原位构筑溴氧化铋/聚吡咯复合材料用于光催化降解阴离子染料

采用光化学反应法在稀酸条件下制备出薄片状溴氧化铋（BiOBr）,将其分散于含有过硫酸铵和十六烷基三甲基溴化铵的水溶液中,通过吡咯的一步聚合反应原位制备出聚吡咯（PPy）修饰的BiOBr复合材料（BiOBr/PPy）。通过扫描电子显微镜、透射电子显微镜、X射线衍射、拉曼光谱、X射线光电子能谱、紫外可见光谱及荧光光谱等综合表征技术对样品的晶体结构、形貌特征和光电特性等进行测试。结果显示,PPy成功修饰到BiOBr薄片上,BiOBr与PPy接触紧密且相互作用强。与纯BiOBr相比,BiOBr/PPy复合材料具有更强的可见光吸收效率和增强的光催化降解甲基橙（MO）染料活性。通过优化PPy和BiOBr的组合比例,当BiOBr质量分数约为7%时,BiOBr/PPy-2在50 min内对MO （30 mg·L^-1）的降解率为87.3%;另外,循环光催化活性虽有降低但仍高于纯BiOBr和纯PPy （10.4%）。这表明BiOBr与PPy之间较强的相互作用和良好的界面结合可以有效地促进光生电子与空穴的分离效率。反应体系中分离的光生空穴、衍生自由基在染料氧化降解中发挥了重要作用。     

Preparation and measurement of properties of BiOBr/BiOCl/PANI ternary nanocomposite for highly efficient visible light photocatalytic applications

In this paper, we report the synthesis of the BiOBr/BiOCl/PANI ternary nanocomposite using a simple co-precipitation method. The modified photocatalyst produced was characterized by the FT-IR, FE-SEM equipped with EDS (as a Map), TEM, XRD, PL, Raman, and UV–Vis DRS analytical techniques. The synergetic effect of PANI and surface defects in nanoplates can prolong the recombination rate of photo-generated charge carriers. Thus, photocatalytic and photoelectrochemical activities of samples have been studied. Then, the methyl orange (MO) degradation performance of PANI/BiOBr and BiOBr/BiOCl/PANI was investigated under visible light irradiation. The lamp used to simulate sunlight in this photocatalytic study process was power down white light (5-W LED), less reported. The results got exhibited that the as-prepared BiOBr/BiOCl/PANI (90:10, Bi:PANI) nanocomposite showed a higher photocatalytic efficiency. Based on the scavenger tests, ^·O₂^? played a significant role in the degradation of MO. The connection between BiOBr, BiOCl, and PANI improved photocatalytic activity, which enhanced migration rate of the photo-generated electrons besides limiting the recombination of photo-generated electron–hole pairs.

     

微波辅助离子热合成具有高光催化活性的BiOBr片层微米立方体

微波辅助离子热合成技术因其加热和反应速度快、反应时间短、产物选择性高、环保、节能等优点, 而广泛应用于纳米棒、纳米线和中空纳米微球等各种形貌功能材料的合成. BiOBr 光催化剂具有毒性低、光生空穴氧化能力强、光降解活性高等优点, 在光催化降解污染物方面研究非常广泛. 虽然各种形貌的 BiOBr 光催化剂可以通过传统的溶剂热法合成,但仍然需要开发绿色和高效节能的合成方法, 来设计新型结构和高光催化降解活性的 BiOBr 光催化剂. 本文首次报道了由微波辅助离子热自组装的方法合成新型结构的 BiOBr 微米立方体. 该 BiOBr 由规则的多层纳米片组成, 其通过在 Br-端表面上选择性吸附离子液体形成, 随后形成氢键的π-π堆叠. 结果显示 BiOBr 是由厚度小于 50 nm 的纳米片组装成为 4 μm 左右的纳米立方块. 其中 Bi:Br:O 摩尔比为 1:1:1, 表明生成纯化学计量比的 BiOBr, 且具有高结晶度的纯四方相. 我们通过添加不同的表面活性剂, 进一步确认氢键-co-π-π叠层在 BiOBr 片层立方块形成中的重要性.将 BiOBr 片层立方块研磨粉碎后其 BET 表面积为从 2.30 急剧增至 17.3 m2/g, 但其降解 RhB 活性却大幅度下降. 由于纳米片层的层间反射和散射, 有效地提升了 BiOBr 的可见光吸收, 光学带隙由 2.66 窄化为 2.56 eV, 因而具有高的可见光光降解活性和优异的稳定性及矿化能力. 光催化降解 180 min 后, 罗丹明 B 的转化率约为 99.57%, 而有机碳去除率高达12.24%; 对于磨碎的 BiOBr 罗丹明 B 的转化率和有机碳去除率分别为 68.68% 和 8.62%. 光催化反应前后的 BiOBr 中, Bi3+离子的 XPS 峰位置没有明显的变化, 进一步表明 BiOBr 光催化剂具有较高的稳定性. 这种具有高活性、优异的稳定性以及高矿化能力的 BiOBr, 在实际应用光催化降解染料废水和清洁能源方面显示出很好的潜力. 此外, 通过光催化反应过程中不同捕获剂的添加确定了光降解的主要活性物种. 当加入硝酸银溶液的时候, 由于光生电子快速被 Ag+离子捕获, 光降解活性明显下降. 活性物种的捕获实验表明, 光生电子为主要的活性物种.     

层级结构BiOBr的离子液体辅助合成及其对苯胺的可见光催化降解

分别以溴代甲基咪唑反应型离子液体[C₄mim]Br、[C₈mim]Br和[C₁₂mim]Br作为溴源和软模板,通过乙二醇溶剂热处理,获得了3种不同形貌结构的溴化氧铋(BiOBr)微粉。 X射线衍射(XRD)、扫描电子显微镜(SEM)和比表面积测定的表征结果证实,产物均属四方晶系,纯度较高,且随着离子液体中阳离子取代基上碳原子数(C_n)的增多,BiOBr晶体沿着(110)晶面择优生长;微米级的BiOBr产物颗粒均是由纳米尺度的花瓣状薄片相互簇集、自组装而形成,呈球心放射状,粒径和表面孔隙均随C_n的增加而减小,但比表面积随之而增大。 可见光降解苯胺的结果表明,3种BiOBr催化剂的催化活性不同,反应280 min时,降解率依次为54.13%、78.67%和95.06%;光生空穴是光降解过程的主要活性物质,羟基自由基所起的作用较小。     

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.     

Constructing recyclable photocatalytic BiOBr/Ag nanowires/cotton fabric for efficient dye degradation under visible light

In this study, a highly-efficient photocatalytic and recyclable BiOBr/Ag nanowires (AgNW)/cotton fabric (CF) composite was fabricated by successive ionic layer adsorption and reaction (SILAR) for rapid treatment of dye wastewater. The integration of AgNW and BiOBr aims to establish a channel for faster and easier charge transfer to enhance the photocatalytic performance. The chemical structure and morphology of BiOBr/AgNW/CF, as well as its photo-degradation of Rhodamine B (RhB) under visible light radiation were explored. Results reveal that BiOBr/AgNW/CF exhibits remarkably enhanced photocatalytic activity over BiOBr/CF, which degrades 97 % of RhB within 90 min. BiOBr/AgNW/CF still maintains 88 % of photocatalytic degradation capacity after five reusing cycles due to the effective encapsulation of BiOBr that protects AgNW from oxidation. Photoluminescence, electron spin resonance, and free radical trapping experiments confirm that the separation efficiency of photo-generated electron-hole pairs plays an important role in improving photocatalytic performance. In all, this work exhibits great potential in the development of textile-based photocatalytic materials that integrates two significant merits, the high degradation efficiency and easy recovery.     

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.     

g-C3N4-BiOBr复合材料制备及可见光催化性能

利用原位沉积法将BiOBr纳米片生长到g-C₃N₄表面,制得g-C₃N₄-BiOBr p-n型异质结复合光催化剂。采用X射线衍射(XRD)、红外光谱(FTIR)、场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、紫外可见漫反射(UV-Vis-DRS)和荧光光谱(PL)等测试对光催化剂结构和性能进行表征。通过可见光辐照降解甲基橙水溶液检测评估复合光催化剂光催化活性。研究结果表明:复合光催化剂由BiOBr和g-C₃N₄两相组成,BiOBr纳米片在片状g-C₃N₄表面快速形核生长形成面-面复合结构。相比于纯相g-C₃N₄和BiOBr,g-C₃N₄-BiOBr复合材料具有更强可见光吸收能力,吸收带边红移。在可见光辐照100 min后,性能最佳的2:8 g-C₃N₄-BiOBr复合光催化剂光催化活性分别是纯相g-C₃N₄和BiOBr的1.8和1.2倍,经过4次循环实验后,其降解率仍达84%,说明复合结构光催化剂催化性能和稳定性增强。复合光催化剂的荧光强度显著降低,说明光生载流子复合得到了有效抑制。复合光催化剂催化性能的提高归因于p-n型异质结促进电荷有效分离、抑制电子-空穴复合和吸收光波长范围的扩展,相比单一成分材料具有更好的催化活性和稳定性。自由基捕获实验证明,可见光降解甲基橙光催化过程中的主要活性成分为空穴,并据此提出了可能的光催化机理。     

BiOBr microspheres for photocatalytic degradation of an anionic dye

BiOBr microspheres were obtained using a solvothermal synthesis route in the presence of ethylene glycol and KBr at 145 °C, for 18 h. BiOBr microspheres were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), nitrogen adsorption-desorption isotherms analysis, diffuse reflectance spectroscopy (DRS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Additionally, the theoretical and experimental isoelectric points (IEP) of BiOBr nanostructured microspheres were determined, and pH's influence on the degradation of an anionic dye (methyl orange) under simulated solar radiation was analyzed. Results show that 97% of methyl orange is removed at pH 2 after 60 min of photocatalytic reaction. Finally, DRIFTS studies permit the proposal of a surface reaction mechanism of the photocatalytic oxidation of MO using BiOBr microspheres.     

n-p异质结型CdS/BiOBr复合光催化剂的制备及性能

采用两步水热法制备了CdS/BiOBr复合光催化剂,并通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和紫外-可见漫反射光谱(UV-Vis DRS)等手段对其物相、表面结构、光响应性等性质进行了表征.结果表明,合成的CdS/BiOBr复合材料是n-p型异质结,由CdS颗粒裹附在BiOBr纳米球的表面构成,这种结构不仅具有良好的可见光响应范围,且有利于光生电子的迁移,并有效地抑制光生电子/空穴对的复合.通过光催化降解模拟染料废水和光催化脱除模拟含硫燃料评价了CdS/BiOBr复合材料的可见光催化性能.结果表明,6%(质量分数)CdS/BiOBr降解次甲基蓝的拟一级动力学常数分别为BiOBr和CdS的5.3和9.6倍,脱除噻吩的拟一级动力学常数分别为BiOBr和CdS的1.9和3.2倍.CdS/BiOBr具有良好的光催化稳定性,循环使用5次后,降解率仍能达到90%以上.     

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。     

Au/BiOBr/石墨烯复合物的制备及其苯酚降解光催化性能

采用水热法和多巴胺还原法制备了Bi OBr、Bi OBr/石墨烯和Au/Bi OBr/石墨烯光催化剂,并利用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、光致发光光谱(PL)和紫外-可见漫反射光谱(UV-vis DRS)等方法表征其形貌、相结构、光谱吸收性质以及组成结构。在可见光照射下,通过对水相中苯酚的降解,考察了Au/Bi OBr/石墨烯复合光催化剂活性。结果表明,由于量子效率的提高、带隙能的降低(2.25 e V)以及Au表面等离子体共振,复合光催化剂表现出比纯Bi OBr更高的光催化活性,Au/Bi OBr/石墨烯复合物在180 min内对苯酚降解率可达到64%。     

不同煅烧温度制备的n-p型CeO_2/BiOBr光催化性能研究

采用微乳法制备了n-p型CeO_2/BiOBr异质结,其中十六烷基三甲基溴化铵(CTAB)既作为Br源,又作为"桥"使CTA~+修饰在CeO_2表面形成了稳定的油包水微乳体系.利用XRD、SEM、HRTEM、UV-Vis DRS、BET、XPS等对样品进行结构、形貌和光学性质进行表征,并对复合光催化剂进行了可见光下降解甲基橙(MO)的光催化活性研究.考察了不同煅烧温度对合成CeO_2/BiOBr的影响.结果表明:CeO_2/BiOBr异质结相比于单体CeO_2和BiOBr来说,它的光响应范围大大增加,在可见光下降解MO具有更高的光催化活性.450℃下煅烧可使MO达到最佳的降解率,而高温则会使催化剂发生烧结.机理研究表明,在CeO_2与BiOBr复合体中,使有机物矿化的主要为CeO_2价带上的光生空穴.CeO_2/BiOBr催化活性增强主要是由于在CeO_2与BiOBr之间形成了n-p型的异质结.     

g-C3N4-BiOBr复合材料制备及可见光催化性能

利用原位沉积法将Bi OBr纳米片生长到g-C_3N_4表面,制得g-C_3N_4-Bi OBr p-n型异质结复合光催化剂。采用X射线衍射(XRD)、红外光谱(FTIR)、场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、紫外可见漫反射(UV-Vis-DRS)和荧光光谱(PL)等测试对光催化剂结构和性能进行表征。通过可见光辐照降解甲基橙水溶液检测评估复合光催化剂光催化活性。研究结果表明:复合光催化剂由Bi OBr和g-C_3N_4两相组成,Bi OBr纳米片在片状g-C_3N_4表面快速形核生长形成面-面复合结构。相比于纯相g-C_3N_4和Bi OBr,g-C_3N_4-Bi OBr复合材料具有更强可见光吸收能力,吸收带边红移。在可见光辐照100 min后,性能最佳的2:8 gC_3N_4-Bi OBr复合光催化剂光催化活性分别是纯相g-C_3N_4和Bi OBr的1.8和1.2倍,经过4次循环实验后,其降解率仍达84%,说明复合结构光催化剂催化性能和稳定性增强。复合光催化剂的荧光强度显著降低,说明光生载流子复合得到了有效抑制。复合光催化剂催化性能的提高归因于p-n型异质结促进电荷有效分离、抑制电子-空穴复合和吸收光波长范围的扩展,相比单一成分材料具有更好的催化活性和稳定性。自由基捕获实验证明,可见光降解甲基橙光催化过程中的主要活性成分为空穴,并据此提出了可能的光催化机理。     

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的可控制备及对废水中卡马西平的有效降解

以Bi(NO₃)₃·5H₂O为原料, 乙醇为介质, KBr和/或十六烷基三甲基溴化铵(CTAB)为溴源, 采用溶剂热法合成了不同结构和性能的BiOBr微纳米材料, 通过 X射线衍射仪(XRD)、 扫描电子显微镜(SEM)、 红外光谱仪(FTIR)、 紫外-可见漫反射光谱(UV-Vis DRS)及比表面积和孔隙度分析仪对产物进行了表征. 结果表明, 溴源(KBr, CTAB)对BiOBr的结晶特性和形貌有重要影响, 其中采用双溴源且KBr与CTAB摩尔比为3∶7时制得的BiOBr(K∶C=3∶7)光催化剂在模拟太阳光下具有最优的光催化性能, 光照20 min后对废水中卡马西平的降解速率常数是以KBr为溴源制备的BiOBr(K)的4.10倍和以CTAB为溴源制备的BiOBr(C)的2.14倍. BiOBr(K∶C=3∶7)优异的光催化活性可归因于其高暴露的(110)晶面、 表面羟基、 疏松的片层状形貌及较大的比表面积和孔体积. 活性物种淬灭实验结果表明, BiOBr(K∶C=3∶7)的光催化活性主要源于光生空穴、 羟基自由基和电子.     

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。     

Enhanced photocatalytic activity and stability of AgBr/BiOBr/graphene heterojunction for phenol degradation under visible light

In this work, we have reported synthesis of AgBr/BiOBr photocatalyst supported on graphene (Gr) using facile precipitation method. AgBr/BiOBr/Gr was characterized using various spectral techniques like FESEM, TEM, XRD, FTIR, XPS, Raman and PL analyses. AgBr/BiOBr/Gr had improved visible light absorption. PL studies indicated the reduction in recombination of photogenerated electron hole pair of AGBr/BiOBr/Gr. AFM analysis confirmed the thickness of AGBr/BiOBr/Gr was less than 8.0 nm. The higher dispersibility of photocatalyst was ascertained by Tyndall effect. AgBr/BiOBr/Gr photocatalyst was effectively used for the photodegradation of phenol from simulated water. The phenol degradation process was remarkably influenced by adsorption process. The concurrent adsorption and photocatalytic was effective for degradation of phenol. The phenol was completely mineralized into CO₂ and H₂O in 6 h. The degradation process followed pseudo first order kinetics. The results confirmed that integration of AgBr/BiOBr with graphene caused an increase in photocatalytic activity due to reduced recombination of photogenerated electron hole pair and electron sink behavior of graphene for photogenerated electrons of BiOBr. AgBr/BiOBr/Gr photocatalyst displayed significant stability and recyclability for ten catalytic cycles.     

Comparative Studies on Degradation of Methyl Orange by Nanostructured Zinc and Zinc Oxide Films

Nanostructured zinc and zinc oxide films were prepared by magnetron sputtering processes and succeeded air annealing treatments. Comparison of reductive degradation rate of methyl orange (MO) by zinc films and photocatalytic degradation rate of MO by zinc oxide films was carried out. Both reductive degradation and photocatalytic degradation process of MO by zinc and zinc oxide films can be described by first order kinetic model. It was found that although MO liquid was most quickly decolorized by metallic zinc films, the mineraliza-tion of MO was not thorough. Observation of extra ultraviolet absorption peaks indicated the formation of aromatic intermediates. On the other hand, although the photocatalytic degradation rate of MO liquid by ZnO films was only as about 1/4 large as the reductive degradation rate by zinc films, no signs of aromatic intermediates were found. Moreover, it was found that partially oxidized zinc oxide film showed higher photocatalytic efficiency than the totally oxidized ZnO films. Synergy effect between zinc and zinc oxide phase in the partially oxidized films was considered to be responsible for the higher photocatalytic efficiency.     

Construction of Recycling Photocatalytic Gels for the Disinfection of Pathogens and Degradation of Organic Pollutants

Bismuth oxybromide (BiOBr) nanosheets are exciting photocatalysts for microbial disinfection and organic dye degradation. However, it remains a great challenge to easily recycle these nanomaterials and improve their photocatalytic ability. Herein, we constructed a novel photocatalytic BiOBr@PAG gel containing BiOBr nanosheets and polyacrylamide gel (PAG), based on peroxydisulfate-induced polymerization reaction. The photocatalytic gel had equally distribution of BiOBr nanosheets on the surface, and could be easily recycled from water. More strikingly, the gel could also rapidly kill all tested pathogenic bacteria (i. e., Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus) under irradiation. Its disinfection activity is attributed to remarkable intracellular ROS production and oxidative cell damage. Furthermore, the gel had higher photocatalytic activity than BiOBr nanosheets alone during degradation of organic dyes. This study developed a novel strategy for preparation of easy-recycling and high-efficiency photocatalytic systems for practical application in environmental treatment and medicinal disinfection.