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（英文）

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,随后形成氢键的兾.π堆叠.结果显示BiOBr是由厚度小于50 nm的纳米片组装成为4μm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 m~2/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,Bi~(3+)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.     

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。     

Ru掺杂BiOBr空心微球的原位合成及其光催化CO_2还原和有机污染物降解性能研究

采用水热法原位合成了Ru掺杂BiOBr空心微球(Ru/BiOBr)复合光催化剂,并对其进行了XRD、 SEM、 TEM、 EDS、 DRS、 EIS等表征.结果表明,所合成的BiOBr材料是由许多小厚度的交错纳米片自组装而成的,同时Ru纳米颗粒成功负载到BiOBr表面,该复合材料对还原CO_2和降解有机模拟污染物(罗丹明B, RhB)具有良好的光催化性能.当Ru的掺杂量为0.4%时复合材料的光催化活性最佳, 4 h后甲醇产量可达1103μmol/g_(cat),并且60 min内对RhB的降解率达到98%.除此之外,还讨论了复合材料的光催化机理和稳定性.     

p-n异质结型光催化剂BiOBr/NaBiO3的制备与可见光催化活性

采用化学蚀刻法在NaBiO3表面利用HBr与NaBiO3的反应原位沉积BiOBr,制备了异质结型光催化剂.利用X射线粉末衍射仪(XRD)、紫外-可见漫反射光谱仪(UV-Vis DRS)和扫描电子显微镜(SEM)等对其相结构、微观形貌和光吸收性能进行了表征.光催化实验结果表明,BiOBr/NaBiO3在可见光下可以有效降解罗丹明B(RhB)溶液,当BiOBr与NaBiO3的摩尔比为40.1%时,BiOBr/NaBiO3具有最大催化活性.通过不同牺牲剂的加入及荧光实验结果推测了该异质结型材料光催化过程中光生载流子的传输方向及活性物种.研究结果表明,BiOBr/NaBiO3催化活性的增强主要归结为两者之间形成了有效的异质结,其内建电场能够促进光生载流子的分离,同时h+在光催化降解过程中是主要的活性物种.     

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.     

圆盘状Bi2WO6-BiPO4异质结的水热合成及光催化性能

采用水热法制备Bi2WO6-BiPO4异质结光催化剂．利用模拟太阳光照射下的罗丹明B降解实验评价了Bi2WO6-BiPO4复合物的光催化性能．结果表明,Bi2WO6-BiPO4光催化活性比Bi2WO6和BiPO4高得多．当Bi2WO6与BiPO4的摩尔比为1：1时复合光催化剂对罗丹明B的降解率最高．Bi2WO6-BiPO4催化活性增强主要归结为两者之间形成了有效的异质结结构,其内建电场能够促进光生载流子的分离．同时,Bi2WO6的加入增强了其对可见光的吸收．研究表明O2^· -和h^＋在光催化降解过程中是主要的活性物种.     

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的光催化性能。结果表明ZnO含量为5%的BiOBr/ZnO光催化活性最优,RhB降解率在50 min后达到98.3%,其降解速率常数是纯ZnO和BiOBr的6.3倍和3.4倍,并且具有较高的稳定性。复合材料光催化性能增强的可能原因为ZnO的引入增强了可见光的吸收和光生载流子的电荷分离效率。     

高效Ag@AgBr等离子体光催化剂的制备及可见光活性研究

采用水热法和光致还原法制备了具有等离子体共振效应的Ag@AgBr可见光催化剂,利用XRD,SEM,EDX,DRS和XPS等手段对产物的结构和性能进行表征,并研究了催化剂在可见光下对罗丹明B(RhB)的光催化降解性能,考察了催化剂的循环使用及捕获剂对Ag@AgBr光催化性能的影响.结果表明:贵金属Ag纳米粒子的表面等离子体共振效应可显著增强Ag@AgBr对可见光的吸收;催化剂对罗丹明B具有较高的可见光降解活性和稳定性,在可见光下照射90 min,对罗丹明B的降解率达95%以上,光催化剂循环使用5次仍具有良好的光催化降解活性;淬灭实验表明在Ag@AgBr降解罗丹明B过程中,吸附在催化剂表面的h+、·OH、O2·-是主要的活性物种.     

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。     

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%。     

Microwave-assisted synthesis of BiOBr/graphene nanocomposites and their enhanced photocatalytic activity

BiOBr/graphene nanocomposites were synthesized by a green single-step microwave strategy and characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activity of the as-prepared BiOBr nanoplates and BiOBr/graphene nanocomposites for the photodegeneration of organic dyes in aqueous solution under visible light irradiation was investigated. The results show that BiOBr/graphene nanocomposites have a higher photocatalytic activity than bare BiOBr nanoplates.     

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.     

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。     

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.     

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.

     

Hierarchical BiOBr microspheres with oxygen vacancies synthesized via reactable ionic liquids for dyes removal

Hierarchical BiOBr microspheres with oxygen vacancies, which can be used for the dyes removal, have been synthesized successfully in the presence of different kinds of ionic liquids. It was revealed that BiOBr prepared by the ionic liquids with short chain length exhibited higher photocatalytic activity in the degradation of methyl orange (MO) under visible light. The experimental results showed that the phenomenon of the photocatalytic degradation of MO can be explained by the photoluminescence spectra.