted surface area of TiO(2) crystals. The theoretical calculations reveal that {001} faceted surface fluorination of anatase TiO(2) can merely occur via dissociative adsorption of HF molecules under acidic conditions while the adsorption of Na(+)F(-) is thermodynamically prohibited. This confirms that the presence of molecular form of HF but not F(-) is essential for preservation of exposed {001} facets of anatase TiO(2). Anatase TiO(2) crystals with exposed {001} facets can be directly fabricated on titanium foil by controlling the solution pH ≤ 5.8. When pH is increased to near neutral and beyond (e.g., pH ≥ 6.6), the insufficient concentration of HF ([HF] ≤ 0.04%) dramatically reduces the extent of surface fluorination, leading to the formation of anatase TiO(2) crystals with {101} facets and titanate nanorods/nanosheets. The anatase TiO(2) nanocrystals with exposed {001} facets exhibits a superior photoelectrocatalytic activity toward water oxidation. The findings of this work clarify the mechanistic role of HF for controlling the crystal facet growth, providing a facile means for massive production of desired nanostructures with high reactive facets on solid substrates for other metal oxides.     

HF酸电解液浓度对TiO2纳米阵列结构的影响

TiO2纳米阵列(纳米管、纳米棒)结构具有良好的力学性能、化学稳定性以及抗腐蚀性能,在许多技术领域具有广阔的应用前景。采用阳极氧化法在工业纯钛片表面制备出高度有序的TiO2纳米管阵列和纳米棒阵列,研究了电解液浓度和阳极氧化时间对TiO2纳米阵列结构的影响,并对其形成机理进行了初步探讨。结果表明,低浓度的HF酸电解液有利于制备纳米管阵列,高浓度的HF酸电解液有利于制备纳米棒阵列。