Photothermal properties of inorganic nanomaterials as therapeutic agents for cancer thermotherapy

In recent years, gold (Au) nanoparticles (NPs) and single-walled carbon nanotubes (SWCNTs) have attracted significant attention as potent therapeutic agents for cancer thermotherapy. In this paper the photothermal properties of inorganic nanomaterials including porous silicon (PSi), titania (TiO2) nanotubes (NTs), TiO2 NPs, and multiwalled carbon nanotubes (MWCNTs), Au NPs and SWCNTs have been systematically investigated. PSi shows by far the largest temperature rise (deltaT), TiO2 NTs the second largest deltaT, and MWCNTs the smallest deltaT upon exposure to near-infrared (NIR) laser. The high photothermal effect of PSi has been found to be attributed to the high absorbance and the high surface-to-volume ratio due to the numerous micropores in PSi In addition, the factors affecting the photothermal effects of nanomaterials have been discussed. Our results suggest that PSi and TiO2 NTs are also potential therapeutic agents for cancer thermotherapy with excellent photothermal properties as well as high biocompatibility.     

Controlling the synthetic pathways of TiO2-derived nanostructured materials

A comprehensive study of the hydrothermal synthesis of TiO2-derived nanostructured materials, including layered protonic trititanate (H2Ti3O7), metal-ion exchangeable titanate (Na(x)H(2-x)Ti3O7), TiO2(B) and anatase nanotubes and TiO2-anatase nanowires, was conducted. Nanoscaled tubular structures were found to be already present in the samples derived from prolonged hydrothermal process of bulk anatase TiO2 and could be converted to various types of nanotubes, nanowires or nanorodes by post-synthesis treatments. 0.1 M HCI acid wash and air annealing were the two key parameters to select the types of nanotubes/nanowires as the final products. XRD, Raman, TG, and XPS core level and valence band studies were carried out to elucidate our proposed synthetic pathways.     

Influence of structure parameters and crystalline phase on the photocatalytic activity of TiO2 nanotube arrays

Titanium oxide nanotube arrays (TiO2-NTAs) with different diameters and lengths are prepared by anodization of titanium foils in a water/ethylene glycol solution (5:95 V/V) containing 0.3 wt% NH4F. The effects of the diameters, lengths and crystalline phases of the NTAs on the photocatalytic (PC) activity are systematically evaluated. Larger pore diameter results in higher PC activity. The PC activity increases initially and then decreases with lengths for TiO2-NTAs and the optimal length that yields the highest PC activity is observed to be 6.2 microm. The crystalline phase and corresponding PC activity depend on the calcination temperature and their relationship is also investigated. The amorphous-to-anatase and anatase-to-rutile phase transitions initially occur at 300 and 500 degrees C, respectively. The PC activity of TiO2-NTAs initially increases with calcination temperature from 250 to 500 degrees C and then decreases at higher calcination temperature. The enhanced PC activity observed from the samples annealed at 250-450 degrees C is attributed to the better anatase crystalline structure at higher calcination temperature. The highest PC activity with regard to photodecomposition of methyl orange is observed from TiO2-NTAs calcined at 500 degrees C, which coincides with the anatse-to-rutile phase transformation. The synergistic effect of the anatase TiO2-NTAs and rutile barrier layers facilitate interfacial electron transfer consequently enhancing the PC activity. Further elevation of the calcination temperatures to 550 and 600 degrees C exhibits diminished PC activity because the NTs become shorter due to conversion of the bottom of anatase NTs into rutile film.     

Hierarchical top-porous/bottom-tubular TiO2 nanostructures decorated with Pd nanoparticles for efficient Photoelectrocatalytic decomposition of synergistic pollutants

In this paper, top-porous and bottom-tubular TiO(2) nanotubes (TiO(2) NTs) loaded with palladium nanoparticles (Pd/TiO(2) NTs) were fabricated as an electrode for an enhanced photoelectrocatalytic (PEC) activity toward organic dye decomposition. TiO(2) NTs with a unique hierarchical top-porous and bottom-tubular structure were prepared by a facile two-step anodization method and Pd nanoparticles were decorated onto the TiO(2) NTs via a photoreduction process. The PEC activity of Pd/TiO(2) NTs was investigated by decomposition of methylene blue (MB) and Rhodamine B (RhB). Because of formation Schottky junctions between TiO(2) and Pd, which significantly promoted the electron transfer and reduced the recombination of photogenerated electrons and holes, the Pd/TiO(2) NT electrode showed significantly higher PEC activities than TiO(2) NTs. Interestingly, an obvious synergy between two dyes was observed and corresponding mechanism based on facilitated transfer of electrons and holes as a result of a suitable energy level alignment was suggested. The findings of this work provide a fundamental insight not only into the fabrication but also utility of Schottky junctions for enhanced environmental remediation processes.     

TiO2纳米管的制备及其光催化性能研究

利用水热法制备了TiO2纳米管，采用TEM、XRD等分析手段对其形貌和晶体相态进行了表征，并进行了光催化实验。实验结果表明，采用该方法制得的TiO2纳米管的管径小、营形均匀，TiO2纳米管的光催化性能明显高于TiO2纳米粒子。     

浸渍-沉积法制备一维Au/TiO_2的光催化性能研究

以钛酸纳米管为载体、HAuCl4为金前驱体,通过浸渍-沉积法制备一维金修饰TiO2光催化剂(Au/TiO2)。通过X射线衍射和紫外-可见漫反射吸收光谱研究材料的结构和性质。以甲基橙溶液作为模拟废液,研究Au/TiO2材料在紫外光条件下的光催化活性。研究表明,由于金可以接受电子,从而促进光生电子和光生空穴的分离,使TiO2的光催化活性提高;Au/TiO2的光催化活性还与金的含量密切相关,金的最佳负载量为1%(质量分数)。     

Synthesis of TiO2 nanotubes coupled with CdS nanoparticles and production of hydrogen by photocatalytic water decomposition

The CdS/TiO₂NTs composite was prepared by a simple two-step chemical solution routes to directly transfer trititanate nanotubes to TiO₂NTs and simultaneously coupled with CdS nanoparticles. The results of XRD, TEM, Diffuse reflectance UV-Visible absorption spectra revealed that the CdS nanoparticles were homogeneously embedded on the surface of TiO₂NTs and the absorption spectrum of TiO₂NTs was extended to visible region. The activity of hydrogen production by photocatalytic water decomposition for the CdS/TiO₂NTs composite was examined under visible light irradiation (λ > 400 nm) and the quantity of H₂ evolution was ca. 1708 μL/g for 6 h.     

Synthesis of mesoporous anatase TiO2 nanotubes by a hydrothermal treatment and their use in solid-state dye-sensitized solar cells

Mesoporous anatase TiO2 nanotubes (NTs) with the diameter of about 7 12 nm and the length of several hundred nanometers were synthesized by a hydrothermal method on commercial TiO2 particles in NaOH followed by HCI washing. The samples were characterized by X-ray diffraction (XRD), transmitting electron microscopy (TEM), and Brunauer-Emmet-Teller (BET) measurements. The hydrothermal treatment temperature at 130 degrees C was shown to affect not only the extent of particle-to-sheet conversion, and thus the resulting structures of the NTs, but also the anatase-to-rutile transformation. The surface area of the NTs was 200 m2g(-1). This value was much higher in comparison to TiO2 nanoparticles of 50 m2g(-1). It was also found that the NT photoelectrodes had a pronounced impact on the performance of solar cells as compared to nanoparticle ones. This was probably due to lead to a significantly higher specific dye loading and, for certain hydrothermal treatments, resulting in a doubling of the solar cell efficiency (in our case from 2.84% to 4.03% of AM 1.5 conditions).     

Synthesis of carbon nanotube-TiO(2) nanotubular material for reversible hydrogen storage

A material consisting of multi-walled carbon nanotubes (MWCNTs) and larger titania (TiO(2)) nanotube arrays has been produced and found to be efficient for reversible hydrogen (H(2)) storage. The TiO(2) nanotube arrays (diameter ～60?nm and length ～2-3?μm) are grown on a Ti substrate, and?MWCNTs a few μm in length and ～30-60?nm in diameter are grown inside these TiO(2) nanotubes using chemical vapor deposition with cobalt as a catalyst. The resulting material has been used in H(2) storage experiments based on a volumetric method using the pressure, composition, and temperature relationship of the storage media. This material can store up to 2.5?wt% of H(2) at 77?K under 25?bar with more than 90% reversibility.     

Structure, wettability and photocatalytic activity of CO(2) laser sintered TiO(2)/multi-walled carbon nanotube coatings

Nanocomposites of titanium dioxide (TiO(2)) and multi-walled carbon nanotubes (MWNTs) were prepared and deposited by sol-gel spin coating on borosilicate substrates and sintered in air at 300?°C for 15?min. Further irradiation of the films with different CO(2) laser intensities (4.3-17?W?m(-2)) was carried out in order to crystallize TiO(2) in the anatase form while preserving the MWNT's structure. The laser irradiation changed the crystal structure of the coatings and also affected the wettability and photocatalytic activity of the films. The anatase phase was only observed when a minimum laser intensity of 12.5?W?m(-2) was used. The contact angle decreased with the enhancement of the laser intensity. The photocatalytic activity of the films was determined from the degradation of a stearic acid layer deposited on the films. It was observed that the addition of carbon nanotubes themselves increases the photocatalytic activity of TiO(2) films. This efficiency is even improved when high CO(2) laser intensities are used during the sintering of the coatings.     

CNT/TiO2复合材料的合成、表征及其光催化性能分析

采用多壁碳纳米管(MWCNTs)为原料,分别以异丙醇钛(TIP)、丙氧基钛(TPP)和四丁氧基钛(TNB)为钛源,苯作为溶刺,制备了CNT/TiO2复合材料.利刖N2吸附等温线,扫描电子显微镜(SEM),X-射线衍射(XRD),能量分散性X-射线分析(EDX)以及紫外吸收光谱对所制CNT/TiO2复合材料进行了表征.并在紫外光照射下,通过亚甲蓝(MB,C16H18N3S·Cl·3H2O)水溶液的转,变测试了CNT/TiO2复合材料的光催化性能.研究结果表明:CNT/TiO2复合材料对MB的降解作用不仅有MWCNT的吸附性和TiO2的光催化性,而且还有MWCNT和TiO2之间的电子转移性.     

Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water

TiO(2) photocatalyst (P-25) (50mgL(-1)) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO(2) were obviously increased. Pulsed high-voltage discharge process with TiO(2) had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10x10(-6) to 1.50x10(-6)Ms(-1), the ozone formation rate from 1.99x10(-8) to 2.35x10(-8)Ms(-1), respectively. In addition, this process had no influence on the photocatalytic properties of TiO(2). The introduction of TiO(2) photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants.     

Synthesis, characterization, and photocatalytic activity of TiO(2-x)N(x) nanocatalyst

Nitrogen-doped titanium dioxide powders were prepared by wet method, that is, the hydrolysis of acidic tetra-butyl titanate using aqueous ammonia solution, followed by calcination at temperatures about 350 degrees C. The catalysts exhibited photocatalytic activity in the visible light region owing to N-doping. The light absorption onset of TiO(2-x)N(x) was shifted to the visible region at 459 nm compared to 330 nm of pure TiO(2). An obvious decrease in the band gap was observed by the optical absorption spectroscopy, which resulted from N2p localized states above the valence band of TiO(2-x)N(x) (compared to TiO(2)). The TiO(2-x)N(x) catalyst was characterized to be anatase with oxygen-deficient stoichiometry by X-ray diffraction (XRD), surface photovoltage spectroscopy (SPS) and X-ray photoelectron spectroscopy (XPS). The binding energy of N1s measured by XPS characterization was 396.6 eV (TiN bonds, beta-N) and 400.9 eV (NN bonds, gamma-N(2)), respectively. The photocatalytic activity of TiO(2-x)N(x) under visible light was induced by the formation of beta-N in the structure. Photocatalytic decomposition of benzoic acid solutions was carried out in the ultraviolet and visible (UV-vis) light region, and the TiO(2-x)N(x) catalyst showed higher activity than pure TiO(2).     

The effects of synthesis procedures on the morphology and photocatalytic activity of multi-walled carbon nanotubes/TiO(2) nanocomposites

This study investigates the microstructures of multi-walled carbon nanotubes (MWNTs)/TiO(2) nanocomposites, obtained by sol-gel and hydrothermal processes. The synthesized nanocomposite materials were characterized by x-ray diffractometry (XRD), Brunauer-Emmett-Teller (BET) adsorption analysis, transmittance electron microscopy (TEM), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy, and x-ray photoelectron spectroscopy (XPS). The effects of the synthetic procedures and MWNTs on the morphology and photocatalytic activity of the nanocomposites were studied. The photocatalytic activity of the MWNTs/TiO(2) nanocomposite was elucidated based on the photooxidation of NO(x) under UV light illumination. A fleck-like and well dispersed TiO(2) microstructure on the surface of the MWNTs was observed in the sol-gel system, while compact and large aggregated particles were found in the hydrothermal procedure. The nanocomposite prepared by the sol-gel system exhibits better photocatalytic activity for NO oxidation (from 20.52 to 32.14%) than that prepared by the hydrothermal method (from 22.58 to 26.51%) with the same MWNT loading (from 0 to 8?wt%), respectively. The optimal MWNT content in the nanocomposite was considered at 8?wt%. Additionally, results confirm that the introduction of MWNTs will cause the NO(2) to be more consumed than NO in the photocatalytic experiments, leading to more complete NO(x) photooxidation. These observations indicate that the different TiO(2) distributions on the MWNT surfaces and MWNT contents in the materials would determine the morphology, the physicochemical and photocatalytic characteristics for the nanocomposite materials.     

Development of photocatalytic TiO2 nanofibers by electrospinning and its application to degradation of dye pollutants

We have developed photocatalytic TiO2 nanofibers for the treatment of organic pollutants by using electrospinning method. We found that the optimized electrospinning conditions (electric field and flow rate) were 0.9 kV cm(-1) and 50 microL min(-1). After annealing at 550 degrees C for 30 min, we fabricated TiO2 nanofibers (average 236 nm thick) with anatase crystalline phase. To increase photocatalytic activity and effective surface area, we coated photocatalytic TiO2 particles on the TiO2 nanofibers by using sol-gel method. The degradation rate (k'=85.4x10(-4) min(-1)) of composite TiO2 was significantly higher than that (15.7x10(-4) min(-1)) of TiO2 nanofibers and that (14.3x10(-4) min(-1)) of TiO2 nanoparticles by the sol-gel method. Therefore, we suggested that the composite TiO2 of nanofibers and nanoparticles be suitable for the degradation of organic pollutants.     

Preparation and characterisation of TiO2 nanoparticle and titanate nanotube obtained from Ti-salt flocculated sludge with drinking water and seawater

This study aimed to prepare and characterise titanium dioxide (TiO2) nanoparticles and titanate nanotubes produced from Ti-sat flocculated sludge with drinking water (DW) and seawater (SW). The Ti-salt flocculated sludge from DW and SW was incinerated at 600 degrees C to produce TiO2 nanoparticles. XRD results showed that the anatase TiO2 structure was predominant for TiO2 from DW (TiO2-DW) and TiO2 from SW (TiO2-SW), which were mainly doped with carbon atoms. Titanate nanotubes (tiNT) were obtained when TiO2-DW and TiO2-SW were hydrothermally treated with NaOH solution. Structure phase, shape, crystallisation and photocatalytic activity of tiNT were affected by the incineration temperature and the amount of sodium present in different tiNT. The tiNT doped with thiourea incinerated at 600 degrees C presented anatase phase, showing a high increase of the degree of crystallisation with nanotube-like structures. The photocatalytic activity of these photocatalysts was evaluated using photooxidation of gaseous acetaldehyde. Thiourea doped tiNT-DW and tiNT-SW showed similar photocatalytic activity compared to commercially available TiO2-P25 under UV light and indicated a photocatalytic activity under visible light.     

Influence of the physical, structural and chemical properties on the photoresponse property of magnetron sputtered TiO2 for the application of water splitting

The production of hydrogen from water (called "water splitting"), utilises sunlight as an energy source (solar-hydrogen) in a photoelectrochemical (PEC) solar cell, is a promising source of green energy. In this work, a PEC was used, for evaluating the photoactivity of a thin film TiO2 based photoanode by measuring photocurrent (which is comparable to hydrogen production rate by water splitting process in PEC). The main focus of this work is to study the effect of the TiO2 nanosurface and bulk properties on the photoresponse properties of the photoanode. The TiO2 coatings (360-400 nm) were deposited using a closed field reactive magnetron sputtering system. The structure and morphology of the TiO2 coatings were systematically altered by varying the deposition pressure between 5 x 10(-4) to 1 x 10(-2) mbar. The properties of the deposited nano-coatings were determined using Ellipsometry, SEM, AFM, profilometry, XPS, Raman and X-ray diffraction (XRD). Coating properties were correlated with the light absorption and photocurrent performance which were evaluated using UV-Vis spectroscopy and tri-electrode potentiostat measurements respectively. It was concluded from this study that the coating deposition pressure has a pronounced effect on the TiO2 photoanode properties leading to a significant enhancement in the photoactivity in PEC cell. Over a six fold increase in photocurrent at applied potential 0 V was observed for TiO2 photoanode prepared at 4 x 10(-3) mbar as compared to 5 x 10(-4) mbar. A correlation has been established between the deposition pressure, nano surface morphology and bulk properties, UV-Vis light absorbance and bandgap value, and the consequently higher (i) photocurrent density, (ii) negative flat band, and (iii) open circuit potential measured in Photoelectrochemical (PEC) cell.     

CdS/CNT-TiO2光催化剂的合成及其对亚甲基蓝的光催化降解（英文）

采用多壁碳纳米管(MWCNTs)为载体,分别以醋酸镉((CH3COO)2Cd.2H2O)和硫化钠(Na2S.5H2O)为镉源和硫源,经简单逐滴滴入途径制备了CdS/CNT复合材料。再以四丁氧基钛(TNB)为钛源,苯为溶剂,成功地将二氧化钛(TiO2)纳米粒子沉积在CdS修饰的MWCNTs表面而得到CdS/CNT-TiO2光催化剂。利用N2吸附等温线、扫描电子显微镜、X射线衍射、能量分散性X射线分析以及透射电子显微镜对所制CdS/CNT-TiO2光催化剂进行表征。CdS/CNT-TiO2复合材料呈多孔结构,MWCNTs均匀分散在材料中,且未出现明显的TiO2和CdS纳米颗粒团聚体。该材料在紫外和可见光照射下对亚甲基蓝具有优异的降解活性。这不仅归因于TiO2对自由基的反应和MWCNTs吸附能力,且归因于引入窄带隙半导体CdS,使粒子在MWCNTs表面的电子转移速率得到提高。     

Crystalline characterization and photodecomposition properties of rod-shaped Na2Ti6O13 powder prepared by molten salt process

To prepare one-dimensional nanostructured Na2Ti6O13 powder, the starting materials of TiO2, NaCl and Na2CO3 were mixed and then heat-treated at 1000 degrees C for 2 hrs in air under molten state of NaCl. Changes in shape and phase, photo absorbance and photocatalytic ability of TiO2 particle were observed controlling added amount of Na2CO3 under constant weight ratio of TiO2 to NaCl using SEM, X-ray diffractometer, Raman spectroscopy, and UV-Vis spectroscopy. The TiO2 particle was changed into rod-shape Na2Ti6O13 with the addition of Na2CO3, showing increase in optical energy band-gap of the powder as well as gradual decrease of the photo-decomposition ability.     

超声波-Fe3＋掺杂TiO2纳米管光催化降解活性艳红X-3B的研究

以超声波作用制备的Fe3＋掺杂TiO2纳米管作为光催化剂,氙灯模拟紫外光为光源,降解活性艳红X-3B,探讨了超声预处理时间、催化剂煅烧温度、pH值、催化剂加入量等因素对活性艳红X-3B降解率的影响,结果表明,超声波预处理时间为20min,催化剂煅烧温度为400℃,pH为强酸或强碱,催化剂加入量为1.0g/L时对活性艳红X-3B处理效果较好。