A P/N type compounded Cu<Subscript>2</Subscript>O/TiO<Subscript>2</Subscript> photo-catalytic membrane for organic pollutant degradation

A heterojunction thin film consisting of n-type titanium dioxide (TiO₂) and p-type cuprous oxide (Cu₂O) was fabricated on an FTO conducting glass. The TiO₂ films were grown on the FTO glass by sol–gel and spray pyrolysis methods, and Cu₂O was deposited on it via the hydrothermal method. The morphology, crystalline structure, and optical absorption characteristics were studied by scanning electron microscopy, X-ray diffraction, and ultraviolet–visible diffuse reflectance spectrum, respectively. The results show that the surface of the Cu₂O/TiO₂ film was composed of net and large grains, which contributed to a large specific surface area. The crystal phase of the TiO₂ in the Cu₂O/TiO₂ film remained anatase. The crystal phase of the Cu₂O could not be detected as it is found in traces. The Cu₂O/TiO₂ film had a stronger optical absorption ability than the pure TiO₂ film. To investigate catalytic activity, a photocatalytic degradation experiment of the Cu₂O/TiO₂ film was performed in a homemade thin-layer micro-reactor. The photocatalytic degradation of methylene blue increased with increasing amounts of deposited Cu₂O until a maximum limit was reached. The photocatalytic activity might have declined with an increase in Cu₂O content. The metallic oxide has the potential to screen other photocatalysts from the UV source.     

Photocatalytic activity of Au/TiO<Subscript>2</Subscript> nanocomposite for azo-dyes degradation

The structural properties of Au/TiO₂ catalyst were studied by X-ray diffraction, UV-visible diffuse reflectance, photoluminescene, scanning transmission and electron microscope, and temperature programmed reduction. The photocatalytic activity of the catalysts was evaluated for the degradation of various azo-dyes such as methylene blue, methyl orange, reactive blue-4, and eosin-B under solar irradiation. It was found that TiO₂ catalyst modified with gold exhibits higher percentage of degradation compared to starting TiO₂. For example, TiO₂ showed 35% of methyl orange degradation whereas gold modified TiO₂ possessed 82%. Effect of different parameters such as pH and dye concentration has been evaluated and the photocatalytic activity was correlated with physico-chemical properties. The dye degradation rate followed first order kinetics.     

Preparation and photocatalytic activity of cuprous oxides

Cuprous oxide (Cu₂O) nanoparticles and microcubes have been successfully fabricated by reduce of CuSO₄ using ascorbic acid at room temperature. The as-synthesized products were easily separation and purification, because there were no template or surfactant has been introduced. All of the samples were characterized by X-ray powder diffractometer (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectrometer (FTIR) and ultraviolet and visible light spectrometer (UV–vis). The microscale Cu₂O samples exhibited a high catalytic activity on photodegradation of methyl orange by visible light. It was found that Cu₂O microcubes have higher photocatalytic activity and the photocatalytic degradation ratio of methyl orange reached to 98.1%.     

Simultaneous removal of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> and SO<Subscript>2</Subscript> by low-temperature selective catalytic reduction over modified activated carbon catalysts

A series of modified porous activated carbon (AC) catalysts prepared by impregnation were investigated for the low-temperature (≤250°C) selective catalytic reduction (SCR) of NO _x with NH₃ with simultaneous removal of SO₂. The effects of various preparation conditions and reaction conditions on NO and SO₂ conversions were observed, such as support type, active components, copper loading, calcination temperature and presence of H₂O and O₂. The modified AC catalysts were characterized by BET, XRD, TG and TPX methods. The activity test results showed that the optimal catalyst is 15% Cu/WCSAC which can provide 52% NO conversion and 68% SO₂ conversion simultaneously at 175°C with a space velocity of 30000 h^?1, and the optimal calcination temperature was 500°C. The presence of H₂O could inhibit NO conversion and promote the SO₂ conversion. The effect of O₂ (0–5%) was evaluated, and the NO and SO₂ conversions were best when the concentration of O₂ was 3%. Research demonstrated that Cu/WCSAC catalyst was a kind of potential catalysts due to the amorphous phase, high specific areas and high active ability.     

金/氧化亚铜异质球的制备及其可见光催化性能

使用L-半胱氨酸作为连接剂, 利用硼氢化钠原位还原预先吸附在介孔氧化亚铜表面的氯金酸根离子,得到了Au/Cu₂O异质结构. 应用X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)、紫外-可见(UV-Vis)光谱和N₂物理吸附等手段对催化剂进行表征, 并以λ>400 nm的可见光作为光源, 评价了该催化剂光催化降解亚甲基蓝(MB)的活性. 实验结果表明, 直径为4 nm的金颗粒完好地负载在介孔氧化亚铜的表面, 并且介孔氧化亚铜的细微结构与孔径均未发生变化. 研究表明, 以乙醇作为反应溶剂有效抑制了AuCl₄^-与Cu₂O之间的氧化还原反应, 从而有利于氧化亚铜介孔结构的保持及金颗粒的原位还原. 光催化降解亚甲基蓝的结果表明, Au/Cu₂O异质结构的光催化活性比纯氧化亚铜光催化活性有明显提高. 推测其光催化性能提高的主要原因如下: 一方面, 金颗粒良好的导电性有利于氧化亚铜表面电子的快速转移, 实现电子-空穴分离; 另一方面, 金颗粒可能存在的表面等离子共振现象加速了光生电子的产生.     

Z型异质结Cu2O/Bi2MoO6的构建及光催化降解性能

通过水热法制备出一系列Z型异质结Cu₂O/Bi₂MoO₆新型光催化剂。采用扫描电子显微镜、粉末X射线衍射、红外光谱、紫外可见吸收光谱等表征手段研究了催化剂的形貌、结构性质和光电化学性质,并以四环素(TC)为降解目标污染物,进一步探究了其催化效率。实验结果表明,Cu₂O的加入提高了复合催化剂的光催化性能,其中20% Cu₂O/Bi₂MoO₆复合催化剂(Cu₂O和Bi₂MoO₆的质量比为20%)降解效果最好,100 min内可降解95%的TC。Cu₂O与Bi₂MoO₆之间的协同作用使其可以吸收更多的可见光,所构建的Z型异质结改变了电子转移途径,提高了电子与空穴的分离效率,光催化活性显著提高。通过自由基捕获实验和能带结构,分析了Z型异质结Cu₂O/Bi₂MoO₆复合催化剂光催化降解TC可能的机理。     

Facile synthesis of core-shell ZnO/Cu<Subscript>2</Subscript>O heterojunction with enhanced visible light-driven photocatalytic performance

As p–n heterojunction photocatalysts usually possess dramatically improved photocatalytic activity than single photocatalysts, a novel ZnO/Cu₂O heterojunction was designed by a facile self-templating method in this study. The crystal structure, chemical composition, surface morphology, and optical property of ZnO/Cu₂O heterojunction were investigated to clarify the structure-property correlation. Scanning electron microscope and transmission electron microscope images proved the uniform core-shell submicrospheres of ZnO/Cu₂O, in which a three-dimensional flower-like ZnO core was coated by a shell comprised of Cu₂O nanoparticles. The photoresponse result showed that the band gap of the ZnO/Cu₂O core-shell submicrospheres became narrow, and the absorption edge shifted from the ultraviolet region (380?nm) to the visible region (500?nm) compared with the pure ZnO microflowers. For the degradation of Rhodamine B under visible light, the photocatalytic efficiency of ZnO/Cu₂O submicrospheres reached 96% within 40?min of reaction time, which was 3.8 times higher than that of pure ZnO microflowers and up to 4.5 times than that for pure Cu₂O nanoparticles. The remarkable visible light-driven photocatalytic performance is mainly attributed to the extended photoresponse range and effective separation of the photo-generated electron-hole pairs in the unique heterojunction.

Open image in new window

ZnO/Cu₂O core-shell microspheres for the degradation of RhB under visible light

     

Effect of copper precursors on the catalytic activity of Cu/ZSM-5 catalysts for selective catalytic reduction of NO by NH<Subscript>3</Subscript>

The Cu/ZSM-5 catalysts prepared by different copper precursors were used for the selective catalytic reduction (SCR) of NO _x with NH₃. The Cu/ZSM-5 catalyst prepared by the copper nitrate (Cu/ZSM-5-N) presented the best performance among the Cu/ZSM-5 catalysts and showed above 90 % NO _x conversion at 225–405 °C. The average particle size of CuO was 5.82, 9.20, and 11.01 nm over Cu/ZSM-5-N, Cu/ZSM-5-S (prepared by copper sulfate), and Cu/ZSM-5-C (prepared by copper chloride), respectively. The Cu/ZSM-5-N catalyst showed the highly dispersed copper species, the strong surface acidity, and the excellent redox ability compared with the Cu/ZSM-5-C and Cu/ZSM-5-S catalysts. The Cu⁺ and Cu²⁺ existed in the Cu/ZSM-5 catalysts and the abundant Cu⁺ over Cu/ZSM-5-N might be responsible for the superior SCR activity.     

Synthesis,characterization of B-doped TiO<Subscript>2</Subscript> nanotubes with high photocatalytic activity

B-doped TiO₂ nanotubes (B/TiO₂ NTs) were prepared by the combination of sol–gel process with hydrothermal treatment. The prepared catalysts were characterized by XRD, TEM and XPS. The photocatalytic activity of B/TiO₂ NTs was evaluated through the photodegradation of aqueous methyl orange. The results demonstrated that the 1.5% B/TiO₂ NTs calcined at 300 °C possessed the best photocatalytic activity. Compared with pure TiO₂ nanotubes, the doping with B significantly enhanced the photocatalytic efficiency.     

Selective Catalytic Reduction of NO by NH<Subscript>3</Subscript> over MoO<Subscript>3</Subscript> Promoted Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalyst

A series of MoO₃ doped Fe₂O₃ catalysts prepared by the co-precipitation method were investigated in the selective catalytic reduction of NO by NH₃ (NH₃-SCR). The catalysts displayed excellent catalytic activity from 225 to 400°C and high tolerance to SO₂/H₂O poisoning at 300°C. To characterize the catalysts the N₂-BET, XRD, Raman, NO-TPD, NH₃-TPD and in situ DRIFTS were carried out. It was found that the main reason explaining a high NH₃-SCR performance might be the synergistic effect between Fe and Mo species in the catalyst that could enhance the dispersion of Fe₂O₃ and increase NH₃ adsorption on the catalyst surface.     

Effective photocatalytic degradation of an azo dye over nanosized Ag/AgBr-modified TiO<Subscript>2</Subscript> loaded on zeolite

Zeolite-based photocatalysts were prepared by the sol-gel and deposition methods. The photocatalysts were characterised by X-ray diffraction, nitrogen adsorption-desorption isotherms, FTIR spectroscopy, scanning electron microscopy and energy-dispersive X-ray spectrometry. The activity of the prepared photocatalysts was evaluated by the UV-induced degradation of acid blue 92, a textile dye in common use. The effect of various parameters, such as catalyst concentration, initial dye concentration, thiosulphate concentration and pH, on the rate and efficiency of the photocatalytic degradation of acid blue 92 was investigated. The results showed that each parameter influenced the degradation rate and efficiency in a particular way. It was also found that, under optimised conditions, Ag/AgBr/TiO₂/zeolite exhibited the highest photocatalytic performance. A comparison of catalytic activity when exposed to visible light under the same conditions showed that the photocatalysts containing AgBr had the highest activity.     

Facile synthesis of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Cu<Subscript>2</Subscript>O nanocomposite and its visible light photocatalytic activity for the degradation of cationic dyes

Iron oxide-loaded Cu₂O photocatalysts were prepared by a facile hydrothermal method. The binary mixed metal oxide photocatalyst was characterized by XRD, FE-SEM, FTIR, UV–Vis-DRS, particle size and zeta potential measurements. XRD analysis showed that Fe₂O₃/Cu₂O catalysts were phase pure and highly crystalline in nature. FE-SEM images revealed the formation of nanospherical Fe₂O₃ over the Cu₂O surface during hydrothermal reaction. From UV–Vis diffuse reflectance spectroscopy studies, the optical band gap of the Fe₂O₃/Cu₂O photocatalyst was found to be slightly red-shifted to 1.85 eV, after loading of Fe₂O₃. The zeta potential analysis revealed that the surface of the Fe₂O₃/Cu₂O photocatalyst was negatively charged in neutral solution. The loading of n-type Fe₂O₃ on p-type Cu₂O augments the charge carrier separation at the interface, which was evident from the enhanced photodegradation of organic pollutants (Methylene blue and Rhodamine B dyes) under visible light irradiation.     

The effect of spinel type support FeAlO<Subscript>3</Subscript>, ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript>, CrAl<Subscript>3</Subscript>O<Subscript>6</Subscript> on physicochemical properties of Cu,Ag, Au,Ru supported catalysts for methanol synthesis

The comparative study of the role of binary oxide support on catalyst physico-chemical properties and performance in methanol synthesis were undertaken and the spinel like type structures (ZnAl₂O₄, FeAlO₃, CrAl₃O₆) were prepared and used as the supports for 5% metal (Cu, Ag, Au, Ru) dispersed catalysts. The monometallic 5% Cu/support and bimetallic 1% Au (or 1% Ru)-5% Cu/support (Al₂O₃, ZnAl₂O₄, FeAlO₃, CrAl₃O₆) catalysts were investigated by BET, XRD and TPR methods. Activity tests in methanol synthesis of CO and CO₂ mixture hydrogenation were carried out. The order of Cu/support catalysts activity in methanol synthesis: CrAl₃O{ia6} > FeAlO₃ > ZnAl₂O₄ is conditioned by their reducibility in hydrogen at low temperature. Gold appeared more efficient than ruthenium in promotion of Cu/support catalysts. Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 2, pp. 242–248. The article is published in the original.     

One-pot sequential synthesis of magnetically separable Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/AgCl photocatalysts with enhanced activity and stability

Magnetically separable Fe₃O₄/AgCl photocatalysts were prepared by a one-pot sequential method. A series of techniques proved the hybrid structure of Fe₃O₄/AgCl composites. Fe₃O₄/AgCl composites had a much higher photocatalytic activity toward Rhodamine B (RhB) degradation than pure AgCl under the simulated solar light irradiation. The existence of metal Ag resulted in high photocatalytic activity of Fe₃O₄/AgCl, which was related with the amount of metallic Ag. The scavenging experiments showed that the degradation reaction most probably was initiated by the photoinduced single-electron transfer, and the generation of superoxide anion (O ₂ ^-· ) played a significant role. The composite photocatalysts could be recycled by applying an external magnetic field, and the reused composites maintained their original photocatalytic activity. Fe₃O₄/AgCl composites were highly efficient, magnetically separable, and recoverable. This proves their potential applications in the photodegradation of organic pollutants.     

Gold catalysts supported on ZnO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> for low-temperature CO oxidation

Gold catalysts with loadings ranging from 0.5 to 7.0 wt% on a ZnO/Al₂O₃ support were prepared by the deposition–precipitation method (Au/ZnO/Al₂O₃) with ammonium bicarbonate as the precipitation agent and were evaluated for performance in CO oxidation. These catalysts were characterized by inductively coupled plasma-atom emission spectrometry, temperature programmed reduction, and scanning transmission electron microscopy. The catalytic activity for CO oxidation was measured using a flow reactor under atmospheric pressure. Catalytic activity was found to be strongly dependent on the reduction property of oxygen adsorbed on the gold surface, which related to gold particle size. Higher catalytic activity was found when the gold particles had an average diameter of 3–5 nm; in this range, gold catalysts were more active than the Pt/ZnO/Al₂O₃ catalyst in CO oxidation. Au/ZnO/Al₂O₃ catalyst with small amount of ZnO is more active than Au/Al₂O₃ catalyst due to higher dispersion of gold particles.     

Effect of the microstructure of the supported catalysts CuO/TiO<Subscript>2</Subscript> and CuO/(CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript>) on their catalytic properties in carbon monoxide oxidation

The effect of the microstructure of titanium dioxide on the structure, thermal stability, and catalytic properties of supported CuO/TiO₂ and CuO/(CeO₂-TiO₂) catalysts in CO oxidation was studied. The formation of a nanocrystalline structure was found in the CuO/TiO₂ catalysts calcined at 500°C. This nanocrystalline structure consisted of aggregated fine anatase particles about 10 nm in size and interblock boundaries between them, in which Cu²⁺ ions were stabilized. Heat treatment of this catalyst at 700°C led to a change in its microstructure with the formation of fine CuO particles 2.5–3 nm in size, which were strongly bound to the surface of TiO₂ (anatase) with a regular well-ordered crystal structure. In the CuO/(CeO₂-TiO₂) catalysts, the nanocrystalline structure of anatase was thermally more stable than in the CuO/TiO₂ catalyst, and it persisted up to 700°C. The study of the catalytic properties of the resulting catalysts showed that the CuO/(CeO₂-TiO₂) catalysts with the nanocrystalline structure of anatase were characterized by the high-est activity in CO oxidation to CO₂.     

Synthesis and photocatalytic activity of TiO<Subscript>2</Subscript> nanoparticles fluorine-modified with TiF<Subscript>4</Subscript>

Fluorine-modified TiO₂ nan oparticles were synthesized by introducing TiF₄ as a fluorine source either before or after the sufficient hydrolysis and condensation of Ti(OEt)₄. The photocatalytic activity of the fluorine-modified catalysts was found to be greatly affected by the fluorine position in TiO₂ nanoparticles. When TiF₄ and Ti(OEt)₄ hydrolyzed with synchronization, the fluorine tended to be doped in the lattice. The formation of Ti³⁺ defects could result in charge recombination in bulk and bring down the photocatalytic activity. In contrast, if TiF₄ was introduced after the sufficient hydrolysis and condensation of Ti(OEt)₄. Ti−F bonds could exist mainly on the TiO₂ particles surface, which not only prevented the growth of anatase crystals but also facilitated the transfer of organic compounds from solution to catalyst surface by reducing the hydrophilic properties.     

Light expanded clay aggregate (LECA) as a support for TiO<Subscript>2</Subscript>, Fe/TiO<Subscript>2</Subscript>, and Cu/TiO<Subscript>2</Subscript> nanocrystalline photocatalysts: a comparative study on the structure,morphology, and activity

In this work, TiO₂ and doped TiO₂ photocatalysts (Fe/TiO₂ and Cu/TiO₂) were synthesized by the sol–gel method. The main objective of this study was to investigate the influence of dopants on the structure, morphology, and activity of the catalysts in powder and immobilized states. XRF, XRD, and SEM methods were used to characterize the catalysts. The structure and phase distribution of the nanocrystalline powders were identified by XRD. Nanoparticles crystallite size and the degree of crystallinity were affected by doping. The anatase contents of catalysts were achieved as follows: TiO₂ (5.89 %) < Fe/TiO₂ (42.17 %) < Cu/TiO₂ (70.28 %). It was indicated that the activity of the catalysts strongly depends on the anatase content. Under the same circumstances, copper-modified TiO₂ exhibited a twofold higher photocatalytic activity compared with TiO₂. The nanostructured catalysts were immobilized on light expanded clay aggregate (LECA) granules in order to investigate the effect of a novel support on the activity of the catalysts. Morphological changes are recognizable in the SEM images. Activity tests indicated that the best catalytic performance was assigned to Cu/TiO₂/LECA. After 120 min of irradiation, 61 % degradation of phenol in synthetic wastewater was achieved. The high photocatalytic activity of Cu/TiO₂/LECA confirms that LECA is as an excellent support.     

脉冲沉积制备Cu2O/TiO2纳米管异质结的可见光光催化性能

在用阳极氧化法制备有序排列TiO₂纳米管阵列薄膜的基础上,引入脉冲沉积工艺,成功实现了均匀、弥散分布的Cu₂O纳米颗粒修饰改性TiO₂纳米管阵列,形成Cu₂O/TiO₂ 纳米管异质结复合材料. 利用场发射扫描电镜（FESEM）、场发射透射电镜（FETEM）、X射线衍射（XRD）、X射线光电子能谱（XPS）和紫外-可见漫反射光谱（UV-Vis DRS）对样品进行表征,重点研究了Cu₂O/TiO₂ 纳米管异质结的光电化学特性和对甲基橙（MO）的可见光催化降解性能. 结果表明,Cu₂O纳米颗粒均匀附着在TiO₂纳米管阵列的管口和中部位置,所制备的Cu₂O/TiO₂ 纳米管异质结具有高效的可见光光催化性能;在浓度为0.01 mol·L^-1的CuSO₄溶液中制得的Cu₂O/TiO₂纳米管异质结表现出最好的电化学特性和光催化性能;另外,对Cu₂O纳米颗粒影响光催化活性的机理进行了讨论.     

Photocatalytic activity of Cu2O nanoparticles prepared through novel synthesis method of precursor reduction in the presence of thiosulfate

A novel fabrication of Cu₂O nanoparticles was successfully achieved through the reduction of Cu²⁺ in the interlayer of montmorillonite (denoted as MT). The Cu₂O nanoparticles formed in the clay interlayer (denoted as Cu₂O/MT) had a lamellate shape of 20–100 nm in width and ca. 0.39 nm in thickness, and thus, the Cu₂O/MT exhibited a higher specific surface area than neat Cu₂O. The Cu₂O/MT was applied to a photocatalyst, and its photocatalytic activity was examined in terms of water reduction (i.e., H₂ evolution) in the presence of methanol (electron donor). The Cu₂O/MT showed a high photocatalytic activity in comparison with neat Cu₂O; moreover, the photocatalytic activity was improved by loading a Pt catalyst onto the surface of Cu₂O. Based on the dependencies of photocatalytic activity on light intensity as well as methanol concentration, it was revealed that the H₂ evolution from water on Cu₂O/MT is the rate-determining step. Thus, the active and efficient photocatalysis of Cu₂O/MT was associated with an increase in specific surface area corresponding to the number of active sites.