Reduction and dephosphorization of molten iron oxide with hydrogen-argon plasma

A laboratory-scale test was made in which iron oxide contained in a water-cooled crucible was melted and reduced by using a 10–50% H₂-Ar transferred arc plasma. The degree of reduction was found to be proportional to the amount of hydrogen fed. The efficiency of hydrogen utilization for the reduction was 50–70%, which is much higher than equilibrium values below 3000 K. This high efficiency was attributable partially to the reactivity of the hydrogen atom in a plasma and partially to the continuous contact of the hydrogen plasma with the molten iron oxide layer floating over the liquid iron formed. During the plasma reduction, evaporative loss of phosphorus was observed. The degree of phosphorus removal depended on the weight ratio, CaO/(SiO₂+Al₂O₃). H₂-Ar plasma was shown to be far superior for the phosphorus removal, compared with Ar and Ar-N₂ plasma.     

Photocatalytic production of hydrogen from water–alcohol media with the participation of mesoporous TiO<Subscript>2</Subscript>

Samples of mesoporous TiO₂ containing 80-85% of anatase and 15-20% of rutile with average particle and pore sizes of ∼10 nm and specific surface areas of 70 m²/g were obtained. The nanohetero structures TiO₂/Cu formed during photocatalytic reduction of Cu^II exhibit photocatalytic activity in the release of hydrogen from water–ethanol mixtures. The quantum yield with respect to atomic hydrogen amounts to 1.5.     

Ultrasonic Preparation of Hierarchical Graphene‐Oxide/TiO2 Composite Microspheres for Efficient Photocatalytic Hydrogen Production

Hierarchical graphene oxide (GO)‐TiO₂ composite microspheres with different GO/TiO₂ mass ratios were successfully prepared by mixing GO and TiO₂ microspheres under ultrasonic conditions. Ultrasonication helped the GO and TiO₂ microsphere to uniformly mix on the microscale. The results showed that the GO‐TiO₂ composites that were prepared by ultrasonic mixing exhibited significantly higher hydrogen‐evolution rates than those that were synthesized by simple mechanical grinding, owing to synergetic effects, including enhanced light absorption and scattering, as well as improved interfacial charge transfer because of the excellent contact between the GO sheets and TiO₂ microspheres. In addition, GO‐TiO₂‐3 (3 wt. % GO) showed the highest hydrogen‐generation rate (305.6 μmol h^?), which was about 13 and 3.3‐times higher than those of TiO₂ microsphere and GO‐P25 (with 3 wt. % GO), respectively. Finally, a tentative mechanism for hydrogen production is proposed and supported by photoluminescence and transient photocurrent measurements. This work highlights the potential applications of GO‐TiO₂ composite microspheres in the field of clean‐energy production.     

Enhanced degradation of organic pollutant 4-chlorophenol in water by non-thermal plasma process with TiO2

The combined application of TiO₂ photocatalyst and pulsed high-voltage electrical discharge process for the degradation of organic pollutant parachlorophenol (4-CP) in aqueous solution was tentatively investigated. The optimum conditions for 4-CP removal were applied voltage at 14 kV, electrode distance at 2 cm, pH at 6.5 (close to neutral solution), TiO₂ concentration at 50 mg/L, gas source O₂ at 100 L/h, and hybrid corona-streamer discharge mode. Introduced TiO₂ into pulsed discharge plasma process under such optimum condition, the rate constant of 4-CP degradation (k _cp) was greatly promoted, from 1.56×10⁻³ to 2.81×10⁻³ s⁻¹, and energy efficiency for 4-CP removal was greatly enhanced by approximately one time, and it was attributed to more amounts of chemically active species (e.g., ozone and hydrogen peroxide, especially hydroxyl radicals) produced in pulsed discharge plasma process in combination with TiO₂ photocatalyst.     

Functionalization of cotton fabrics with corona/air RF plasma and colloidal TiO2 nanoparticles

This study discusses the possibility of using a corona discharge at atmospheric pressure and air RF plasma at low pressure for the cotton fibre activation prior to deposition of colloidal TiO₂ nanoparticles in order to enhance antibacterial, UV protective and self-cleaning properties. X-ray photoelectron spectroscopy (XPS) analysis confirmed the presence of TiO₂ nanoparticles on the surface of cotton fibres. XPS elemental mapping indicated that TiO₂ nanoparticles were more evenly distributed across the surface of untreated and corona pre-treated cotton fabrics in comparison with RF plasma pre-treated fabric. Atomic absorption spectroscopy measurements revealed that the equivalent total content of TiO₂ in the cotton fabrics pre-treated by corona and RF plasma was 31% higher than in the fabric that did not undergo any treatment prior to loading of TiO₂ nanoparticles. In order to achieve maximum bacteria (Gram-negative bacteria Escherichia coli) reduction, untreated cotton fabric had to be loaded with colloidal TiO₂ nanoparticles twice, but only once following corona or RF plasma pre-treatment. Deposition of TiO₂ nanoparticles onto cotton fabrics provided maximum UV protective rating of 50+. Extraordinary photocatalytic activity of TiO₂ nanoparticles deposited onto cotton fabrics was proved by self-cleaning of blueberry juice stains and photodegradation of methylene blue in aqueous solution under UV illumination.     

Photocatalytic hydrogen evolution over mesoporous TiO2/metal nanocomposites

Na⁺ complex with the dibenzo-18-crown-6 ester was used as a template to synthesize mesoporous titanium dioxide with the specific surface area 130–140 m²/g, pore diameter 5–9 nm and anatase content 70–90%. The mesoporous TiO₂ samples prepared were found to have photocatalytic activity in Cu^II, Ni^II and Ag^I reduction by aliphatic alcohols. The resulting metal–semiconductor nanostructures have remarkable photocatalytic activity in hydrogen evolution from water–alcohol mixtures, their efficiency being 50–60% greater than that of the metal-containing nano-composites based on TiO₂ Degussa P25.The effects of the thermal treatment of mesoporous TiO₂ upon its photocatalytic activity in hydrogen production were studied. The anatase content and pore size were found to be the basic parameters determining the photoreaction rate. The growth of the quantum yield of hydrogen evolution from TiO₂/Ag⁰ to TiO₂/Ni⁰ to TiO₂/Cu⁰ was interpreted in terms of differences in the electronic interaction between metal nanoparticles and the semiconductor surface. It was found that there is an optimal metal concentration range where the quantum yield of hydrogen production is maximal. A decrease in the photoreaction rate at further increment in the metal content was supposed to be connected with the enlargement of metal nanoparticles and deterioration of the intimate electron interaction between the components of the metal–semiconductor nanocomposites.     

Photoassisted hydrogen production from a methanol-water mixture on platinized Cr2O3-DOPED TiO2

In situ reduction of previously adsorbed Pt⁴⁺ species on TiO₂ (anatase) was employed to obtain highly active catalysts for hydrogen photoevolution from a methanol-water solution. A quantum yield as high as 22% was observed. Optimum platinum coverage and the most favourable reaction conditions were established. The influence of surface Cr₂O₃ admixtures on photoactivity of TiO₂ was investigated. It was found that although the dopant shifts the anatase spectrum into the visible, it was not possible to obtain hydrogen with light of energy smaller than the bandgap of TiO₂. However, a small amount of Cr₂O₃ on the TiO₂ surface acts as a poor catalyst for hydrogen evolution.     

Converting red mud wastes into mesoporous ZSM-5 decorated with TiO2 as an eco-friendly and efficient adsorbent-photocatalyst for dyes removal

Red mud wastes have been converted into mesoporous zeolite socony mobile-5 (ZSM-5) followed by deposited titanium dioxide (TiO₂) nanoparticles to generate synergy adsorption-photodegradation for removal of dye removal in waste water. The amount of TiO₂ loading was varied to achieve optimum photocatalytic activity while maintaining the mesoporosity and high surface area of ZSM-5. Sol-gel method facilitated the formation of anatase TiO₂ on the ZSM-5. The fourier transform infrared spectra clarified the formation of Si–O–Ti at 957 cm^?1 by the exchanging the hydrogen ion with titanium ion, which proved by decreasing the absorption band of Si–OH and Si–O interaction at 964 and 944 cm^?1, respectively. Sol-gel method also preserved the mesopore diameter of ZSM-5 at 3.5 nm which allow the diffusion of methylene blue (MB) molecules into the pores. However, the surface area and the pore volume were slightly reduced with increasing the TiO₂ loading. The adsorption performance of samples showed that the increasing in the TiO₂ loading led to the decreasing in the adsorption capacity. All samples showed the suitability towards the pseudo second order kinetic. The Langmuir isotherm was suitable to describe the adsorption mechanism by monolayer adsorption. Mesoporosity of ZSM-5 accelerated the adsorption of dye via the increase of mass transfer in the pore channel which confirmed by the low intercept of intraparticle diffusion model at the first stage. The photocatalytic test showed that 10% TiO₂ loading on the ZSM-5 exhibited the highest methylene blue removal followed by 5% and 20% TiO₂ loading. Optimization on the amount of photocatalyst and the pH of solution indicated the reaction favoured 1 g L^?1 of catalysts and at alkaline pH. 10% TiO₂/ZSM-5 also exhibited high stability and reusability up to four reaction cycles. Photocatalytic performance of 10% TiO₂/ZSM-5 was further investigated on photodegradation of malachite green and rhodamine B organic dyes, which showed the photocatalytic efficiency of 73 and 88%, respectively. Superoxide radical, hydroxyl radical, and photogenerated electron were identified as the main active species for MB photodegradation based on the reduction of degradation rate following the addition scavenger molecules.     

Performance of a photocatalytic hybrid system coupled with a stainless steel membrane for removal of humic acid

The objective of this study was to evaluate the performance of a photocatalysis/H₂O₂/metal membrane hybrid system in the degradation of humic acid. A metal membrane of nominal pore size 0.5 μm was used in the experiment for separation of TiO₂ particles. Hydrogen peroxide was tested as an oxidant. The efficiency of removal of COD_Cr and color increased rapidly for initial hydrogen peroxide concentrations up to 50 mg L⁻¹. The efficiency of removal of COD_Cr and color by 50 mg L⁻¹ initial hydrogen peroxide concentration was approximately 95 and 98%, respectively. However, addition of hydrogen peroxide over 50 mg L⁻¹ inhibited the efficiency of the system. Addition of hydrogen peroxide to a UV/TiO₂ system enhanced efficiency of removal of COD_Cr and color compared with no addition of hydrogen peroxide. This may be ascribed to capture electrons ejected from TiO₂ and to the production of OH radicals. Application of the metal membrane in the UV/TiO₂/H₂O₂ system enhanced the efficiency of removal of COD_Cr and color because of adsorption by the metal membrane surface and the production of OH radicals. By application of a metal membrane with a nominal pore size of 0.5 μm, TiO₂ particles were effectively separated from the treated water by metal membrane rejection. The photocatalytic metal membrane had much less resistance than the humic acid, TiO₂, and humic acid/TiO₂ because of the degradation of humic acid by the photocatalytic reaction.     

The kinetics of reduction of synthetic ulvospinel in a hydrogen atmosphere

Ulvospinel, having the composition Fe₂TiO₄, was prepared by heating an intimate mixture of Fe₂O₃ and TiO₂ in a controlled atmosphere of CO₂ and H₂. The kinetics of its reduction by H₂ was studied. The parameters controlling the rate of reduction, such as temperature, granulometry and hydrogen partial pressure were investigated. The optimum temperature range for reduction of the ulvospinel to TiO₂ and Fe was established to be between 600° and 800°; above 800° reduction of the TiO₂ commenced.     

Hydrothermal Preparation and Characterization of TiO2/BiVO4 Composite Catalyst and its Photolysis of Water to Produce Hydrogen

In the present work, bismuth vanadate composited photocatalysts were synthesized and characterized. X‐ray diffractometry and Raman results showed that the particles were well crystallized, and formed by the complex of monoclinic BiVO₄ and TiO₂. On electron microscopy, the photocatalyst exhibited high crystallization, agglutination and irregular shape, and was surrounded by numerous TiO₂ particles. The study of surface areas showed that the specific surface area of 30‐BiVO₄/TiO₂ composited was 112 m²·g^?1, which was nearly 10 times that of pure BiVO₄. The ultraviolet–visible diffuse reflectance spectra indicated the composited photocatalyst were activated in visible light. The activity of photocatalytic water splitting was studied. The results showed that monomer BiVO₄ photocatalyst was not able to produce hydrogen under any light source. BiVO₄/TiO₂ composited photocatalysts, however, were capable of generating hydrogen. Under UV light irradiation for 120 min, 1 g catalyst dispersed in 50 mL deionized water produced almost 1 mL hydrogen, such that the productivity of hydrogen was higher than that of P25‐TiO₂. Photocatalytic decomposition of water under visible light also confirmed that the BiVO₄/TiO₂ composited photocatalyst had the ability of water splitting.     

Visible Light Photocatalytic Activity of Pt/N‐TiO2 towards Enhanced H2 Production from Water Splitting

Present work mainly focuses on experimental investigation to improvement of hydrogen production by water photoelectrolysis. An experimental facility was designed and constructed for visible light photocatalysis. A series of N‐TiO₂ photocatalysts impregnated with platinum on the surface of N‐TiO₂ were prepared. Hydrogen production upon irradiating aqueous Pt/N‐TiO₂ suspension with visible light was investigated. The shift in excitation wavelength of TiO₂ was 380 nm improved the yield of hydrogen production by N‐TiO₂ and Pt/N‐TiO₂. We used a 400 W mercury arc lamp combined with a 400 nm cutoff filter eliminating all the wavelengths under 400 nm. Pt/N‐TiO₂ material was characterized with TPR, reflective UV/Visible spectroscopy and TEM. The best hydrogen production rate obtained for this setup for N/Ti = 10, 0.05 wt% Pt/N‐TiO₂, through water splitting was about 772 μmolh^?1g^?1.     

Application of Pulsed Traveling Hydrogen Arcs for Metal Oxide Reduction

A plasma reactor that has a transient traveling arc has been used to study hydrogen in relation to in-flight reduction of metal oxide particles. Experiments were done to determine the nature of the arc and its interaction with the reactor gas. The lifetime of the excited atomic hydrogen was measured and it was found to be more than 4 ms after the arc had ceased. Powders and tablets of oxides were exposed to the pulsed-arc treated hydrogen and found to react much more rapidly and intensely than when exposed to hot molecular hydrogen. The results suggest that atomic hydrogen will exist throughout the volume of such a reactor for a period that is sufficient to reduce particles of FeO, Cr₂O₃, and TiO₂.     

贵金属负载TiO2对光催化还原CO2选择性的影响

利用光沉积方法在TiO₂表面分别负载1%(质量分数) Pt、Pd、Au和Ag助催化剂.用TEM、XRD、UV-vis等技术对催化剂进行了表征,并利用连续瞬态电流时间响应和线性扫描伏安法等电化学方法,对贵金属负载的TiO₂光催化剂在光照条件下的电流响应强度及电催化析氢电位等特性加以测试.分析了贵金属助催化剂对光催化还原CO₂性能的差异.结果表明,负载贵金属助催化剂能显著加速光生电子空穴的分离,降低复合率;另外,助催化剂对还原CO₂选择性的顺序为Ag>Au>Pd>Pt.贵金属助催化剂还原CO₂的加氢选择性和析氢过电位存在相关性,即越不利于析氢过程的助催化剂,其催化CO₂加氢还原产物的选择性越高.     

Photocatalytic activity of TiO2 prepared by adding polyethyleneglycol

TiO₂ was produced by the sol-gel method with the addition of polyethyleneglycol (PEG) to study the effects of the molecular weight and the addition percentage of PEG. Bisphenol A (BPA) degradation rate constants were highest as 3.07, 4.02 and 4.23 h⁻¹ at PEG addition percentages of 10%, 5% and 0.5%. After 12 h reaction, the total organic carbon (TOC) reductions in UV/TiO₂, UV/TiO₂/PEG(200, 10%), UV/TiO₂/PEG(600, 5%) and UV/TiO₂/PEG(3500, 0.5%) systems were 44%, 24%, 19% and 23%, in order. The results demonstrated that adding an appropriate percentage of PEG to the TiO₂ preparation processes increased the BPA degradation and TOC reduction.     

Au改性TiO2纳米复合物对人结肠癌细胞的光催化杀伤作用

提出了通过TiO₂表面修饰纳米Au的方法来提高纳米TiO₂光催化杀伤癌细胞的效率. 采用化学还原法合成了Au改性的TiO₂ (Au/TiO₂)纳米复合物, 并研究了不同掺杂量(1 wt%, 2 wt%, 4 wt%)的Au/TiO₂对人结肠癌LoVo细胞的光催化杀伤效应. 结果显示, Au的掺杂大大地提高了TiO₂纳米粒子光催化杀伤结肠癌LoVo细胞的效率, 而且Au掺杂量的高低影响Au/TiO₂光催化杀伤癌细胞的效率, 掺金量为2%的Au/TiO₂对结肠癌LoVo细胞具有最高的光催化杀伤效率. 在光强为1.8 mW/cm²的紫外灯(λ_max＝365 nm)下光照110 min, 50 μg/mL掺金量为2%的Au/TiO₂能够杀死所有的癌细胞, 而同样浓度的TiO₂只能杀死70%的癌细胞.     

蜂窝状Ho改性Fe-Mn/TiO2催化剂的制备及其低温选择催化还原(SCR)脱硝性能

采用模压法制备了蜂窝状Ho改性的Fe-Mn/TiO₂催化剂,研究了结构助剂、黏合剂和造孔剂等对成型催化剂低温选择催化还原（SCR）脱硝性能的影响。优选出一套理想的成型参数：水粉质量比为40%且逐次分批加入;结构助剂玻璃纤维的用量为10%（质量分数）;黏合剂羧甲基纤维素的用量为5%（质量分数）;助挤剂甘油的添加量为10%（质量分数）且分批加入;造孔剂活性炭粉的用量为2%（质量分数）。该蜂窝状催化剂在120 ℃下脱硝率维持在90%以上,并且在SO₂体积分数低于0.02%时具有一定的抗硫抗水性。表征结果表明,成型后蜂窝状催化剂比表面积降低,颗粒分散程度明显减弱,并且表面酸量和表面Mn⁴⁺含量下降,对催化活性有一定的影响。     

In situ FT-IR studies of NO decomposition on Pt/TiO2 catalyst under UV irradiation

Photodecomposition of NO on the well-dispersed Pt/TiO₂ catalyst under UV irradiation was studied by in situ DRIFT (Diffuse-Reflectance Infrared Fourier-Transform) spectroscopy. 2 wt% Pt/TiO₂ catalyst was prepared by photochemical deposition method. The photocatalytic activity of Pt/TiO₂ is highly dependent on its pretreatment. Although the catalyst exhibited a highly adsorption capability to NO after hydrogen reduction or thermal evacuation at 500°C, no evidence upon NO decomposition was observed under UV irradiation. While reducing the catalyst at 300°C in the hydrogen flow, it not only exhibited an intense NO adsorption but also conducted a direct decomposition of NO to N₂ and O₂ under UV irradiation. The hydrogen reduction at 200°C led to a weaker NO adsorption. During UV irradiation, the IR peaks of NO fully disappeared and N₂O was formed. It is concluded that the photochemical prepared Pt/TiO₂ catalyst after activating at mild reduction conditions is highly active for NO photodecomposition. The effective oxidation states of the active components, the surface structure and the reaction mechanisms will be discussed.     

TiO2-Al2O3载体的制备方法对其负载的磷化镍催化剂加氢脱氮反应性能的影响

采用共沉淀法和原位溶胶-凝胶法制备了TiO₂-Al₂O₃复合载体,其负载的磷化镍催化剂采用等体积浸渍法和H₂原位还原法制备. 通过N₂吸附（BET）、X射线衍射（XRD）、透射电镜（TEM）、程序升温还原（TPR）,X射线光电子能谱（XPS）和等离子体发射光谱（ICP-AES）表征技术对催化剂进行了表征,并通过喹啉的加氢脱氮反应评价了催化剂的加氢脱氮性能. 结果表明,原位溶胶-凝胶法制成的复合载体基本保留了原有的γ-Al₂O₃的孔特征,具有较大的比表面积和较宽的孔分布,TiO₂主要以表面富集的形式分散在管状的γ-Al₂O₃表面,其负载的磷化镍催化剂还原后所形成的活性相为Ni₂P和Ni₁₂P₅;而共沉淀法制成的复合载体比表面积较小,孔径分布更加集中,TiO₂趋于在块状的Al₂O₃表面均匀分散,其负载的磷化镍催化剂具有更好的可还原性,还原后所形成的活性相为Ni₂P. 不同的载体制备方法和不同的钛铝比对催化剂加氢脱氮性能影响较大,当n（Ti）/n（Al）=1/8时,共沉淀法载体负载的催化剂表现出最佳的加氢脱氮性能,在340 ℃,3 MPa,氢油体积比500,液时空速3 h^-1的反应条件下,喹啉的脱氮率可以达到91.3%.     

In Situ Raman Monitoring and Manipulating of Interfacial Hydrogen Spillover by Precise Fabrication of Au/TiO2/Pt Sandwich Structures

The spillover of hydrogen species and its role in tuning the activity and selectivity in catalytic hydrogenation have been investigated in situ using surface‐enhanced Raman spectroscopy (SERS) with 10 nm spatial resolution through the precise fabrication of Au/TiO₂/Pt sandwich nanostructures. In situ SERS study reveals that hydrogen species can efficiently spillover at Pt‐TiO₂‐Au interfaces, and the ultimate spillover distance on TiO₂ is about 50 nm. Combining kinetic isotope experiments and density functional theory calculations, it is found that the hydrogen spillover proceeds via the water‐assisted cleavage and formation of surface hydrogen–oxygen bond. More importantly, the selectivity in the hydrogenation of the nitro or isocyanide group is manipulated by controlling the hydrogen spillover. This work provides molecular insights to deepen the understanding of hydrogen activation and boosts the design of active and selective catalysts for hydrogenation.