Room temperature ferromagnetism in Mn-doped ZnS nanocrystalline thin films grown by sol–gel dip coating process

Nanocrystalline Zn_1?xMn_xS (x = 0.00, 0.01, 0.02, 0.03, 0.05, and 0.1) thin films having different Mn content were grown by the sol–gel dip coating process. The effect of Mn content on the structural, optical and magnetic properties of Zn_1?xMn_xS nanocrystalline thin films were investigated. X-ray diffraction results showed the presence of single hexagonal phase corresponding to ZnS with a preferred orientation along the ZnS (002) hexagonal plane direction without any detectable secondary phase, suggesting the incorporation of Mn ions into the ZnS lattice. Scanning electron microscope revealed the surface of the nanocrystalline films to be homogeneous and dense and the grains of the film surface were randomly scattered. In ultraviolet–visible measurements, the band gap energy corresponding to the absorption edge estimated were found to be 3.59–3.23 eV depending on the Mn doping ratio. Magnetic measurements showed that a paramagnetic behavior at 5 K and ferromagnetic behavior at 300 K.     

具有主导晶面的BiOIO3/BiOCl异质结制备与光催化性能

分别以乙二醇/去离子水为溶剂,通过溶剂热/水热法分别制备了具有不同主导晶面的BiOIO₃/{110}BiOCl和BiOIO₃/{001}BiOCl异质结。采用X射线衍射、扫描电子显微镜、能量色散谱和紫外可见漫反射光谱对制备的BiOIO₃/BiOCl光催化剂进行了表征。在可见光照射下,通过对罗丹明 B和苯酚水溶液的光催化降解,考察了 BiOIO₃/BiOCl异质结的光催化活性。结果显示25% BiOIO₃/{110}BiOCl异质结具有最高的光催化效率。BiOIO₃/{110}BiOCl较好的光催化性能是由于其在可见光区较强的光吸收,以及异质结结构和BiOCl所具有的(110)主导晶面有利于光生载流子的分离。超氧自由基(·O₂^-)和空穴(h⁺)是光催化过程中的主要活性物质。此外,根据实验结果探讨了光催化性能增强的机理。     

Immobilization of bismuth oxychloride on cellulose nanocrystal for photocatalytic sulfonylation of arylacetylenic acids with sodium arylsulfinates under visible light

As a promising semiconductor photocatalyst, BiOCl has been widely used in the field of environmental protection. However, due to its weak ability to absorb visible light, the application of BiOCl in other important photocatalytic fields has been significantly limited, such as organic synthesis. In this work, a facile method was used to prepare a highly efficient heterogeneous nano-photocatalyst BiOCl/cellulose nanocrystal (CNC). Subsequently, the BiOCl/CNC was verified by XPS, ESR, BET and other characterization methods. The results show that not only the strong interaction between BiOCl and CNC increases the visible light absorption intensity of the composite, but also the combination of BiOCl and CNC makes the specific area of the catalyst more than twofold. In addition, a large number of hydroxyl groups contained in CNC can be combined with the BO bond in BiOCl through hydrogen bonds, forming abundant oxygen vacancies on BiOCl/CNC. Excitedly, these changes enable BiOCl/CNC to exhibit excellent photocatalytic performance and regeneration performance in the sulfonation reaction of arylacetylene acid and sodium arylsulfinate, with a yield of up to 96%. This work represents a step towards a low-cost, environmentally friendly composite of cellulose and BiOCl, which will provide useful enlightenment for future exploration in related fields.     

具有主导晶面的BiOIO3/BiOCl异质结制备与光催化性能

分别以乙二醇/去离子水为溶剂,通过溶剂热/水热法分别制备了具有不同主导晶面的BiOIO₃/{110}BiOCl和BiOIO₃/{001}BiOCl异质结。采用X射线衍射、扫描电子显微镜、能量色散谱和紫外可见漫反射光谱对制备的BiOIO₃/BiOCl光催化剂进行了表征。在可见光照射下,通过对罗丹明B和苯酚水溶液的光催化降解,考察了BiOIO₃/BiOCl异质结的光催化活性。结果显示25%BiOIO₃/{110}BiOCl异质结具有最高的光催化效率。BiOIO₃/{110}BiOCl较好的光催化性能是由于其在可见光区较强的光吸收,以及异质结结构和BiOCl所具有的(110)主导晶面有利于光生载流子的分离。超氧自由基(·O₂^-)和空穴(h⁺)是光催化过程中的主要活性物质。此外,根据实验结果探讨了光催化性能增强的机理。     

Ho改性的Mn-Ce/TiO2催化剂低温脱硝性能的评价和表征

作为引起酸雨、光化学烟雾、雾霾等大气污染问题的主要根源,氮氧化物(NOx)的防治已成为亟待解决的问题.选择性催化还原技术作为最成熟有效的脱硝技术,目前已经被广泛应用于各燃煤电厂.低温脱硝催化剂具有优秀的低温活性,使得脱硝装置可以安放在脱硫装置和除尘装置下游,受到了学者广泛的研究.目前低温脱硝催化剂的研究主要是对催化剂进行改性以提高催化剂的性能,已有许多研究报道了Sn、Ni、Co、Zr、Cr、Ni等对催化剂的改性影响.Ho作为一种改性元素被应用于光催化领域,能提高TiO2的光催化能力.但Ho应用于脱硝领域的研究鲜有报道,其氧化物具有酸性位点有助于脱硝反应,因此研究Ho对低温SCR催化剂的改性作用具有重要意义.本文采用浸渍法制备Ho掺杂的Mn-Ce/TiO2催化剂,研究了Ho的掺杂对于Mn-Ce/TiO2催化剂低温脱硝性能的影响,同时还研究了烟气中的SO2和H2O对催化剂活性的影响,并利用XPS、XRD、H2-TPR、NH3-TPD等表征方法从物理性质和化学性质两方面对Ho改性的影响机理进行了研究.研究发现,Ho的掺杂能提高Mn-Ce/TiO2催化剂的脱硝能力,有助于催化剂N2选择性的提高.分析表明,Ho的掺杂有助于催化剂比表面积的提升,且能提高催化剂的酸性,有利于催化剂对NH3的吸附,从而提高催化剂的性能.XPS表征结果表明Ho掺杂后的催化剂具有更高的化学吸附氧浓度和较高的Mn4+/Mn3+比例, 使得脱硝反应更容易进行.改性后催化剂的抗水抗硫实验结果表明,Ho的掺杂能够提高催化剂的抗水抗硫性能.XRD结果表明,抗水抗硫实验后催化剂表面形成了硫酸铵盐,硫酸铵盐的形成会堵塞催化剂表面的活性位,限制脱硝反应的进行,从而影响催化剂的脱硝活性.同时,400°C下进行再生实验后的催化剂活性有所恢复,但是未能达到抗水抗硫实验前的活性,表明在抗水抗硫实验中催化剂表面形成了除硫酸铵盐以外的其他硫酸盐类.结合XPS和XRD表征结果,推断生成的盐类物质为硫酸锰和硫酸铈,从而导致再生后的催化剂的脱硝活性无法恢复到最初的活性水平.由此可以看出,硫酸盐的形成是催化剂在含硫气氛中失活的主要原因.     

Hydrothermal synthesis and characterization of In<Superscript>3+</Superscript> modified BiVO<Subscript>4</Subscript> nanoparticles with enhanced photocatalytic activity

In³⁺-doped BiVO₄ nanoparticles with enhanced visible light activity have been successfully synthesized by a hydrothermal method. The synthesized materials were characterized by X-ray diffraction, Raman, X-ray photoelectron spectroscopy, scanning electron microscopy, BET surface areas analysis, and ultraviolet–visible diffuse reflectance spectra. In comparison with pure BiVO₄, the In³⁺-doped BiVO₄ displayed greater photocatalytic activity in the degradation of methyl blue under visible light illumination. All samples possessed a single monoclinic structure. The introduction of In ions resulted in structural distortion and the decreased band gap energy, producing more electrons and holes for photocatalytic reaction. In the meantime, the doping In ions entails a red shift in the absorption edge and an increase in the intensity of light absorption. The best photocatalytic performance was obtained with the BiVO₄ sample containing 5.0 mol% In ions.     

Effect of Cu Doping on the SCR Activity of Mn‒Ce/ATP Catalyst

In this study, the Cu-doped Ce?Mn/ATP denitration catalyst was prepared by impregnation method and heterogeneous precipitation method and its denitrification performance was tested. It was found that the denitrification effect was obviously improved after Cu doping. And the denitration effect of the catalyst prepared by the heterogeneous precipitation method was better and the denitrification rate was above 98%. Under this method, n(Cu: Mn) = 1 had the best denitration effect, with a maximum of 99.76%. The prepared catalysts were characterized by means of XRD, XPS, BET, and SEM. The results showed that CuMn₂O₄ and CuO appeared in the Cu doped catalysts. Moreover, the doping of Cu enriched the pore structure and surface morphology of the catalyst, so that the catalyst showed good denitrification performance.

     

Preparation of mesoporous TiO2/CNT nanocomposites by synthesis of mesoporous titania via EISA and their photocatalytic degradation under visible light irradiation

Stabilized mesoporous TiO₂ was synthesized by evaporation induced self assembly (EISA) method and mechanically incorporated into single-walled carbon nanotubes (SWCNT) with different ratios. The physicochemical properties of the nanocomposites (mesoporous TiO₂/SWCNT) materials were investigated by Brunauer–Emmett–Teller (BET) measurement, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), photoluminescence (PL) and ultraviolet–visible (UV–Vis) spectroscopy measurements. The catalytic activity of mesoporous TiO₂ and nanocomposites were assessed by examining the degradation of rhodamine B as model aqueous solution under visible light. CNTs are facilitating the photocatalytic activity of mesoporous TiO₂ in the degradation of rhodamine B efficiently.     

Room Temperature Synthesis and Photocatalytic Activity of Magnetically Recoverable Fe3O4/BiOCl Nanocomposite Photocatalysts

Magnetically recoverable Fe₃O₄/BiOCl nanocomposite photocatalysts were fabricated by a simple chemical coprecipitation method at room temperature. The amount of Fe₃O₄ incorporated into BiOCl was varied from 0 to 20 wt%. The as-synthesized samples were characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy, UV–Vis diffuse reflectance spectroscopy, and vibrating sample magnetometer. The obtained results show that the as-synthesized samples mainly contain both crystalline phases (Fe₃O₄ and BiOCl) and are composed of flower-like nanostructures. Compared to UV light-responsive BiOCl, all the nanocomposite photocatalysts show a strong light absorbance in the range of 250–800 nm, demonstrating that the Fe₃O₄/BiOCl nanocomposites can respond to visible as well as UV light. Moreover, visible light absorbance was increased with the increase in the Fe₃O₄ amount in the composite. The photocatalytic activity of nanocomposite photocatalysts was evaluated by the photodegradation of Rhodamine B (RhB) over the samples under visible light irradiation. The 10 wt% Fe₃O₄/BiOCl nanocomposite photocatalyst shows the highest photocatalytic efficiency among the samples. The Fe₃O₄/BiOCl nanocomposite photocatalyst was stable under visible light irradiation to efficiently degrade RhB molecules after five cycles and could be easily recovered with a magnet after each cycle.     

Fabrication of FeOOH/BiOCl Nanocomposites with Enhanced Visible Light Photocatalytic Activity

BiOCl as a two‐dimensional layer ternary oxide semiconductor, has been widely used in energy and environmental area due to its non‐toxicity, price and the good photocatalytic performance. However, BiOCl has a wide bandgap and can only absorb ultraviolet light, which limits its solar energy conversion efficiency for practical application. Herein, we report a facile synthesis of FeOOH/BiOCl nanocomposites by hydrothermal method. The results of XPS and FT‐IR indicated that FeOOH has been loaded on the nanocomposites. The chemical and optical properties of the nanocomposite are well‐characterized. The nanocomposite showed much more excellent photocatalytic performance compared with the individual FeOOH and BiOCl single component. Reactive specie trapping experiment indicated that · O^2– and h⁺ were the two main active species during the photocatalytic process of FeOOH/BiOCl nanocomposites.     

Cr掺杂金红石相TiO2(110)单晶薄膜的制备、表征及光催化活性

采用脉冲激光沉积术(PLD)同质外延生长了表面原子级平整的6%(原子比)Cr 掺杂的金红石相TiO₂(110)单晶薄膜, 采用扫描隧道显微镜(STM)、扫描隧道谱(STS)、X 射线光电子能谱(XPS)和紫外光电子能谱(UPS)对其进行了表征. 结果表明: Cr 掺杂对TiO₂(110)-(1×1)表面的形貌没有明显影响, 但是提高了掺杂薄膜在负偏压的导电性; Cr与晶格O键合而呈现+3价态, 由此在TiO₂的价带顶上方~0.4 eV处引入杂质能级. 紫外-可见光吸收谱显示薄膜的光吸收能力被扩展到~650 nm, 处于可见光范围. 借助STM以单个甲醇分子的光解反应检测了薄膜的光催化活性. 仅观察到紫外光照射下甲醇分子的脱氢反应, 在可见光照射下(λ>430 nm)甲醇分子没有发生反应, 表明单独的Cr掺杂可能不足以提高TiO₂在可见光下的催化活性.     

One-step synthesis of nanocrystalline N-doped TiO2 powders and their photocatalytic activity under visible light irradiation

Nanocrystalline N-doped TiO₂ powders were successfully prepared by hydrothermal reaction for 2 h at low temperature (120 °C) and at an applied pressure of 3 MPa. The grain size of the powders (calculated by use of Scherrer’s method) ranged from 8.2 to 10.2 nm. The BET specific surface area ranged from 151.0 to 220.0 m²/g. A significant shift of the light absorption edge toward the visible light zone was observed in the UV–visible spectra. XPS results showed that nitrogen atoms were incorporated into the TiO₂ lattice. The photocatalytic activity of the synthesized N-doped TiO₂ powders was evaluated by measurement of photodegradation of methylene blue (MB) in aqueous solution under visible light irradiation. The amount of MB degraded increased with increasing illumination intensity.     

镧、锰掺杂改性CeO2-ZrO2-Al2O3固溶体的性能

采用共沉淀法制备了一系列La, Mn共掺杂的CeO2-ZrO2-A12O3(CZA)复合氧化物, 采用BET, XRD, H2-TPR, XPS和XRF等方法对样品进行表征. 结果表明, 全部样品均形成了稳定的CZA固溶体, 经600 ℃焙烧后表现出良好的织构性能, 1000 ℃老化后, La, Mn共掺杂样品具有最佳的高温稳定性; H2-TPR测试表明, La, Mn之间存在正协同效应, 共掺杂的样品具有最佳的低温还原性能和高温稳定性; XPS结果表明, 掺杂La可有效抑制在焙烧过程中Mn向表面的迁移, 从而保持较高的表面吸附氧浓度.     

Visible‐light‐driven photocatalytic degradation using Mn‐doped SrMoO4 nanoparticles

Mn‐doped SrMoO₄ nanocrystals were synthesized by thermal decomposition of metal–organic salt in an organic solvent with the doping content in the range 0–12 mol%. The structures, morphologies and optical properties were characterized using various techniques. The results suggest that Mo sites in the SrMoO₄ lattice are substituted by the Mn dopant, the adsorption bands are found to be shifted toward the visible light region and the band gap becomes narrower correspondingly. The photocatalytic performance of the as‐synthesized product was determined using the degradation of methylene blue by visible light irradiation. The photocatalytic performance is enhanced with Mn doping, and the optimal degradation rate is 85% in 140 min for 5 mol% Mn doping. The enhanced photocatalytic activity with Mn doping may be ascribed to the energy band adjustment and effective photogenerated electron–hole separation caused by the Mn doping. A possible photocatalytic mechanism is also discussed.     

Removal of an organic pollutant from waste water by photocatalytic behavior of AgX/TiO2 loaded on mordenite nanocrystals

Mordenite (MOR) nanocrystals were synthesized using the hydrothermal method. Sol–gel and deposition methods were utilized to modify the zeolite surface with TiO₂ and then AgBr or AgCl particles. Photocatalysts were characterized by using X-ray diffraction, Brunauer–Emmett–Teller (BET), and scanning electron microscopy techniques. Activity was evaluated by photodegradation of Acid Blue 92 as an azo dye. The effect of silver halide deposition on the photocatalytic behavior of the prepared nanocomposites was studied under both ultraviolet (UV) and visible light, and the results were compared. The results showed that AgCl/TiO₂/MOR was more active under UV, while with visible source, AgBr/TiO₂/MOR exhibited better photocatalytic performance. A mechanism for the reaction is also proposed.     

Ｂｉ（ Ｎｂ） ＯＣｌ 光 催 化 剂 的 制 备 及 其 可 见 光 降 解罗 丹 明 Ｂ 溶 液 的 性 能

半导体光催化剂作为环境净化材料,具有稳定性好、光效率高、无二次污染等特点,具有广泛的应用前景.过去的研究大都集中在以TiO2为基础的光催化剂上.本文制备了具有层状结构的Bi基氧氯化物Bi(Nb)OCl光催化剂,用XRD、BET和UV-VIS吸收对样品进行了晶相、孔结构和光吸收性能表征,用罗丹明B的降解表征了材料的光催化活性.结果表明,BiOCl和Bi4NbO8Cl均具有可见光光催化降解活性,但两者的反应机理不同,Bi4NbO8Cl是光催化机制,BiOCl是染料光敏化机制.     

Mn/Ce掺杂改性半焦对模拟煤气中单质汞的脱除性能研究

制备了Mn改性半焦(Mn-SC)及Mn/Ce掺杂改性半焦(Mn/Ce-SC)吸附剂,在小型固定床吸附反应器上考查了改性半焦对模拟煤气中单质汞的吸附特性,并利用BET比表面积测试、X射线衍射、X射线光电子能谱等手段对半焦吸附剂进行了表征。结果表明,Mn改性后半焦的比表面积、总孔容和平均孔径都有所增加,而Mn/Ce掺杂改性半焦的孔隙结构发达程度有一定程度的降低;Mn_xO_y及Ce_xO_y均以高分散的无定形态存在于半焦表面;Mn/Ce-SC的脱汞效率明显高于Mn-SC和SC,其脱汞性能随吸附温度的升高会有所下降,但总体保持较高的水平。当煤气中有1%的O_2存在时,Mn/Ce-SC表面会发生Ce~(4+)/Ce~(3+)间的氧化还原反应循环,从而将煤气中的气相氧转化为高氧化活性的晶格氧,使Mn/Ce-SC的脱汞效率一直稳定在95%以上,Hg0在Mn/Ce-SC半焦表面的吸附符合Mars-Maessen机制。     

Structural,optical, electrical,and photocatalytic properties of manganese doped zinc oxide nanocrystals

Manganese-doped and undoped ZnO nanocrystals were synthesized via wet-chemical methods. The structure, physico-chemical, electrical and optical properties of the as-prepared products were characterized by using the X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PLS) and electrochemical impedance spectroscopy (EIS) techniques. The photocatalytic activity of Mn-doped ZnO nanocrystal (mixed phases) has been examined under the visible-irradiation by using photocatalytic oxidation of rhodamine B (RhB) dye as a model reaction, and compared with that of known system such as pure ZnO nanocrystal (single-phase). The results showed that Mn doped ZnO nanocrystals bleaches RhB much faster than undoped ZnO upon its exposure to the visible light. The enhancement of the photocatalytic activity was discussed as an effect due to the Mn doping in the Mn-doped ZnO semiconductors, which shifts the optical absorption edge to the visible region and alters the electron-hole pair separation conditions. These factors are responsible for the higher photocatalytic performance of Mn/ZnO composites.     

Photocatalytic degradation of organic compounds in aqueous systems by Fe and Ho codoped TiO<Subscript>2</Subscript>

Undoped, single-doped, and codoped TiO₂ nanoparticles were prepared by the sol-gel method and characterized with X-ray diffraction (XRD), the Brunauer-Emmett-Teller (BET)-specific surface area (S_BET), UV-Vis absorption spectra (UV-Vis), and X-ray photoelectron spectroscopy (XPS). Their photocatalytic activity was evaluated by methyl orange (MO) degradation in an aqueous suspension under UV or simulated solar light illumination. XRD showed that all samples calcined at 600°C preserved the anatase structure, and doping inhibited the increase of crystallite size. The BET result revealed that doping improved the surface area of TiO₂. UV-Vis indicated that Fe³⁺-doping broadened the absorption profile of TiO₂. XPS demonstrated that doping was advantageous to absorb more surface hydroxyl groups or chemisorbed water molecules. Photocatalytic degradation showed that the photocatalytic activity of TiO₂ codoped with Fe³⁺ and Ho³⁺ ions was markedly improved. This was ascribed to the fact that there was a cooperative action in the two doped elements. Fe³⁺-doping broadens the absorption profile, improves photo utilization of TiO₂, and then generates more electronhole pairs. Ho³⁺-doping restrains the increase in grain size and retards the recombination of photo-generated electrons and holes.     

WO3/BiOCl, a novel heterojunction as visible light photocatalyst

A bismuth oxychloride (BiOCl) nanostructure is prepared by a new low temperature route using sodium dodecyl sulfate as template and urea as hydrolytic agent. A novel heterojunction is developed between BiOCl and tungsten oxide (WO(3)) to make it an efficient visible light photocatalyst. The catalysts were characterized by X-ray diffraction analysis, Raman spectroscopy, thermogravimetric analysis, energy-dispersive X-ray spectroscopy, scanning electron microscopy, transmission electron microscopy, and N(2) sorption isotherms. The WO(3)/BiOCl heterojunction system extends the absorption edge to the visible region efficiently. BiOCl works as a main photocatalyst while WO(3) acts as the photosensitizer absorbing visible light in the WO(3)/BiOCl composite. The individual BiOCl and WO(3) show very low photocatalytic efficiency under visible light irradiation but their heterojunction provides unexpectedly high efficiency in decomposing rhodamine B as compared to Degussa P25, pure BiOCl, and WO(3).