NaF浸泡处理对BiOBr光催化降解有机染料罗丹明B的影响

以五水硝酸铋(Bi(NO_3)_3·5H_2O)和溴代十六烷基吡啶(CPB)为原料,通过水热法合成溴氧化铋(BiOBr)光催化剂,并在pH=3.3的条件下分别用0.01 mol/L、0.1 mol/L、0.3 mol/L NaF溶液对其进行浸泡氟化处理得新催化剂BiOBr-F_(0.01)、BiOBr-F_(0.1)和BiOBr-F_(0.3).运用XRD(X-射线衍射)、SEM(扫描电镜)、UV-Vis DRS(紫外-可见漫反射光谱)、XPS(X-射线光电子能谱)、FL(荧光光谱)等技术对催化剂的物理结构及性质进行表征并研究了其在可见光(λ≥420 nm)下对有机染料罗丹明B(Rhodamine B,RhB)的催化降解活性.结果表明,随着NaF浓度增加,催化剂的结构及性质均发生一定程度的改变.氟化使得BiOBr对RhB的矿化能力减弱;但BiOBr-F_(0.1)使RhB褪色加快.RhB在降解过程中涉及到超氧自由基(O_2~(·-))、羟基自由基(·OH)及空穴(h~+)氧化,矿化率减小归因于活性物种产量降低,BiOBr-F_(0.1)使褪色加速则是加快了RhB的脱烷基过程,使最大吸收峰快速蓝移.     

Novel Bi/BiOBr/AgBr composite microspheres: Ion exchange synthesis and photocatalytic performance

Novel Bi/BiOBr/AgBr composite microspheres were prepared by a rational in situ ion exchange reaction between Bi/BiOBr microspheres and AgNO₃. The characteristic of the as-obtained ternary microspheres was tested by X-ray diffraction (XRD), energy dispersive X-ray spectrometer (EDS), scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (UV–vis DRS) and photoluminescence (PL). Under visible light irradiation, Bi/BiOBr/AgBr microspheres exhibited an excellent photocatalytic efficiency for rhodamine B (RhB) degradation, which was about 1.4 and 4.9 times as high as that of Bi/BiOBr and BiOBr/AgBr, demonstrating that the highest separation efficiency of charge carriers in the heterostructured Bi/BiOBr/AgBr. The photocatalytic activity of Bi/BiOBr/AgBr microspheres just exhibited a slight decrease after three consecutive cycles. The photocatalytic mechanism investigation confirmed that the superoxide radicals (O₂^•−) were the dominant reactive oxygen species for RhB degradation in Bi/BiOBr/AgBr suspension.     

BiOBr/HPW/Au的制备及其光催化性能的研究

采用水热法和光还原法制备了BiOBr/HPW/Au光催化剂。表征结果表明，BiOBr/HPW/Au光催化剂成功制备，在可见光照射下，BiOBr/HPW/Au具有良好的光催化降解罗丹明B活性，其一级反应动力学速率常数是BiOBr的3.55倍。捕获剂实验结果表明，该反应过程中主要的活性物种是·O₂^-，BiOBr/HPW/Au具有高光催化活性的主要因为是BiOBr、HPW和Au纳米粒子三者的相互作用，提高了BiOBr对可见光的吸收以及电子-空穴对的分离效率，进而提高BiOBr的可见光催化活性。     

Improved visible light photocatalytic activity of sphere-like BiOBr hollow and porous structures synthesized via a reactable ionic liquid

BiOBr uniform flower-like hollow microsphere and porous nanosphere structures have been successfully synthesized through a one-pot EG-assisted solvothermal process in the presence of reactable ionic liquid 1-hexadecyl-3-methylimidazolium bromide ([C(16)mim]Br). The as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and diffuse reflectance spectroscopy (DRS). Possible formation mechanism for the growth of hollow microspheres was discussed. During the reactive process, ionic liquid [C(16)mim]Br played the role of solvent, reactant and template at the same time. Moreover, the photocatalytic activities of BiOBr flower-like hollow and porous structures were evaluated on the degradation of rhodamine B (RhB) under visible light irradiation. The results assumed that BiOBr porous nanospheres sample showed much higher photocatalytic activity than the conventionally prepared sample and TiO(2) (Degussa, P25). The relationship between the structure of the photocatalyst and the photocatalytic activities were also discussed in detail; it can be assumed that the enhanced photocatalytic activities of BiOBr materials could be ascribed to a synergistic effect, including high BET surface area, the energy band structure, the smaller particle size and light absorbance.     

Synthesis and photocatalytic properties of sunlight-responsive BiOBr–CoWO4 heterostructured nanocomposites

Efficient sunlight-responsive BiOBr–CoWO₄ heterostructured nanocomposite photocatalysts were prepared via a chemical precipitation route at 100°C in 4 hours. The prepared BiOBr–CoWO₄ heterostructures were characterized for phase identification, chemical composition, surface morphology, optical properties and surface area using various techniques. The X-ray diffraction pattern of the BiOBr–CoWO₄ nanocomposite was composed of diffraction peaks equivalent to both the tetragonal phase of BiOBr and the monoclinic phase of CoWO₄ nanoparticles. X-ray photoelectron spectral study of the BiOBr–CoWO₄ nanocomposite revealed orbitals of both BiOBr and CoWO₄ compounds. Transmission electron microscopy images revealed that spherical particles of CoWO₄ (20–25 nm) were dispersed on the surface of BiOBr. UV–visible–near-infrared spectral study of the BiOBr–CoWO₄ nanocomposite showed good visible-light absorption. Among the manufactured materials, BiOBr–CoWO₄-2 nanocomposite showed better charge carrier separation efficiency, as demonstrated by photoluminescence and time-resolved fluorescence. To study the practical utility of the prepared materials, their photocatalytic capability was examined for the degradation of rhodamine B (RhB) aqueous solution under sunlight irradiation. The photodegradation results showed that BiOBr–CoWO₄-2 nanocomposite degraded 98.69% RhB solution and the degradation constant was 0.067 min⁻¹, which was 5.6 and 22.5 times larger than that of pure BiOBr and CoWO₄ nanoparticles, respectively, after 60 minutes of sunlight irradiation. The superior photoactivity was facilitated by electron–hole pair separation and transfer driven by the heterostructure interface between BiOBr particles and CoWO₄ nanoparticles. The removal of RhB was initiated by photogenerated h⁺, O₂^{• −} and ^•OH reactive species based on the scavenger effect.     

Enhanced photocatalytic performance of carbon quantum dots/BiOBr composite and mechanism investigation

Novel CQDs/BiOBr composite photocatalysts are constructed via a simple hydrothermal synthesis and show superior activity in photocatalytic degradation of organic pollutants.     

Heterojunction of BiPO4/BiOBr photocatalysts for Rhodamine B dye degradation under visible LED light irradiation

BiOBr synthesized by alcoholysis precipitation is used in the preparation of BiPO₄/BiOBr composites by adding H₃PO₄. Pristine BiOBr and a series of BiPO₄/BiOBr composites have been successfully synthesized using an entirely room-temperature production process. X-ray powder diffraction, scanning electron microscopy, High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, UV–vis absorption spectroscopy were used to investigated the bulk structure, surface morphology, element composition and optical properties of the samples. The degradation effect of different proportions of BiPO₄/BiOBr composites, BiOBr and BiPO₄ on Rhodamine B (RhB) was evaluated under visible LED light irradiation. Compared to pure BiOBr and BiPO₄, the as-synthesized BiPO₄/BiOBr composites showed enhanced performance, with 30% BiPO₄/BiOBr composite showing the best performance, as it could degrade 95.66% of RhB (100 ml, 15 mg/L) within 120 min. The enhanced photocatalytic activity of BiPO₄/BiOBr was attributed to the heterojunction formation between BiOBr and BiPO₄ and efficient charge separation.     

溶剂对BiOBr结构和光催化降解RhB的影响

以水热法合成了不同形貌的BiOBr样品.采用X射线衍射(XRD)、扫描电子显微镜(SEM)、氮气吸附脱附曲线和紫外可见漫反射光谱(UV-Vis DRS)研究溶剂对BiOBr样品的晶形、形貌、孔径分布和比表面积、光学性质的影响;以罗丹明B(RhB)为目标降解物,研究溶剂对BiOBr的可见光催化性能的影响.实验结果表明,采用EG为溶剂的BiOBr在可见光降解RhB中表现出最佳的降解效果,因其较采用HNO_3、GL和PVP为溶剂的样品具有更高I_((001))/I_((102)),更小的禁带宽度和更均一的纳米片形貌.此外,阐述了溶剂对光催化降解RhB的影响机理.     

油水自组装制备Ag@AgBr/BiOBr高效可见光催化剂

采用油水自组装法制备Ag@AgBr表面修饰三维花状结构BiOBr复合光催化剂(Ag@AgBr/BiOBr),利用XRD、SEM、TEM、EDX、DRS、XPS、PL及EIS等手段对光催化剂的结构和性能进行了表征,并研究了可见光下降解亚甲基蓝(MB)的催化性能.研究表明:Ag@AgBr粒径约为20nm,均匀分散在花状微球BiOBr表面上;贵金属Ag的表面等离子体效应可显著增强可见光利用率,并有效促进光生电子空穴对的分离,Ag@AgBr(15wt%)/BiOBr光催化剂展现出最优的催化活性,可见光照射30min对MB的降解率将近90%,淬灭实验表明·O₂^-,h⁺和Br⁰均为活性物种.结合理论分析与实验结果提出复合光催化剂的降解机理.     

油水自组装制备Ag@AgBr/BiOBr高效可见光催化剂

采用油水自组装法制备Ag@Ag Br表面修饰三维花状结构Bi OBr复合光催化剂(Ag@Ag Br/Bi OBr),利用XRD、SEM、TEM、EDX、DRS、XPS、PL及EIS等手段对光催化剂的结构和性能进行了表征,并研究了可见光下降解亚甲基蓝(MB)的催化性能。研究表明:Ag@Ag Br粒径约为20 nm,均匀分散在花状微球Bi OBr表面上;贵金属Ag的表面等离子体效应可显著增强可见光利用率,并有效促进光生电子空穴对的分离,Ag@Ag Br(15wt%)/Bi OBr光催化剂展现出最优的催化活性,可见光照射30 min对MB的降解率将近90%,淬灭实验表明·O2-,h+和Br0均为活性物种。结合理论分析与实验结果提出复合光催化剂的降解机理。     

ZnO修饰提升花状BiOBr的可见光催化降解罗丹明B性能

以Bi(NO3)3·5H2O、Zn(CH3COO)2·2H2O和NaBr为前驱体,采用简单溶剂热法制备BiOBr/ZnO三维花状微纳米复合材料.采用X射线衍射、扫描电子显微镜、X射线光子能谱、N2吸附-脱附、光致发光和电子顺磁共振等分析技术对其理化性质进行了表征.通过可见光催化降解罗丹明B(RhB)的实验测试了复合材料...     

Significantly enhanced photocatalytic performance of zinc oxide via bismuth oxybromide hybridization and the mechanism study

A highly efficient and stable ZnO–BiOBr composite photocatalyst was prepared by a facile one-pot solvothermal method. A variety of sophisticated techniques such as X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), UV–Vis diffuse reflectance spectra, photoluminescence spectra and photoelectrochemical measurement, and so on were employed to characterize the materials. The as-prepared ZnO–BiOBr nanocrystalline showed strong photocatalytic activity for decomposition of methylene blue (MB), Orange II and biphenol A (BPA) under simulated visible light illumination. The possible working principle for the superior photocatalytic properties and reusability of the ZnO–BiOBr hybrid was surveyed to disclose contributions of various effects for the photoactivity enhancement. It was pointed out that *OH and holes take priority over ?O₂ ^? radicals in serving as the main oxidant in the reaction system. The experimental results indicated that the ZnO–BiOBr composite is highly photostable and valuable for real environmental applications.     

花状ZnO/ZnS异质结构的简易合成、结构表征及光催化活性

采用简便的两步溶液相化学方法,在较低温度下(80℃),制备出了花状的ZnO/ZnS异质结构。分别利用X射线衍射、X射线光电子能谱仪、扫描电子显微镜、透射电子显微镜、紫外-可见光谱仪等测试手段对所制备的样品进行表征,结果表明ZnO/ZnS异质结构是由花状ZnO纳米结构和ZnS纳米粒子组成。在光降解罗丹明B(RhB)的测试中,ZnO/ZnS异质结构样品体现出了比ZnO前驱物和商业P25光催化剂更高的光催化效率,这主要可归因于异质结构更有利于电子-空穴的有效分离。ZnO/ZnS光催化剂体现出良好的循环稳定性。     

Fabrication of dual Z-scheme photocatalyst via coupling of BiOBr/Ag/AgCl heterojunction with P and S co-doped g-C3N4 for efficient phenol degradation

Advances in noble metal mediated Z-scheme photocatalytic system have ushered in a climax on environmental remediation. Herein, graphitic carbon nitride (GCN) and phosphorus sulphur co-doped graphitic carbon nitride (PSCN) were synthesized via calcination process. GCN, PSCN and Z-scheme visible light driven (VLD) ternary BiOBr/PSCN/Ag/AgCl nanophotocatalyst were characterized by X-ray diffraction pattern (XRD), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV–visible diffuse reflectance spectra (UV–vis DRS). BiOBr/PSCN/Ag/AgCl nanocomposite exhibited superior visible light driven photocatalytic ability as compared to pristine PSCN, AgCl and BiOBr towards degradation of phenol. The results explicated promising photocatalytic activity along with space separation of photocarriers caused via formation of BiOBr/PSCN/Ag/AgCl Z-scheme heterojunction. The visible light absorption efficacy of BiOBr/PSCN/Ag/AgCl photocatalyst was confirmed by photoluminescence (PL) spectra. Finally, recycling experiments were explored for the mechanistic detailing of phenol photodegradation employing BiOBr/PSCN/Ag/AgCl photocatalyst. After seven successive cycles photodegradation efficacy of photocatalyst was reduced to 90% from 98%. Proposed mechanism of BiOBr/PSCN/Ag/AgCl nanophotocatalyst for degradation of phenol was discussed. OH and O₂⁻ radicals were main reactive species responsible for photocatalytic phenol degradation.     

Photodegradation of Rhodamine B over unexcited semiconductor compounds of BiOCl and BiOBr

This study reported, for the first time systematically, photodegradation of Rhodamine B (RhB) in aqueous solution over BiOCl and BiOBr semiconductors. Under visible light irradiation (λ>400 nm, λ>420 nm and λ=550±15 nm), RhB adsorbed on the surface of BiOCl and BiOBr was photosensitized and decomposed effectively over unexcited BiOCl and BiOBr. The degradation of Methyl Orange (MO) and Methylene Blue (MB) over BiOCl and BiOBr was investigated as well, and the results were compared with RhB photodegradation. It was found that MB molecules having the lowest LUMO could not be degraded by this process. Utilizing the quantum chemical calculation (Gaussian 03 program), the relationship between frontier orbital energy of selected dye molecules and photodegradation rate was established for the first time in this study.     

Microwave-Assisted Hydrothermal Preparation, Characterization and Photocatalytic Properties of a Chrysanthemum-Shaped ZnWO4 Photocatalyst

A novel chrysanthemum-shaped monocline ZnWO₄ photocatalyst was synthesized by microwave-assisted hydrothermal method with Na₂WO₄·2H₂O and Zn(NO₃)₂·6H₂O as raw materials at different reaction temperatures. The prepared ZnWO₄ photocatalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Field emission scanning electron microscopy (FE-SEM), Transmission electron microscopy, Photoluminescence spectrum (PL) and UV–Vis absorption spectrum (UV–Vis). The photocatalytic property of the prepared chrysanthemum-shaped monocline ZnWO₄ photocatalyst was evaluated by the degradation of Rhodamine B (RhB) in aqueous solution. The effects of reaction temperature on the photocatalytic degradation efficiency of RhB were investigated. The results indicated that the chrysanthemum-shaped monocline ZnWO₄ photocatalyst is prepared by foliated powders with the sizes of about 30 nm and 500 nm respectively at 160 and 220 °C. The PL relative intensity of prepared ZnWO₄ photocatalyst is apparently intensifying with increasing temperature. The photocatalytic property decreases with the increasing recombination probability of the excited electrons and holes. The chrysanthemum-shaped monocline ZnWO₄ photocatalyst prepared at 160 °C possesses the best photocatalytic property, and the degradation efficiency of RhB at 180 min UV-light irradiation is achieved 75 %. The ZnWO₄ has good reusability property on degradation of RhB and the degradation rate is still higher than 65 % after three cycles.     

CNTs/TiO2多孔复合膜的组装及光催化性能

提出了一种在掺氟的SnO2(FTO)导电玻璃上组装碳纳米管(CNTs)/Fe-Ni/TiO2多孔复合膜光催化剂的新方法.采用喷涂热解法(SPD)将掺杂镍和铁的含有嵌段聚合物P123的二氧化钛前驱体溶胶涂覆在FTO导电玻璃上,制备Fe-Ni/TiO2多孔膜,再采用化学气相沉积法(CVD)在Fe-Ni/TiO2膜上原位生长CNTs,得到CNTs/Fe-Ni/TiO2多孔复合膜光催化剂.CNTs/Fe-Ni/TiO2复合膜具有多级孔结构特征,在TiO2表面原位生长的CNTs不但具有较好的石墨化结构,且CNTs较均匀地分布在整个膜层的孔中.考察了CNTs/Fe-Ni/TiO2复合膜光催化剂的结构和性能,并通过降解甲基橙溶液评价了复合膜的光催化活性.结果表明,CNTs的复合及铁和镍的掺杂等改性显著提高了TiO2膜材料的光催化活性.     

One‐Pot Synthesis,Characterization, and Enhanced Photocatalytic Activity of a BiOBr–Graphene Composite

Herein, a chemically bonded BiOBr–graphene composite (BiOBr–RG) was prepared through a facile in situ solvothermal method in the presence of graphene oxide. Graphene oxide could be easily reduced to graphene under solvothermal conditions, and simultaneously BiOBr nanoplates with pure tetragonal phase were grown uniformly on the graphene surface. The structure and photoelectrochemical properties of the resulting materials were characterized by transmission electron microscopy (TEM), X‐ray diffraction (XRD), Fourier‐transform infrared (FTIR) spectroscopy, Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and impedance and photocurrent action measurements. The combination of BiOBr and graphene introduces some properties of graphene into the photocatalysis reaction, such as excellent conductivity, adsorptivity, and controllability. A remarkable threefold enhancement in the degradation of rhodamine B (RhB) was observed with as‐prepared BiOBr–RG as compared with pure BiOBr under visible light (λ>420 nm). The enhanced photocatalytic activity could be attributed to the great adsorptivity of dyes, the extended photoresponse range, the negative shift in the Fermi level of BiOBr–RG, and the high migration efficiency of photoinduced electrons, which may effectively suppress the charge recombination.     

g-C_3N_4/BiOBr异质结光催化剂的制备与可见光催化活性

以三聚氰胺作为合成g-C_3N_4纳米片的前躯体,以Bi(NO3)3·5H2O和KBr作为合成BiOBr的原料,采用水热法构建g-C_3N_4/Bi OBr二维异质结可见光催化剂,有效的晶面复合和合适的能带组合有助于增强g-C_3N_4和BiOBr的可见光催化活性。利用X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS)、光致发光光谱(PL)和紫外-可见漫反射光谱(UVvis DRS)等方法表征其结构、光学性质以及组成结构。在可见光(λ420 nm)下以光催化降解RhB来评价合成催化剂的光催化活性,结果表明,g-C_3N_4/BiOBr光催化降解罗丹明B(Rh B)的效率高于单体g-C_3N_4和BiOBr,并对g-C_3N_4/BiOBr增强可见光催化RhB机理进行解释。     

BiOBr hierarchical microspheres: Microwave-assisted solvothermal synthesis, strong adsorption and excellent photocatalytic properties

Two kinds of BiOBr nanosheets-assembled microspheres were successfully prepared via a facile, rapid and reliable microwave-assisted solvothermal route, employing Bi(NO(3))(3)·5H(2)O and cetyltrimethylammonium bromide (CTAB) as starting reagents in the absence or presence of oleic acid. The phase and morphology of the products were characterized by powder X-ray diffraction (XRD), energy dispersive spectrometry (EDS), selected area electron diffraction (SAED), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM). Experiments indicated that the formation of these building blocks of microspheres could be ascribed to the self-assembly of nanoparticles according to mesocrystal growth mode. Interestingly, both samples exhibited not only strong adsorption abilities, but also excellent photocatalytic activities for methyl orange (MO), rhodamine B (RhB) and phenol. The resulting BiOBr hierarchical microspheres are very promising adsorbents and photocatalysts for the treatment of organic pollutants.