Design and fabrication of a TiO2/nano-silicon composite visible light photocatalyst

Nano-silicon (nc-Si) was utilized as the charges generator to promote the photocatalytic and super-hydrophilic reactivity of TiO₂ film under visible light irradiation. The photocatalytic ability of TiO₂/nc-Si composite photocatalyst was evaluated by a set of experiments to photodecompose 100 ppm methylene blue (MB) in aqueous solution. And the super-hydrophilic property was characterized by measuring the water droplet contacts angle, under visible light irradiation in atmospheric air and at room temperature. Under 100 mW/cm² visible light irradiation, the droplet contact angles were reduced to 0° within 4 h with nc-Si charge generator. Additionally, the rate constant of MB photo-degradation was promoted 6.6 times.     

Enhanced diamond nucleation on copper substrates by graphite seeding and CO2 laser irradiation

Diamond nucleation on copper (Cu) substrates was investigated by graphite seeding and CO₂ laser irradiation at initial stages of the combustion-flame deposition. A graphite aerosol spray was used to generate a thin layer of graphite powders (less than 1 μm) on Cu substrates. The graphite-seeded Cu substrates were then heated by a continuous CO₂ laser to about 750 °C within 1 min. It was found that diamond nucleation density after this treatment was more than three times as much as that on the virgin Cu substrates. As a consequence, diamond films up to 4 μm were obtained in 5 min. The enhancement of diamond nucleation on the graphite-seeded Cu substrates was attributed to the formation of defects and edges during the etching of the seeding graphite layers by the OH radicals in the flame. The defects and edges served as nucleation sites for diamond formation. The function of the CO₂ laser was to rapidly heat the deposition areas to create a favorable temperature for diamond nucleation and growth.     

Fabrication and characterization of a Cu seed layer on a 60-nm trench-patterned SiO2 substrate by a self-assembled-monolayer (SAM) process

Continuous electroless deposition of a 10-nm thick layer of Cu was successfully performed on a SiO₂/Si substrate coated with a 3-nm Au catalytic layer. The Au catalytic layer was formed by a self-assembled monolayer (SAM) process terminated with NH₂ headgroups, upon which negatively charged Au particles were deposited via electrostatic interaction with the positively charged NH₂-SAM. The Au and NH₂-SAM layers were analyzed by X-ray photoelectron spectroscopy (XPS) and contact angle analysis. Atomic force microscopy, field emission scanning electron microscopy, and XPS revealed that the Cu layer formed by this electroless processes had good step-coverage, small grain size, and excellent adhesion to the substrate. The proposed process is a very promising method for fabrication of a conductive Cu seed layer in a 60-nm trench-pattern.     

GROWTH MODEL OF TEXTURED DIAMOND (111) FILM IN CH4/O2/H2 ATMOSPHERE

Partially oriented and highly textured diamond films on Si( 111 ) substrates were achieved by hot-filament chemical vapor deposition(HFCVD). High nucleation density greater than 5×10⁸cm^-2 was realiged in 3 min by near-surface glow discharge. The os-grown films were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD) and Raman spectroscopy. It was found that by adding a small amount of oxygen to the mixture of CH₄/H₂, the appearance of facet(111) was well controlled, and the secondary nucleation on the facet(111) was suppressed greatly. Growth feature of homoepitaxy on diamond (111) surface was demonstrated to be in Stranski-Krastanov model by SEM.     

Photosensitization of nanocrystalline TiO2 film electrode with cadmium sulphoselenide

Nanocrystalline titanium dioxide (TiO₂) thin films composed of densely packed nanometer-sized grains have been successfully deposited onto an indium-doped-tin oxide (ITO) substrate. Then cadmium sulphoselenide (CdSSe) thin film was deposited onto pre-deposited TiO₂ to form a TiO₂/CdSSe film, at low temperature using a simple and inexpensive chemical method. The X-ray diffraction, selected area electron diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and water contact angle techniques were used for film characterization. Purely rutile phase of TiO₂ with super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 30-40 (±2) nm was observed. The increase in optical absorption was observed after CdSSe film deposition. Nest like surface morphology of CdSSe on TiO₂ surface results in air trapping in the crevices which prevents water from adhering to the film with increase in water contact angle. Photosensitization of TiO₂ with CdSSe was confirmed with light illumination intensity of 80 mW/cm².     

Electrochemical deposition of silver nanoparticles on TiO2/FTO thin films

Silver nanoparticles were deposited on titanium oxide^IV (TiO₂) thin films supported on FTO (fluorine-doped tin oxide^IV) glass using a double pulse electrochemical deposition method. A systematic study of particle nucleation and growth is presented as a function of applied potential and time. Samples were analyzed by grazing-angle X-ray diffraction (GIXRD) technique and morphology was observed using Scanning Electron Microscopy and Energy Dispersive Spectroscopy device (SEM-EDS). Our results confirm the possibility of controlled electrochemical homogeneous deposition of metallic silver particles over TiO₂ surface, which exhibit a potential application in catalytic processes.     

Effect of surface species on Cu-TiO2 photocatalytic activity

The Cu-TiO₂ nanoparticles with different Cu dopant content were prepared by sol-gel method. The structure of the as-prepared catalysts and the surface species of Cu-TiO₂ were determined using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and diffuse reflection spectroscopy (DRS). The relationship between the photocatalytic activity and the surface species of Cu-TiO₂ was revealed via the measurement of surface photovoltage spectroscopy (SPS) as well as the degradation of the rhodamine B (RhB). The experimental results suggest that the Cu-TiO₂ photocatalysts with appropriate content of Cu (about 0.06 mol%) possess abundant electronic trap, which effectively inhibits the recombination of photoinduced charge carriers, improving the photocatalytic activity of TiO₂. While at high Cu dopant region (>0.06 mol%), the excessive oxygen vacancies and Cu species can become the recombination centers of photoinduced electrons and holes. Meanwhile, at heavy Cu doping concentration, excessive P-type Cu₂O can cover the surface of TiO₂, which leads to decrease in the photocatalytic activity of photocatalyst. The photocatalytic experimental results are in good agreement with the conclusions of SPS measurements, indicating that there is a close relationship between the photocatalytic activity and the intensity of SPS spectra.     

Photocatalytic TiO2 thin films deposited on flexible substrates by radio frequency (RF) reactive magnetron sputtering

Titanium dioxide (TiO₂) thin films were deposited on flexible polycarbonate (PC) substrates by radio frequency (RF) reactive magnetron sputtering. The target was metallic titanium, argon was the plasma gas and oxygen was the reactive gas. Taguchi’s method, which uses an L₉ (3⁴) orthogonal array, signal-to-noise ratio and analysis of variance (ANOVA), was employed to study the performance of the deposition process. The effects of the deposition parameters on the structure, morphology and photocatalytic performance of the TiO₂ films were analyzed using scanning electron microscopy (SEM), X-ray diffraction, and UV-vis-NIR spectroscopy. Experiments varied RF power (50, 100, 150 W), deposition time (2, 3, 4 h), O₂/(Ar + O₂) argon/oxygen ratios (40, 60, 80%) and substrate temperatures (room, 80, 120 °C), to optimize the photoinduced decomposition of methylene blue (MB). The experimental results illustrate the effectiveness of this approach.     

Shape evolution, photoluminescence and degradation properties of novel Cu2O micro/nanostructures

Three kinds of novel cuprous oxide (Cu₂O) micro/nanostructures are synthesized via a facile template-free hydrothermal method. Two factors are critical for the growth process of typical samples: the concentration of copper ions (Cu(II)) and the addition of Polyvinylpyrrolidone (PVP) as surfactant. It is found that the application of ethanol as solvent speeds up the reduction rate of Cu(II), and it promotes the aggregating of Cu₂O nanocrystals at the preliminary stage to form irregular spherical structures. Photoluminescence (PL) properties of the three kinds of samples and their photocatalytic activities for degradation of Methyl Orange (MO) are also measured. The sample with higher concentration of copper vacancy (V _Cu) defects has better photocatalytic ability, indicating that besides the morphology of Cu₂O nano/microcrystals, the defects in crystalline structures can also influence their electrical characteristics, and thus change their photocatalytic activity. This provides a potential method to improve the photocatalytic performances of Cu₂O crystals.     

One-step chemically vapor deposited hybrid 1T-MoS2/2H-MoS2 heterostructures towards methylene blue photodegradation

The photocatalytic degradation of methylene blue is a straightforward and cost-effective solution for water decontamination. Although many materials have been reported so far for this purpose, the proposed solutions inflicted high fabrication costs and low efficiencies. Here, we report on the synthesis of tetragonal (1T) and hexagonal (2H) mixed molybdenum disulfide (MoS₂) heterostructures for an improved photocatalytic degradation efficiency by means of a single-step chemical vapor deposition (CVD) technique. We demonstrate that the 1T-MoS₂/2H-MoS₂ heterostructures exhibited a narrow bandgap ∼ 1.7 eV, and a very low reflectance (<5%) under visible-light, owing to their particular vertical micro-flower-like structure. We exfoliated the CVD-synthesised 1T-MoS₂/2H-MoS₂ films to assess their photodegradation properties towards the standard methylene blue dye. Our results showed that the photo-degradation rate-constant of the 1T-MoS₂/2H-MoS₂ heterostructures is much greater under UV excitation (i.e., 12.5 × 10⁻³ min⁻¹) than under visible light illumination (i.e., 9.2 × 10⁻³ min⁻¹). Our findings suggested that the intermixing of the conductive 1T-MoS₂ with the semi-conducting 2H-MoS₂ phases favors the photogeneration of electron-hole pairs. More importantly, it promotes a higher efficient charge transfer, which accelerates the methylene blue photodegradation process.     

Morphology, structure and photocatalytic performance of ZnIn2S4 synthesized via a solvothermal/hydrothermal route in different solvents

Hexagonal ZnIn₂S₄ photocatalysts with different morphology and crystallinity (micro-structures) were prepared in aqueous-, methanol- and ethylene glycol-mediated conditions via a solvothermal/hydrothermal method. The aqueous- and methanol-mediated ZnIn₂S₄ presented to be Flowering-Cherry-like microsphere, while the ethylene glycol-mediated ZnIn₂S₄ presented to be micro-cluster. In comparison with two other products, aqueous-mediated ZnIn₂S₄ possessed the best crystallinity (micro-structure), which resulted in the highest photocatalytic activity for hydrogen evolution under visible-light irradiation. Additionally, aqueous-mediated ZnIn₂S₄ was found to be more stable than the other two ZnIn₂S₄ photocatalysts while undergoing the photocatalytic process. During the photocatalytic reaction, the average rates for hydrogen production over aqueous-, methanol- and ethylene glycol-mediated ZnIn₂S₄ were determined to be 27.3, 12.4 and 9.1 μmol h^-1, respectively, in the present photocatalytic systems.     

Temperature dependence of Cu2O orientations in oxidation of Cu (111)/ZnO (0001) by oxygen plasma

The role of temperature on the oxidation dynamics of Cu₂O on ZnO (0001) was investigated during the oxidation of Cu (111)/ZnO (0001) by using the oxygen plasma as oxidant. A transition from single crystalline Cu₂O (111) orientation to micro-zone phase separation with multiple orientations was revealed when the oxidation temperature increased from 300 ℃ to higher. The experimental results clearly showed the effect of oxidation temperature with the assistance of oxygen plasma on changing the morphology of Cu (111) film and enhancing the lateral nucleation and migration abilities of cuprous oxides. A vertical top-down oxidation mode and a lateral migration model were proposed to explain the different nucleation and growth dynamics of the temperature-dependent oxidation process in the oxidation of Cu (111)/ZnO (0001).     

Substrate and pretreatment dependence of Cu nucleation by metal–organic chemical vapor deposition

The nucleation of copper (Cu) with (hfac)Cu(VTMS) organometallic precursor is investigated for Si, SiO₂, TiN, and W₂N substrates. As the deposition temperature is increased, the dominant growth mechanism is observed to change from the nucleation of Cu particles to the clustering of Cu nuclei around 180 °C independent of the employed substrates. It is also observed that the cleaning of substrate surfaces with the diluted HF solution improves the selectivity of Cu nucleation between TiN and SiO₂ substrates. Dimethyldichlorosilane treatment is found to passivate the surface of TiN substrate, contrary to the generally accepted belief, when the TiN substrate is cleaned by H₂O₂ solution before the treatment.     

Conversion behavior comparison of TFA–MOD and non-fluorine solution-deposited YBCO films

The densification behavior during conversion of YBa₂Cu₃O_7−x (YBCO) films formed by the trifluoroacetate (TFA)-based metal–organic deposition (MOD) technique was compared to a non-fluorine oxycarbonate-based MOD process and nitrate-based polymer-assisted deposition (PAD). The critical current densities obtained in all processes exceeded 10⁶ A/cm² in films at least 300 nm thick. Rapid densification of films was observed in all processes, beginning at 700 °C in the TFA and PAD processes and 650 °C in the oxycarbonate process. YBCO nucleation occurred shortly after densification began in all processes. Residual carbon measurements were performed using wavelength dispersive spectroscopy (WDS). Carbon persisted in films from all processes until after densification began, but it was reduced to background levels soon after YBCO nucleation. Film density and second phase morphology were controlled through adjustments to the ambient oxygen partial pressure. Morphological evidence of extensive transient liquid phase formation was observed in PAD films and is consistent with the densification and nucleation behavior. The common behavior between the PAD, oxycarbonate–MOD, and TFA–MOD processes suggests that a melt forms in all systems, but the extent of this melt varies.     

Photocatalytic properties of TiO2 thin films obtained by glancing angle deposition

Titanium dioxide (TiO₂) thin films with different nanostructures such as nano-particles and separated vertical columns were grown by glancing angle deposition (GLAD) in an electron beam evaporation system. The photocatalytic properties of grown TiO₂ films with different deposition angles and different annealing temperatures were evaluated by following decomposition of methyl orange under ultraviolet (UV) light irradiation. The results suggest that increased surface area due to the GLAD process could improve the photocatalytic properties of TiO₂ films.     

Combination of ultrasound-treated 2D g-C3N4 with Ag/black TiO2 nanostructure for improved photocatalysis

Herein, nanosheets of g-C₃N₄ (CN), prepared using a green ultrasonication process under various conditions, were combined with Ag/black TiO₂ nanocomposites (AgBT) to create two-dimensional (2D) CN/Ag/black TiO₂ tri-composites (CNAgBT). The thickness of the CN sheets varied with the ultrasonication conditions. The CNAgBT sample prepared using ultrasound-treated CN exhibited the highest average photocatalytic efficiencies for the degradation of two model pollutants, followed in decreasing order by AgBT, black TiO₂ (BT), sheet CN, bulk CN, and TiO₂. The order of pollutant degradation efficiencies by the photocatalysts was consistent with that of the charge carrier separation efficiencies. The degradation efficiency of the CNAgBT increased as the CN-to-AgBT ratio increased from 0.05 to 0.1, but decreased gradually for higher ratios between 0.15 and 0.20, indicating a lower optimal CN-to-AgBT ratio. A plausible photocatalytic degradation mechanism for the CNAgBT nanocomposites was proposed. Additionally, CNAgBT with a CN-to-AgBT ratio of 0.1 displayed a higher hydrogen generation rate with a maximum value of 21.5 mmol g⁻¹ over 5 h than those of the AgBT and BT. Overall, the CNAgBT prepared using ultrasonication-treated CNs showed enhanced photocatalytic performance for both pollutant degradation and hydrogen generation.     

Synthesis, characterization and effect of calcination temperature on phase transformation and photocatalytic activity of Cu,S-codoped TiO2 nanoparticles

A novel copper and sulfur codoped TiO₂ photocatalyst was synthesized by modified sol-gel method using titanium(IV) isopropoxide, CuCl₂·2H₂O and thiourea as precursors. The samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy equipped with energy dispersive X-ray micro-analysis (SEM-EDX), transmission electron microscopy (TEM) and Fourier transform infrared (FT-IR) analysis. The XRD results showed undoped and Cu,S-codoped TiO₂ nanoparticles only include anatase phase. Effect of calcination temperature showed rutile phase appears in 650 and 700 °C for undoped and 0.1% Cu,S-codoped TiO₂, respectively. The SEM analysis revealed the doping of Cu and S does not leave any change in morphology of the catalyst surface. The increase of copper doping enhanced “red-shift” in the UV-vis absorption spectra. The TEM images confirmed the dopants suppressed the growth of TiO₂ grains. The photocatalytic activity of samples was tested for degradation of methyl orange (MO) solutions. The results showed photocatalytic activity of the catalysts with 0.05% Cu,0.05% S and 0.1% Cu,0.05% S were higher than that of other catalysts under ultraviolet (UV) and visible irradiation, respectively. Because of synergetic effect of S and Cu, the Cu,S-codoped TiO₂ catalyst has higher activity than undoped and Cu or S doped TiO₂ catalysts.     

FeTPP-Cr-TiO2微球的制备及其可见光催化性能

通过四苯基铁卟啉敏化Cr掺杂TiO₂微球成功合成了一种复合改性可见光催化剂FeTPP-Cr-TiO₂.利用XRD、FT-IR、SEM、XPS、UV-Vis和N₂吸附-脱附等温线等技术对其结构和形貌进行了表征.以亚甲基蓝为目标降解物,在150 W氙灯的辐照下,考察了其可见光催化活性.结果表明FeTPP-Cr-TiO₂呈锐钛矿相,表面积为74.7 m²/g.与Cr-TiO₂和FeTPP-TiO₂相比,FeTPP-Cr-TiO₂表现出很好的可见光降解性能.以三种喹诺酮类抗生素（洛美沙星、诺氟沙星和氧氟沙星）为实验对象,考察了FeTPP-Cr-TiO₂降解水体中抗生素的可行性,对三种抗生素均有很高的降解率,降解过程符合一级动力学模型,反应动力学常数分别为3.02×10^-2、2.81×10^-2和3.86×10^-2min^-1,半衰期为22.9、24.6及17.9 min.     

Effects of steps and defects on O2 dissociation on clean and modified Cu(1 0 0)

Dissociative chemisorption of O₂ on Cu(1 0 0), S/Cu(1 0 0) and Ag/Cu(1 0 0) surface alloy has been investigated by Auger electron spectroscopy (AES). A strong reduction in the initial O₂ chemisorption probability (S₀) from 0.05 to 7.4 × 10⁻³ is observed already at an Ag coverage of 0.02 ML. Further Ag deposition results only in a moderate decrease in S₀. Similar inhibition of O₂ dissociation is observed on S/Cu(1 0 0). It is concluded that at very low Ag coverages, the reduced reactivity of Ag/Cu(1 0 0) towards O₂ dissociation is primarily due to the steric blocking of the surface defects and that any electronic effects are only secondary and present only at higher Ag coverages.