Au负载N掺杂TiO2纳米管阵列的制备及其性能

TiO₂ 纳米管阵列较大的禁带宽度是导致其光催化效率较低的重要原因,采用磁控溅射、阳极氧化以及气氛退火相结合的方法对 TNAs 改性后制备了 Au 负载 N 掺杂 TiO₂ 纳米管阵列(Au@ N-TNAs),然后以甲基橙为目标污染物, 进一步分析了 Au@ N-TNAs 在不同 Au 负载量时光降解效率的变化情况。 采用 SEM、XRD、TEM 和 X 射线光电子能谱 (XPS)等对 Au 和 N 在 Au@ N-TNAs 中的存在形式进行表征和分析,发现 Au 主要是负载在 TiO₂ 纳米管阵列上,而 N 元素则是以掺杂的方式进入 TiO₂ 纳米管阵列的晶格中。 此外,在光降解试验中发现通过 Au 负载与 N 掺杂相结合的方法对 TiO₂ 纳米管阵列进行复合改性后,TiO₂ 纳米管阵列的光催化效率得到显著提升,其中 20s-Au@ N-TNAs 具有最佳的光降解效率。 但 Ti-N 薄膜中间的 Au 层太厚时会影响阳极氧化过程中 TiO₂ 纳米管阵列的生长,而且过量的 Au 在退火处理时很难及时地扩散均匀,进而使得改性后的 TiO₂ 纳米管阵列(40s-Au@ N-TNAs)的光催化效率明显降低。     

新型TiO2 NTs制备和结构控制及其硝基苯光催化性能研究

实验采用二次阳极氧化法制备高度有序的阵列式TiO2纳米管（TiO2 NTs）,分别利用扫描电镜（SEM）、能谱仪（EDS）、X射线衍射仪（XRD）和紫外-可见漫反射光谱仪（UV-vis DRS）对制得的TiO2 NTs的微观形貌及光响应范围进行表征与测试。SEM显示经过二次阳极氧化处理后,TiO2 NTs的形貌发生较大改变,呈现出良好的阵列效果。UV-vis DRS光谱显示光响应范围明显发生红移。将硝基苯作为目标有机污染物,利用TiO2 NTs作为光催化剂对其进行光催化降解。结果显示,TiO2 NTs能有效降解废水中的硝基苯,并且经二次阳极氧化制得的阵列式TiO2纳米管（2-step TiO2 NTs）的光催化活性远远优于经一次氧化的TiO2纳米管（1-step TiO2 NTs）,能显著提高对硝基苯的降解效率。推测活性增加的原因是经二次氧化形成的阵列式双层纳米管结构增大了催化剂的比表面积,同时增加光通道,使TiO2纳米管吸光范围显著增大,提升硝基苯的降解速率。     

SnO2@TiO2核-壳纳米线的制备及其光催化性能研究

本文通过固-液-气(VLS)生长机制,利用化学气相沉积法(CVD)制备SnO₂纳米线。利用原子层沉积(ALD)以钛酸四异丙酯为前驱体在SnO₂纳米线表面沉积不同厚度的TiO₂壳层,形成SnO₂@TiO₂核-壳纳米线结构。通过中间Al₂O₃插层,分别制备出金红石和锐钛矿两种不同晶型的TiO₂,从而制备出两种不同复合结构的SnO₂@TiO₂核-壳纳米线。实验研究该复合结构中TiO₂的厚度与晶型对紫外光下光催化降解甲基橙溶液活性的影响。     

铜掺杂TiO2纳米管阵列薄膜的制备及表征

本文提出了一种磁控溅射和阳极氧化相结合制备Cu掺杂TiO₂纳米管(Cu-TNT)阵列的方法。掺杂后的样品通过扫描电镜(SEM)、X射线衍射(XRD)、透射电镜(TEM)和X射线光电子能谱(XPS)等手段对其结构和光电性能做了研究与分析。研究结果表明：Cu以离子形态均匀地掺杂进入TiO₂纳米管中,且为取代掺杂;Cu掺杂对TiO₂纳米管(TNT)的生长具有抑制作用,对TNT的形貌有明显影响;Cu掺杂对TNT晶体生长取向也有明显影响,抑制锐钛矿(101)晶面的生长,使(101)晶面产生晶格畸变、晶面间距变宽并促进锐钛矿(004)晶面的择优生长。瞬态光电流响应分析表明Cu掺杂TNT有利于抑制光生电子-空穴对的复合速率,提高太阳能利用率。     

Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

飞秒激光刻蚀微结构对NaOH水热法制备TiO_2光催化性能的影响

Ti基底三维微纳米结构TiO_2(3D-TiO_2)具有比表面积大、光捕获能力强、电荷传输快、可循环利用的优点,在光催化领域具有重要的研究意义和应用前景。采用飞秒激光刻蚀复合Na OH水热法制造Ti基底3D-TiO_2,并研究飞秒激光刻蚀的微阵列结构对3D-TiO_2光催化性能的影响。采用激光共聚焦显微镜(LSCM)、SEM、TEM、XRD对3DTiO_2进行表征分析,并对3D-TiO_2在紫外光照下进行甲基橙降解性能测试。结果表明,复合方法制备的3D-TiO_2由飞秒激光刻蚀的微阵列和Na OH水热法制备的TiO_2纳米线组成。与采用Na OH水热法直接在平整Ti表面制备的TiO_2纳米线相比,3D-TiO_2的染料吸附能力提升100%,光催化性能提升37%。微阵列结构尺寸对3D-TiO_2的性能具有明显影响,随着微阵列宽度的减小或高度的增加,3D-TiO_2的比表面积增大、入射光反射率降低、光催化性能提高。     

水热法制备C3N4/CuGaO2 复合物及其气敏性能

采用简单水热法合成了一系列C₃N₄/CuGaO₂复合材料。采用XRD、SEM、TEM和XPS对制备的样品进行了表征。研究了一系列C₃N₄/CuGaO₂复合材料的气敏性能。结果表明,基于C₃N₄/CuGaO₂-0.3复合材料（C₃N₄与CuGaO₂的摩尔比为0.3:1）的气体传感器对甲苯的传感性能优于CuGaO₂传感器。相比较于CuGaO₂传感器的工作温度（140 ℃）,C₃N₄/CuGaO₂-0.3复合材料传感器的最佳工作温度仅为25 ℃,对100 μL/L甲苯气体的响应达到28,检出限低至0.01 μL/L。对100 μL/L甲苯气体的响应时间和恢复时间分别为114.2和27.4 s。此外,用于检测甲苯的C₃N₄/CuGaO₂-0.3复合材料传感器还具有优异的长期稳定性、良好的重复性和优异的抗湿性能。     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

W18O49@Cu2O纳微米复合材料的制备及其光催化性能研究

本文首先用热蒸发方法制备得到了W₁₈O₄₉纳微米棒,然后经醋酸铜饱和溶液浸泡后再热处理的办法成功在W₁₈O₄₉纳微米棒表面负载Cu₂O制得得到了W₁₈O₄₉@Cu₂O纳微米复合材料;采用X-射线衍射仪、扫描电子显微镜、X-射线能谱分析及透射电子显微镜对样品进行分析表征;最后选用亚甲基蓝溶液作为目标降解物模拟污水处理测试材料的光催化性能。实验结果表明,W₁₈O₄₉纳微米棒在饱和醋酸铜溶液中浸泡时间越长,所得到的催化剂中Cu₂O的负载量越多,且所制备的W₁₈O₄₉@Cu₂O的纳微米复合材料相对于纯W₁₈O₄₉纳微米棒,其光催化效率得到了显著提高。     

Ni2Cr(BO3)O2涂层的制备及其红外发射性能

通过喷雾造粒和高温焙烧制备Ni_2Cr(BO_3)O_2粉末后利用等离子喷涂得到一种高红外发射涂层,并研究了该种涂层的红外发射性能。SEM观察涂层的表面、断面形貌,发现涂层与基体结合紧密、无脱落;XRD对焙烧后的粉末物相组成进行了表征,主要以Ni_2Cr(BO_3)O_2为主。对涂层红外波段发射率的测试表明,在0.76~2.5μm波段的发射率为0.896、2.5~14μm波段发射率为0.925,具有优异的红外发射性能。Ni_2Cr(BO_3)O_2晶胞内的畸变、非对称性以及电子转移跃迁是导致Ni_2Cr(BO_3)O_2这种材料具有高红外发射率的主要原因。Ni_2Cr(BO_3)O_2涂层能够经受37次"900℃~水冷"热震循环。该种涂层由于其高红外发射性能、优异的耐热震性能和热稳定性能而具有较高的实用价值。     

Modification of Parylene film-coated glass with TiO2 nanoparticles and its photocatalytic properties

A titania film was deposited on Parylene-coated glass by a one-step, ultrasound-assisted procedure. The TiO₂ nanoparticles formed during the sonochemical hydrolysis of Ti(i-OPr)₄ were thrown to the surface and strongly attached to the Parylene substrate. By using different solvents (water, ethanol or their mixture) and reagent concentrations, the thickness, uniformity and crystallinity of the deposited layer were regulated. PVP was used to stabilize the highly homogeneous distribution of TiO₂ nanocrystals on the Parylene surface. The morphology and structure of the coated films were characterized by physical and chemical methods such as: X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), Rutherford backscattering spectrometry (RBS), and optical spectroscopy. The photocatalytic activity of the titania-modified Parylene film in the photo discoloration of methylene blue was demonstrated. The experimental results revealed a correlation between the uniformity of the nanostructured anatase titania film and its photocatalytic properties.     

N-doped TiO2/ZnO composite powder and its photocatalytic performance for degradation of methyl orange

The N-doped TiO₂/ZnO composite powder with a molar ratio of Ti to Zn of 3/1 was prepared via sol–gel process and then ammonia treated with NH₃ mass fractions of 0%, 7%, and 28% for 24 h at room temperature followed by thermal calcinations in air for 2 h at various temperatures of 500, 600, and 700 °C. The as-prepared composite powder was characterized in detail through thermo-gravimetric analyzer, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The results showed that the phase transformation of anatase to rutile has been successfully retarded via the ammonia treating process, leading to the presence of anatase phase in the composite. The particle crystallization of the composite powder was significantly promoted with the increase of the calcining temperature. The photocatalysis evaluation through MO degradation revealed an enhanced photocatalytic activity for the composite powder that might be related to the good crystallization, the presence of anatase phase, and the particle size reduction of the powder.     

Effect of Nd2O3 addition on the surface phase of TiO2 and photocatalytic activity studied by UV Raman spectroscopy

TiO₂ modified with Nd₂O₃ (Nd-TiO₂) nanoparticles were prepared by a co-precipitation method and utilized as the photocatalysts for the degradation of Rhodamine B (RhB). The influence of Nd₂O₃ on the bulk and surface phase, surface area, particle size, and optical response of TiO₂ was investigated by X-ray diffraction (XRD), UV Raman spectroscopy, transmission electron microscopy (TEM), BET, and UV-visible diffuse reflectance spectra. It is found that the crystalline phase and phase composition in the bulk and surface region of Nd-TiO₂ calcined at high temperatures can be tuned by changing the amount of Nd₂O₃. Based on the results from XPS, EDX, XRD, and UV Raman spectra, it is assumed that Nd³⁺ ions do not enter the TiO₂ lattice, but highly disperse onto the Nd-TiO₂ particle surface in the form of Nd₂O₃ crystallites. These crystallites inhibit the agglomeration, growth in crystal size, and anatase-to-rutile phase transformation of TiO₂. In the photocatalytic degradation of RhB reaction, Nd-TiO₂ nanoparticles with higher surface area and wider optical response are more reactive in case of the same surface anatase phase. When the mixed phases of anatase and rutile exist in the surface region of Nd-TiO₂, the synergetic effect over surface area and optical response is the important parameter which determines optimal photocatalytic activity.     

Microstructure characterization and photocatalytic activity of mesoporous TiO2 films with ultrafine anatase nanocrystallites

A series of mesoporous TiO₂ films on borosilicate glass with ultrafine anatase nanocrystallites were successfully synthesized using a non-acidic sol gel preparation route, which involves the use of nonionic surfactant Tween 20 as template through a self assembly pathway. The microstructure of these TiO₂ films was characterized by XRD, SEM, HR-TEM, UV-Vis spectroscopy, and N₂ adsorption-desorption isotherm analysis. Their photocatalytic activities were investigated by using creatinine as a model organic contaminate in water. It was found that all mesoporous TiO₂ films prepared with Tween 20 exhibited a partially ordered mesoporous structure. The photocatalytic activity of the TiO₂ films could be remarkably improved by increasing Tween 20 loading in the sol at the range of 50% (v/v), which yielded large amount of catalyst (anatase) on the glass support and enhanced specific surface area. The optimum Tween 20 loading was 50% (v/v) in the sol, above which good adhesion between TiO₂ films and borosilicate glass could not be maintained. The final TiO₂ film (Tween 20: final sol = 50%,v/v) exhibits high BET surface area (∼ 120 m²/g) and pore volume (0.1554 cm³/g), ultrafine anatase nanocrystallinity (7 nm), uniform and crack free surface morphology, and improved photocatalytic activity.     

Photocatalytic performance of nano-photocatalyst from TiO2 and Fe2O3 by mechanochemical synthesis

Nano-particles of homogeneous solid solution between TiO₂ and Fe₂O₃ (up to 10 mol%) have been prepared by mechanochemical milling of TiO₂ and yellow Fe₂O₃/red Fe₂O₃/precipitated Fe (OH)₃ using a planetary ball mill. Such novel solid solution cannot be prepared by conventional co-precipitation technique. A preliminary investigation of photocatalytic activity of mixed oxide (TiO₂/Fe₂O₃) on photo-oxidation of different organic dyes like Rhodamine B (RB), Methyl orange (MO), Thymol blue (TB) and Bromocresol green (BG) under visible light (300-W Xe lamp; λ > 420 nm) showed that TiO₂ having 5 mol% of Fe₂O₃ (YFT1) is 3-5 times higher photoactive than that of P25 TiO₂. The XRD result did not show the peaks assigned to the Fe components (for example Fe₂O₃, Fe₃O₄, FeO₃, and Fe metal) on the external surface of the anatase structure in the Fe₂O₃/TiO₂ attained through mechanochemical treatment. This meant that Fe components were well incorporated into the TiO₂ anatase structure. The average crystallite size and particle size of YFT1 were found to be 12 nm and 30 ± 5 nm respectively measured from XRD and TEM conforming to nanodimensions. Together with the Fe component, they absorbed wavelength of above 387 nm. The band slightly shifted to the right without tail broadness, which was the UV absorption of Fe oxide in the Fe₂O₃/TiO₂ particle attained through mechanochemical method. This meant that Fe components were well inserted into the framework of the TiO₂ anatase structure. EPR and magnetic susceptibility show that Fe³⁺ is in low spin state corresponding to μ_B = 1.8 BM. The temperature variation of μ_B shows that Fe³⁺ is well separated from each other and does not have any antiferromagnetic or ferromagnetic interaction. The evidence of Fe³⁺ in TiO₂/Fe₂O₃ alloy is also proved by a new method that is redox titration which is again support by the XPS spectrum.     

Modification of TiO2 nanorods by Bi2MoO6 nanoparticles for high performance visible-light photocatalysis

In this work, TiO₂ nanorods were prepared by a hydrothermal process and then Bi₂MoO₆ nanoparticles were deposited onto the TiO₂ nanorods by a solvothermal process. The nanostructured Bi₂MoO₆/TiO₂ composites were extensively characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Bi₂MoO₆/TiO₂ composites was evaluated by degradation of methylene blue. The Bi₂MoO₆/TiO₂ composites exhibit higher catalytic activity than pure Bi₂MoO₆ and TiO₂ for degradation of methylene blue under visible light irradiation (λ > 420 nm). Further investigation revealed that the ratio of Bi₂MoO₆ to TiO₂ in the composites greatly influenced their photocatalytic activity. The experimental results indicated that the composite with Bi₂MoO₆:TiO₂ = 1:3 exhibited the highest photocatalytic activity. The enhancement mechanism of the composite catalysts was also discussed.     

Laser-induced enhancement of the surface hardness of nanoparticulate TiO2 self-cleaning layer

We here report that the abrasion resistance of nanoparticulate TiO₂ self-cleaning layers can be highly enhanced without a considerable loss of photocatalytic capability. TiO₂ coating layers solution-deposited onto the glass substrate were irradiated by a pulsed ultraviolet (UV) laser at 355 nm, which modified the surface morphologies via laser-induced local melting of TiO₂ nanoparticles. The surface hardness, measured by pencil scratch test, improved with increasing laser power (P). While an unmodified TiO₂ layer revealed a hardness of 6B, it increased to 2H after the surface was irradiated at P = 0.3 W. Almost all of the stearic acid deposited on an unmodified sample disappeared after UV exposure for 12 h. The photocatalytic decomposition was slowed down on laser-irradiated TiO₂ surfaces and this is attributed to the reduction of specific surface areas as a result of the morphological modifications. However, a TiO₂ layer hardened to 2H still exhibited fairly good photocatalytic activity, decomposing more than 75% of the stearic acid after exposure for the same duration.     

Effect of Na diffusion from glass substrate on the microstructural and photocatalytic properties of post-annealed TiO2 films synthesised by reactive sputtering

Amorphous columnar TiO₂ films were synthesised by reactive sputtering on cold soda–lime glass substrates (TiO₂/glass films). The films were subsequently heated in order to crystallise the photoactive anatase phase. The surface chemical composition assessment demonstrates the occurrence of metallic Na, the amount of which increases with the annealing temperature. The evolution of the structural, microstructural and photocatalytic properties of the films with the annealing temperature was investigated and compared to that of TiO₂ films deposited in same conditions, but on glass pre-coated with a SiN_x diffusion barrier (TiO₂/SiN_x/glass films). Once crystallised, both series of TiO₂ films exhibit [001] preferential orientation corresponding to the columnar growth. Grain coalescence associated to a modification of the grain shape is only observed in TiO₂/glass films for annealing temperatures higher than 450 °C, whereas neither microstructural nor structural change is observed in TiO₂/SiN_x/glass films. The Na-contaminated TiO₂ films exhibit different photocatalytic behaviour with the annealing temperature compared to the Na-free TiO₂ films. A discussion is finally based on these differences.     

Amphiphilic and photocatalytic behaviors of TiO2 nanotube arrays on Ti prepared via electrochemical oxidation

Amphiphilic TiO₂ nanotube arrays (TiO₂ NTs) were fabricated through electrochemical oxidation of Ti in solution containing H₃PO₄ and NaF. Scanning electron microscopic analysis shows that the as-prepared TiO₂ NTs have an average pore diameter of 100 nm and a wall thickness of 15 nm. The electrochemical oxidation of Ti can be divided into four stages. In the first stage, when the potential is very low, oxygen formation and Ti dissolution are the major reactions. The second stage corresponds to a slightly higher potential, but less than 2.5 V. In this stage, the formation of TiO₂ film occurs. When the potential is increased to the even higher range from 2.5 V to 6 V, the TiO₂ film dissolves and nanoporous surface structure is generated. This is the third stage. Further increase of the potential enters stage four. The high potentials cause the self-organization of the nanostructure and allow the formation of well-aligned TiO₂ NTs. We also found that the change in surface condition of Ti by annealing heat treatment affects the film dissolution kinetics. As compared with TiO₂ thin film, the TiO2 NTs show higher photocatalytic activity on decomposing Rhodamine B. The surface of the TiO₂ NTs can be wetted by both water and oil. Such an amphiphilic property comes from the capillary effect of the nanochannel structure of the TiO₂ NTs. Because of the amphiphilic property and the photocatalytic activity, we conclude that the TiO₂ NTs have the capability of self-cleaning.