Probing hot electron flow generated on Pt nanoparticles with Au/TiO2 Schottky diodes during catalytic CO oxidation

Hot electron flow generated on colloid platinum nanoparticles during exothermic catalytic carbon monoxide oxidation was directly detected with Au/TiO2 diodes. Although Au/TiO2 diodes are not catalytically active, platinum nanoparticles on Au/TiO2 exhibit both chemicurrent and catalytic turnover rate. Hot electrons are generated on the surface of the metal nanoparticles and go over the Schottky energy barrier between Au and TiO2. The continuous Au layer ensures that the metal nanoparticles are electrically connected to the device. The overall thickness of the metal assembly (nanoparticles and Au thin film) is comparable to the mean free path of hot electrons, resulting in ballistic transport through the metal. The chemicurrent and chemical reactivity of nanoparticles with citrate, hexadecylamine, hexadecylthiol, and TTAB (tetradecyltrimethylammonium bromide) capping agents were measured during catalytic CO oxidation at pressures of 100 Torr O2 and 40 Torr CO at 373-513 K. We found that chemicurrent yield varies with each capping agent but always decreases with increasing temperature. We suggest that this inverse temperature dependence is associated with the influence of charging effects due to the organic capping layer during hot electron transport through the metal-oxide interface.     

Plasmon resonant enhancement of photocatalytic water splitting under visible illumination

We demonstrate plasmonic enhancement of photocatalytic water splitting under visible illumination by integrating strongly plasmonic Au nanoparticles with strongly catalytic TiO2. Under visible illumination, we observe enhancements of up to 66× in the photocatalytic splitting of water in TiO2 with the addition of Au nanoparticles. Above the plasmon resonance, under ultraviolet radiation we observe a 4-fold reduction in the photocatalytic activity. Electromagnetic simulations indicate that the improvement of photocatalytic activity in the visible range is caused by the local electric field enhancement near the TiO2 surface, rather than by the direct transfer of charge between the two materials. Here, the near-field optical enhancement increases the electron-hole pair generation rate at the surface of the TiO2, thus increasing the amount of photogenerated charge contributing to catalysis. This mechanism of enhancement is particularly effective because of the relatively short exciton diffusion length (or minority carrier diffusion length), which otherwise limits the photocatalytic performance. Our results suggest that enhancement factors many times larger than this are possible if this mechanism can be optimized.     

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)。     

Effect of surface plasmon resonance on the photocatalytic activity of Au/TiO2 under UV/visible illumination

In this study, gold-loaded titanium dioxide was prepared by an impregnation method to investigate the effect of surface plasmon resonance (SPR) on photoactivity. The deposited gold nanoparticles (NPs) absorb visible light because of SPR. The effects of both the gold content and the TiO2 size of Au/TiO2 on SPR and the photocatalytic efficiency were investigated. The morphology, crystal structure, light absorption, emission from the recombination of a photoexcited electron and hole, and the degree of aggregation were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-visible-diffuse reflectance spectra (UV-VIS-DRS), photoluminescence (PL) spectroscopy, and turbidimetry, respectively. Photocatalytic activity was evaluated by the decolorization of methyl orange solution over modified titania under UV and UV/GLED (green light emitting diode) illumination. Au/TiO2 NPs exhibited an absorption peak (530-570 nm) because of SPR. The results of our photocatalytic experiments indicated that the UV-inducedly photocatalytic reaction rate was improved by simultaneously using UV and green light illumination; this corresponds to the adsorption region of SPR. Au/TiO2 could use the enhanced electric field amplitude on the surface of the Au particle in the spectral vicinity of its plasmon resonance and thus improve the photoactivity. Experimental results show that the synergistic effect between UV and green light for the improvement of photoactivity increases with increasing the SPR absorption, which in turn is affected by the Au content and TiO2 size.     

Formation of TiO2 nanoparticles by reactive-layer-assisted deposition and characterization by XPS and STM

Stoichiometric TiO2 nanoparticles (1-5 nm) were prepared by reactive-layer-assisted deposition (RLAD), in which Ti was initially deposited on a multilayer of H2O (or NO2) on a Au(111) substrate at approximately 90 K. The composition and atom-resolved structure of the nanoparticles were studied by XPS and STM. The approximately 5 nm TiO2 particles had either a rutile or anatase phase with various crystal facets. STS of the nanoparticles suggests size-dependent electronic structure. These well-defined nanoparticles can be used in molecular-level studies of the reactions and mechanisms of photocatalytic processes on TiO2 nanoparticle surfaces.     

One-dimensional TiO2 nanomaterials: preparation and catalytic applications

This work reports on the syntheses of one-dimensional (1D) H2Ti3O7 materials (nanotubes, nanowires and their mixtures) by autoclaving anatase titania (Raw-TiO2) in NaOH-containing ethanol-water solutions, followed by washing with acid solution. The synthesized nanosized materials were characterized using XRD, TEM/HRTEM, BET and TG techniques. The autoclaving temperature (120-180 degrees C) and ethanol-to-water ratio (V(EtOH)/V(H2O) = 0/60 approximately 30/30) were shown to be critical to the morphology of H2Ti3O7 product. The obtained H2Ti3O7 nanostructures were calcined at 400-900 degrees C to prepare 1D-TiO2 nanomaterials. H2Ti3O7 nanotubes were converted to anatase nanorods while H2Ti3O7 nanowires to TiO2(B) nanowires after the calcination at 400 degrees C. The calcination at higher temperatures led to gradual decomposition of the wires to rods and phase transformation from TiO2(B) to anatase then to rutile. Photocatalytic degradation of methyl orange was conducted to compare the photocatalytic activity of these 1D materials. These 1D materials were used as new support to prepare Au/TiO2 catalysts for CO oxidation at 0 degrees C and 1,3-butadiene hydrogenation at 120 degrees C. For the CO oxidation reaction, Au particles supported on anatase nanorods derived from the H2Ti3O7 nanotubes (Au/W-180-400) were 1.6 times active that in Au/P25-TiO2, 4 times that in Au/Raw-TiO2, and 8 times that on TiO2(B) nanowires derived from the H2Ti3O7 nanotubes (Au/M-180-400). For the hydrogenation of 1,3-butadiene, however, the activity of Au particles in Au/M-180-400 was 3 times higher than those in Au/W-180-400 but similar to those in Au/P25-TiO2. These results demonstrate that the potential of 1D-TiO2 nanomaterials in catalysis is versatile.     

TiO_2纳米管负载纳米金的制备及其在紫外光下的光电性能(英文)

利用直流磁控溅射法制备纳米金颗粒表面改性TiO2纳米管,并通过XRD,FESEM对其结构进行表征.在紫外光下测试其光电效应,结果发现在定电位和动电位下,纳米金改性后的TiO2纳米管产生的光电流都要比未改性的TiO2纳米管大.在定电位下(1.0V),Au/TiO2纳米管产生的光电流为0.4mA,是TiO2纳米管的1.8倍.在动电位下(-1.5～1.5V),当电位达1.5V时,Au/TiO2纳米管产生的光电流为0.75mA,是TiO2纳米管的3.75倍.     

Studies on the photo-catalytic activity of semiconductor nanostructures and their gold core-shell on the photodegradation of malathion

This work is devoted to the synthesis of different semiconductor nanoparticles and their metal core-shell nanocomposites such as TiO2, Au/TiO2, ZnO, and Au/ZnO. The morphology and crystal structures of the developed nanomaterials were characterized by transmission electron microscopy (TEM) and x-ray diffraction (XRD). These materials were used as catalysts for the photodegradation of malathion, which is one of the most commonly used pesticides in developing countries. The degradation of 10 ppm malathion under ultraviolet (UV) and visible light in the presence of different synthesized nanocomposites was analyzed using high performance liquid chromatography (HPLC) and UV-visible spectra. A comprehensive study was carried out for the catalytic efficiency of the prepared nanoparticles. Moreover, the effects of different factors that could influence catalytic photodegradation, such as different light sources, surface coverage and the nature of the organic contaminants, were investigated. The results indicate that the core-shell nanocomposite of semiconductor-gold serves as a better catalytic system than the semiconductor nanoparticles themselves.     

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.     

Photocatalytic degradation of azo dyes using Au:TiO2, gamma-Fe2O3:TiO2 functional nanosystems

We report photocatalytic degradation studies on Navy Blue HE2R (NB) dye on significant details as a representative from the class of azo dyes using functional nanosystems specifically designed to allow a strong photocatalytic activity. A modified sol-gel route was employed to synthesize Au and gamma-Fe2O3 modified TiO2 nanoparticles (NPs) at low temperature. The attachment strategy is better because it allows clear surface of TiO2 to remain open for photo-catalysis. X-ray diffraction, Raman and UV-VIS spectroscopy studies showed the presence of gold and iron oxide phases along-with the anatase TiO2 phase. TEM studies showed TiO2 nanocomposite particles of size approximately 10-12 nm. A detailed investigation on heterogeneous photocatalytic performance for Navy Blue HE2R dye was done using the as-synthesized catalysts Au:TiO2 and gamma-Fe2O3:TiO2 in aqueous suspension under 8 W low-pressure mercury vapour lamp irradiation. Also, the photocatalytic degradation of Amranth and Orange G azo dyes were studied. The surface modified TiO2 NPs showed significantly improved photocatalytic activity as compared to pure TiO2. Exposure of the dye to the UV light in the presence of pure and gold NPs attached TiO2 catalysts caused dye degradation of about approximately 20% and approximately 80%, respectively, in the first couple of hours. In the presence of gamma-Fe2O3 NPs attached TiO2, a remarkable approximately 95% degradation of the azo dye was observed only in the first 15 min of UV exposure. The process parameters for the optimum catalytic activity are established which lead to a complete decoloration and substantial dye degradation, supported by the values of the Chemical Oxygen Demand (COD) approximately 93% and Total Organic Carbon (TOC) approximately 65% of the treated dye solution after 5 hours on the employment of the UV/Au:TiO2/H2O2 photocatalytic process.     

Schottky barrier characteristics and internal gain mechanism of TiO2 UV detectors

High-responsivity metal-semiconductor-metal TiO(2) UV photodetectors with Ni and Au electrodes were fabricated identically. Their Schottky barrier heights and photocurrent gain mechanism were studied. The effective barrier height Φ and ideality factor n were evaluated according to the thermionic emission theory. The result that Φ(Ni) was lower than Φ(Au) may be attributed to the electron transfer from Ni to the TiO(2) substrate, which would lead to a dipole layer and, accordingly, decrease the barrier height. In addition, the I-V characteristics of the Ni/TiO(2)/Ni and Au/TiO(2)/Au photodetectors were observed. A significant internal gain was obtained, and the mechanism of the internal gain was studied by the phototransistor model in detail.     

Optimized method for preparation of TiO2 nanoparticles dispersion for biological study

The objective of the present study was to develop a practical method to prepare a stable dispersion of TiO2 nanoparticles for biological studies. To address this matter a variety of different approaches for suspension of nanoparticles were conducted. TiO2 (rutile/anatase) dispersions were prepared in distilled water following by treated with different ultrasound energies and various dispersion stabilizers (1.0% carboxymethyl cellulose, 0.5% hydroxypropyl methyl cellulose K4M, 100% fetal bovine serum, and 2.5% bovine serum albumin). The average size of dispersed TiO2 (rutile/anatase) nanoparticles was measured by dynamic light scattering device. Agglomerate sizes of TiO2 in distilled water and 100% FBS were estimated using TEM analysis. Sedimentation rate of TiO2 (rutile/anatase) nanoparticles in dispersion was monitored by optical absorbance detection. In vitro cytotoxicity of various stabilizers in 16-HBE cells was measured using MTT assay. The optimized process for preparation of TiO2 (rutile/anatase) nanoparticles dispersion was first to vibrate the nanoparticles by vortex and disperse particles by ultrasonic vibration in distilled water, then to add dispersion stabilizers to the dispersion, and finally to sonicate the nanoparticles in dispersion. TiO2 (rutile/anatase) nanoparticles were disaggregated sufficiently with an ultrasound energy of 33 W for 10 min. The formation of TiO2 (rutile/anatase) agglomerates in distilled water was decreased obviously by addition of 1.0% CMC, 0.5% HPMC K4M, 100% FBS and 2.5% BSA. For the benefit of cell growth, FBS is the most suitable stabilizer for preparation of TiO2 (rutile/anatase) particle dispersions and subsequent investigation of the in vivo and in vitro behavior of TiO2 (rutile/anatase) nanoparticles. This method is practicable to prepare a stable dispersion of TiO2 (rutile/anatase) nanoparticles for at least 120 h.     

Nanocrystalline brookite with enhanced stability and photocatalytic activity: influence of lanthanum(III) doping

Metastable TiO(2) polymorphs are more promising materials than rutile for specific applications such as photocatalysis or catalysis support. This was clearly demonstrated for the anatase phase but still under consideration for brookite, which is difficult to obtain as pure phase. Moreover, the surface doping of anatase with lanthanum ions is known to both increase the thermal stability of the metastable phase and improve its photocatalytic activity. In this study, TiO(2) nanoparticles of almost only the brookite structure were prepared by a simple sol-gel procedure in aqueous solution. The nanoparticles were then doped with lanthanum(III) ions. The thermal stability of the nanoparticles was analyzed by X-ray diffraction and kinetic models were successfully applied to quantify phases evolutions. The presence of surface-sorbed lanthanum(III) ions increased the phase stability of at least 200 °C and this temperature shift was attributed to the selective phase stabilization of metastable TiO(2) polymorphs. Moreover, the combination of the surface doping ions and the thermal treatment induces the vanishing of the secondary anatase phase, and the photocatalytic tests on the doped brookite nanoparticles demonstrated that the doping increased photocatalytic activity and that the extent depended on the duration of the sintering treatment.     

Development of novel supported gold catalysts: A materials perspective

Since Haruta et al. discovered that small gold nanoparticles finely dispersed on certain metal oxide supports can exhibit surprisingly high activity in CO oxidation below room temperature, heterogeneous catalysis by supported gold nanoparticles has attracted tremendous attention. The majority of publications deal with the preparation and characterization of conventional gold catalysts (e.g., Au/TiO₂), the use of gold catalysts in various catalytic reactions, as well as elucidation of the nature of the active sites and reaction mechanisms. In this overview, we highlight the development of novel supported gold catalysts from a materials perspective. Examples, mostly from those reported by our group, are given concerning the development of simple gold catalysts with single metal-support interfaces and heterostructured gold catalysts with complicated interfacial structures. Catalysts in the first category include active Au/SiO₂ and Au/metal phosphate catalysts, and those in the second category include catalysts prepared by pre-modification of supports before loading gold, by post-modification of supported gold catalysts, or by simultaneous dispersion of gold and an inorganic component onto a support. CO oxidation has generally been employed as a probe reaction to screen the activities of these catalysts. These novel gold catalysts not only provide possibilities for applied catalysis, but also furnish grounds for fundamental research.     

Electrostatic Self‐Assembly of Au Nanoparticles onto Thermosensitive Magnetic Core‐Shell Microgels for Thermally Tunable and Magnetically Recyclable Catalysis

A facile route to fabricate a nanocomposite of Fe₃O₄@poly[N‐isopropylacrylamide (NIPAM)‐co‐2‐(dimethylamino)ethyl methacrylate (DMAEMA)]@Au (Fe₃O₄@PND@Au) is developed for magnetically recyclable and thermally tunable catalysis. The negatively charged Au nanoparticles with an average diameter of 10 nm are homogeneously loaded onto positively charged thermoresponsive magnetic core‐shell microgels of Fe₃O₄@poly(NIPAM‐co‐DMAEMA) (Fe₃O₄@PND) through electrostatic self‐assembly. This type of attachment offers perspectives for using charged polymeric shell on a broad variety of nanoparticles to immobilize the opposite‐charged nanoparticles. The thermosensitive PND shell with swollen or collapsed properties can be as a retractable Au carrier, thereby tuning the aggregation or dispersion of Au nanoparticles, which leads to an increase or decrease of catalytic activity. Therefore, the catalytic activity of Fe₃O₄@PND@Au can be modulated by the volume transition of thermosensitive microgel shells. Importantly, the mode of tuning the aggregation or dispersion of Au nanoparticles using a thermosensitive carrier offers a novel strategy to adjust and control the catalytic activity, which is completely different with the traditional regulation mode of controlling the diffusion of reactants toward the catalytic Au core using the thermosensitive poly(N‐isopropylacrylamide) network as a nanogate. Concurrent with the thermally tunable catalysis, the magnetic susceptibility of magnetic cores enables the Fe₃O₄@PND@Au nanocomposites to be capable of serving as smart nanoreactors for thermally tunable and magnetically recyclable catalysis.     

退火温度对TiO2基电阻开关器件性能的影响

采用直流磁控溅射法在n+-Si上制备了TiO2薄膜,采用电子束蒸发镀膜仪在TiO2薄膜上沉积Au电极,获得了Au/TiO2/n+-Si结构的器件.研究了退火温度对薄膜结晶性能及器件电阻开关特性的影响.Au/TiO2/n+-Si结构的器件具有单极性电阻开关特性,置位(set)电压,复位(reset)电压、reset电流及功率的大小随退火温度的不同而不同,并基于灯丝理论对器件的电阻开关效应的工作机理进行了探讨.研究结果表明,500℃退火的器件具有良好的非易失性.器件高低阻态的阻值比大于103,其信息保持特性可达10年之久.在读写次数为100次时,器件仍具有电阻开关效应.     

Preparation and characterization of monodispersed microfloccules of TiO₂ nanoparticles with immobilized multienzymes

Microfloccules of TiO(2) nanoparticles, on which glycerol-dehydrogenase (GDH), 1,3-propanediol-oxidoreductase (PDOR), and glycerol-dehydratase (GDHt) were coimmobilized, were prepared by adsorption-flocculation with polyacrylamide (PAM). The catalytic activity of immobilized enzyme in the glycerol redox reaction system, the enzyme leakage, stabilities of pH and temperature, as well as catalytic kinetics of immobilized enzymes relative to the free enzymes were evaluated. Enzyme loading on the microfloccules as much as 104.1 mg/g TiO(2) (>90% loading efficiency) was obtained under the optimal conditions. PAM played a key role for the formation of microfloccules with relatively homogeneous distribution of size and reducing the enzyme leakage from the microfloccules during the catalysis reaction. The stabilities of GDH against pH and temperature was significantly higher than that those of free GDH. Kinetic study demonstrated that simultaneous NAD(H) regeneration was feasible in glycerol redox system catalysted by these multienzyme microfloccules and the yield of 1, 3-popanediol (1, 3-PD) was up to 11.62 g/L. These results indicated that the porous and easy-separation microfloccules of TiO(2) nanoparticles with immobilized multienzymes were efficient in term of catalytic activity as much as the free enzymes. Moreover, compared with free enzyme, the immobilized multienzymes system exhibited the broader pH, higher temperature stability.     

Preparation, characterization, and photocatalytic activity of Gd3+ doped TiO2 nanoparticles

TiO2 and Gd3+ doped TiO2 nanoparticles were prepared by sol-gel method and the materials were characterized by XRD, TEM, SEM-EDX, BET, FT-IR, UV-Vis absorption, and Raman spectral analysis. The photocatalytic activity of nano TiO2 and Gd/TiO2 nanoparticles was evaluated using a model pollutant propoxur, a carbamate pesticide, in a batch type UV photoreactor. The results revealed higher photocatalytic activity for Gd/TiO2 nanoparticles than both TiO2 nanoparticles and commercial TiO2 (Degussa P-25). The enhanced photocatalytic activity of Gd/TiO2 relative to TiO2 is attributed to its increased band gap energy as evidenced from the blue shift to shorter wavelength observed in the UV-Vis abso4ption spectra. The recombination rate of photogenerated electron-hole pair decreased due to increase in the band gap, which enhanced the charge transfer efficiency of Gd/TiO2 nanoparticles. Gd3+ with its half filled 7 f subshell facilitated rapid electron transfer at solid-liquid interface by shallowly trapping the electrons. Among the various dopant level of gadolinium, 0.3 wt% Gd/TiO2 nanoparticles showed higher activity than others due to its higher surface area.     

Au(Ru)-SiO2纳米-微米复合粒子的制备及精细结构研究

在制备出高性能的Au(Ru)-SiO2纳米-微米复合粒子的基础上，使用高分辨透射电镜、电子探针和X-射线衍射等现代手段，研究了该复合粒子的精细结构。研究结果表明：所制备的纳米-微米复合粒子在结构上呈现类似天体星云式的多层次结构，可区分为三级，其中一级结构是在微米尺度上，该层次上的SiO2微粒是整个复合粒子的承载骨架，其粒度均匀，分散性好，这在一定程度上大大降低了其所包含的功能金、钌纳米粒子的团聚问题；二级结构是在纳米尺度上，观察发现，金、钌纳米粒子相对均匀地镶嵌在第一结构层次的SiO2微粒中，它们是整个材料的性能载体，对材料性能起决定作用，研究指出进一步适度降低第一层次的SiO2微粒的粒径有望进一步降低甚至消除其中金、钌纳米粒子间的团聚；三级结构为金、钌纳米晶粒的高分辨晶格像，表明纳米晶表面原子点阵存在畸变。研究还指出，在该纳米-微米复合粒子中，金属金、钌的纳米粒子是以机械混合形式存在，不形成合金，也不形成固溶体。     

Diode behavior of electrophoretically deposited polyaniline on TiO2 nanoparticulate thin film electrode

An inorganic/organic hetrostructure diode was constructed by the electrophoretic deposition of the p-type polyaniline (PANI) on an n-type titanium oxide (TiO2) nanoparticulate thin film. The bonding and internalization of PANI to TiO2 nanoparticulate thin film were confirmed by the morphological, structural and optical studies of electrophoretically deposited PANI/TIO2 nanoparticulate thin film. The increased size of TiO2 nanoparticles indicated the well penetration of PANI molecules into the pores of mesoporous TiO2 nanoparticulate thin film. The XPS studies of PANI/TiO2 heterostructure exhibited the surface bonding and interaction between PANI molecules and TiO2 nanoparticles. The current-voltage (I-V) characterization of PANI/TiO2 heterostructure was carried out in the forward and the reverse bias at the applied voltage ranges from -1 V to +1 V with a scan rate of 2 mV/s. The constructed Pt/PANI/TiO2 heterostructure device established diodic behavior with non-linear nature of I-V curves.