铋系复合光催化剂的制备及其对双酚A光催化降解研究

将氧化铋(Bi_2O_3)与三聚氰胺或盐酸胍混合煅烧,通过原位晶相合成法制备了界面紧密接触的碳三氮四复合碳酸氧铋(g-C_3N_4/Bi_2O_2CO_3)和碳三氮四复合氯氧化铋(g-C_3N_4/BiOCl)复合光催化剂。采用X射线衍射仪、扫描电子显微镜、紫外-可见漫反射光谱仪等分析手段对复合光催化剂的结构和性能进行了分析表征。结果表明:Bi_2O_2CO_3和BiOCl纳米片均是从g-C_3N_4体相中生长出来,从而导致铋系氧化物和g-C_3N_4界面间的紧密接触。紫外-可见漫反射光谱分析结果表明,g-C_3N_4/Bi_2O_2CO_3和g-C_3N_4/BiOCl复合光催化剂的可见光吸收能力均优于g-C_3N_4和Bi_2O_3。在可见光照射下,复合光催化剂对双酚A表现出优越的降解性能。此外,探讨了复合光催化剂的光催化机理。由于g-C_3N_4和Bi_2O_2CO_3或BiOCl界面间的紧密接触导致了光生载流子的有效分离,从而提高了复合光催化剂的光催化活性。     

Bi2S3@BiOBr的原位合成及其可见光催化性能

采用溶剂热法合成BiOBr空心微球,并利用简单的离子交换原位生成Bi_2S_3,得到类核-壳结构的Bi_2S_3@BiOBr复合光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(FE-SEM)和紫外-可见漫反射光谱(UV-Vis DRS)等手段对催化剂进行表征,并对其进行光电化学性能测试。实验表明,BiOBr与Bi_2S_3形成的异质结促进了光生载流子的转移和分离。Bi_2S_3@BiOBr在可见光作用下可以有效降解甲基橙,当Bi_2S_3的摩尔分数为8%时,样品具有最好的光催化性能。·O_2~-和h~+是Bi_2S_3@BiOBr光催化降解甲基橙的主要活性物种。     

Bi_2O_3-ZnO复合材料的制备及其性能

以Bi_2O_3纳米棒为前驱体,通过溶剂热法合成了一维Bi_2O_3-ZnO复合材料光催化剂。XRD物相分析,复合材料光催化剂为六方纤锌矿结构的ZnO和四角形结构的Bi_2O_3;SEM形貌观察,复合材料光催化剂为棒状Bi_2O_3,平均直径为(450±50)nm,长度为(5±1)μm,以及少量的ZnO纳米粒/片生长在Bi_2O_3的表面。在可见光照射下,分别以纯的Bi_2O_3、ZnO和Bi_2O_3-ZnO为光催化剂,通过降解染料亚甲基蓝(MB)和苯酚进行光催化性能研究。     

Fe_3O_4/G-BiOCl纳米复合光催化剂的制备及光催化性能研究

以自制的氧化石墨烯、BiOCl/Fe_3O_4为原料,以水合肼为还原剂,制备出Fe_3O_4/石墨烯(G)-BiOCl复合光催化剂。运用X射线衍射、透射电镜和扫描电镜对Fe_3O_4/G-BiOCl的组成和形貌进行了表征,运用振动样品磁强计对其磁性进行了测试;对照研究了Fe_3O_4/G-BiOCl、BiOCl/Fe_3O_4和纯BiOCl对罗丹明B的光催化降解能力以及Fe_3O_4/G-BiOCl光催化活性的循环稳定性。结果表明:Fe_3O_4/G-BiOCl复合光催化剂分布均匀,具有超顺磁性;Fe_3O_4/G-BiOCl的光催化性能优于纯BiOCl和BiOCl/Fe_3O_4,可回收再利用,并具有良好的循环稳定性。     

g-C3N4/BiOCl复合光催化剂作为2D/2D异质结用于光催化降解染料性能研究

为扩大BiOCl的太阳光吸收范围,获得更高效的光催化剂,本文通过水热法制备了石墨相氮化碳(g-C₃N₄)/BiOCl (2D/2D)复合光催化剂并对其进行详细表征。结构与形貌表征结果显示BiOCl纳米片沉积在层状g-C₃N₄表面,形成了2D/2D面-面复合结构;光电化学性质分析表明形成的异质结构能有效扩展光吸收频率范围,促进光生载流子分离和迁移,从而有利于光催化性能的提高。以500 W氙灯模拟太阳光源,光催化降解罗丹明B(RhB)的结果表明g-C₃N₄/BiOCl异质结的光催化降解活性远高于单纯的g-C₃N₄和BiOCl。其中9wt%g-C₃N₄/BiOCl表现出了最优越的光催化活性,在180 min内对RhB的降解率为94%,其表观速率常数K_app值为g-C₃N₄和BiOCl的5.7和3.6倍。同时对g-C₃N₄/BiOCl异质结的光催化机制展开研究,结合复合催化剂电子结构和自由基捕获实验提出了在染料敏化作用下RhB的光催化降解机制。      

零维/二维Bi_2S_3/g-C_3N_4异质结的原位构建及光催化性能

采用简单的一步溶剂热法,以硝酸铋为铋源,硫代硫酸钠为硫源,将Bi_2S_3纳米粒子原位修饰在g-C_3N_4纳米片上,成功制备了零维/二维Bi_2S_3/g-C_3N_4异质结。利用XRD、SEM、TEM、UV-Vis、荧光光谱以及电化学分析方法等手段对所制备的光催化材料进行了表征。在可见光照射下,以罗丹明B(RhB)为模型污染物,研究其光催化降解效率。结果表明,Bi_2S_3以纳米颗粒的形式分散于g-C_3N_4纳米片上,形成了零维/二维异质结结构,拓宽了g-C_3N_4在可见光区的吸收,降低了电子-空穴对的复合概率;与纯g-C_3N_4相比,Bi_2S_3/g-C_3N_4异质结表现出更高的光催化效率。同时,Bi_2S_3/g-C_3N_4催化剂具有良好的光催化稳定性,经过5次循环后其光催化活性基本稳定。     

Bi2O3/BiOCl异质复合材料的制备及其光催化性能

本文以五水硝酸铋和氯化钾为原料,利用水热法一步制备了Bi2O3/BiOCl异质复合光催化材料,采用X射线粉末衍射(XRD)、扫描电镜(SEM)和紫外可见漫反射光谱(UV-Vis)对样品进行了表征。以罗丹明B为目标降解物,研究n(Bi)/n(Cl)摩尔比对合成Bi2O3/BiOCl异质复合光催化剂的形貌和光催化性能的影响。结果表明:随着n(Bi)/n(Cl)摩尔比的增加,Bi2O3/BiOCl的光催化活性显著增强,在n(Bi)/n(Cl)=1.75时,制备的Bi2O3/BiOCl异质复合光催化材料具有最高的光催化活性。     

g-C3N4/BiOCl复合材料的制备及其光催化性能研究

高温缩聚法合成g-C₃N₄和水热法制备的BiOCl,在室温下通过简单的物理搅拌使片层状g-C₃N₄附着在菊花状的BiOCl上，控制g-C₃N₄的质量分数分别为5%、10%、15%、20%和25%,合成g-C₃N₄/BiOCl复合光催化剂。通过扫描电镜(SEM)、EDS能谱和BET比表面表征方法，揭示了g-C₃N₄/BiOCl复合光催化剂的微观结构；紫外-可见光(UV-Vis)结果显示g-C₃N₄/BiOCl可将光吸收范围延伸到可见光范围，其中BiOCl/CN-10具有更窄的禁带宽度；荧光光谱(PL)证实BiOCl/CN-10抑制光生载流子的复合能力最强；同时对g-C₃N₄/BiOCl降解染料废水罗丹明B(RhB)、亚甲基蓝(MB)和甲基橙(MO)的光催化能力进行了评估，结果表明g-C...     

还原氧化石墨烯/SnS_2纳米复合物的制备与可见光光催化性能

以氧化石墨烯(GO)和SnCl_4·5H_2O为前驱体,通过水热法制备了SnS_2/还原氧化石墨烯(RGO)复合材料。用X射线衍射(XRD)、扫描电镜(SEM)、拉曼光谱和紫外-可见(UV-Vis)吸收光谱表征了所制备的样品。在可见光(λ≥420nm)光照下光催化降解甲基橙水溶液来检测SnS_2/RGO复合物的光催化活性。结果表明:所制备的SnS_2/RGO复合物表现出增强的可见光光催化活性,其中,含1%(wt,质量分数,下同)石墨烯的复合光催化剂活性最好。SnS_2/RGO复合物光催化活性的增强是由于石墨烯是优秀的电子受体和传输体,它减少了光生载流子的复合,从而提高了光催化活性。     

α-Fe2O3-ZnO/煤矸石复合光催化剂的制备及其降解五氯酚性能的研究

以氯化铁(FeCl_3)、氯化锌(ZnCl_2)、煤矸石和氢氧化钠(NaOH)为原料,采用沸腾回流法制得了一系列纳米三氧化二铁(α-Fe_2O_3)和氧化锌(ZnO)不同摩尔配合比的纳米三氧化二铁-氧化锌/煤矸石复合光催化剂(α-Fe_2O_3-ZnO/煤矸石复合光催化剂),并对产物进行了表征。以五氯酚(PCP)为目标降解物,考察了模拟太阳光照条件下样品的光催化降解效果。结果表明,将球形α-Fe_2O_3-ZnO复合物负载于改性煤矸石表面可有效提高其光催化活性,且α-Fe_2O_3-ZnO/煤矸石复合光催化剂的性能与α-Fe_2O_3和ZnO的摩尔配合比有关,在α-Fe_2O_3与ZnO的摩尔配合比为1∶5,光照4h条件下,α-Fe_2O_3-ZnO/煤矸石复合光催化剂对PCP的降解率达到100%,具有最佳的光催化降解效果,此外还具有可重复使用的特点。     

研磨-焙烧法制备La2O3/BiOCl复合光催化剂及其对高浓度染料降解性能

首先利用沉淀法合成了BiOCl纳米片, 然后利用研磨-焙烧法将La₂O₃纳米颗粒复合到BiOCl纳米片中, 制备了一系列La₂O₃/BiOCl复合光催化剂(La₂O₃: 1wt%、2wt%、4wt%、8wt%)。运用X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、傅里叶红外光谱(FT-IR)和光致发光(PL)谱等对样品的晶相、光吸收和表面性能等进行了表征。以紫外灯(λ = 254 nm)为光源, 评价了所制备样品光催化降解高浓度染料酸性橙II(40×10^-6)的活性。结果表明, 经过研磨-焙烧后该系列催化剂均具有较好的结晶性能, 同时2~5 nm的La₂O₃纳米粒子粘附在BiOCl纳米片表面。200℃焙烧制备的1wt%La₂O₃/BiOCl催化剂具有丰富的表面羟基, 对染料表现出较强的吸附性能。该催化剂表现了最高的光催化活性, 活性为纯BiOCl的2.4倍。另外, La₂O₃/BiOCl中的La³⁺提供的氧化-还原势阱可能捕获光生电子, 从而阻止了光生电子(e^-)和空穴(h⁺)的复合, 有利于光催化活性的提高。     

Facile preparation of Sn/BiOCl composite oxides and their photocatalytic performance

Sn-doped BiOCl (Sn/BiOCl) photocatalysts were synthesized by a precipitation method using Bi(NO₃)₃?·?5H₂O as a bismuth source, SnCl₂ as an Sn source, imidazole hydrochloride as a chlorine source, a solvent, and a template agent. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, surface area analysis (Brunauer, Emmett and Teller [BET]), and diffuse reflectance spectroscopy. The XRD results showed a greater increase in the peak intensity of Sn/BiOCl because of its high degree of crystallinity. The UV–Vis results indicated a redshift from 368?nm (BiOCl) to 418?nm (Sn/BiOCl), leading to the reduced band gap of BiOCl because of Sn doping in BiOCl. The Sn/BiOCl not only retained ultraviolet photocatalytic activity of BiOCl but also showed visible photocatalytic activity. The BET results showed that the surface area of Sn/BiOCl (23.35?m²?) was bigger than that of BiOCl (13.54?m²?g). The bigger surface show higher photocatalytic activity due to more contact opportunity between reactants. Hence, the increased photocatalytic activity of Sn/BiOCl in the degradation of rhodamine B can be attributed to a higher degree of crystallinity, larger surface area, and broader range of optical absorption. The Sn/BiOCl needed only 20?min under visible light and 40?min under ultraviolet light to completely degrade rhodamine B. Moreover, the photocatalytic experiment did not require any other chemical reagent such as H₂O₂. The microstructures of BiOCl and Sn/BiOCl ensured that the catalyst still has high recovery rate when it is reused. The microstructures of catalyst have a little of loss.     

Synthesis and photocatalytic activity of BiOCl/diatomite composite photocatalysts: Natural porous diatomite as photocatalyst support and dominant facets regulator

BiOCl/diatomite composite with enhanced photocatalytic property for the degradation of liquid Tetracycline hydrochloride (TC) and gaseous formaldehyde (HCHO) were successfully prepared by a facile hydrothermal method at different pH value. The structure and morphology characterizations of BiOCl/diatomite composite exhibit that diatomite not only acts as a natural porous support of photocatalyst but also acts as dominant facets regulator at pH = 3 when the doping amount is change, owing to the surface electrical property of the diatomite and interaction between diatomite and BiOCl. This interaction is certified by XPS and FT-IR which indicate that Bi in layer structure of [Bi₂O₂]²⁺ group interacts with the O in SiOSi bond when the formation of BiOCl with the participation of diatomite. The BET characterization confirms that the increasing amount of diatomite enables the composite with more reaction points for light harvest and molecule adsorption than pure BiOCl. Furthermore, TC and formaldehyde are targeted as degradation objects to test the photocatalytic property of BiOCl/diatomite composite. The optimum photocatalytic property are BiOCl(3–1.2) and BiOCl(12–0.6) at TC degradation and BiOCl(3–0.3) and BiOCl(12–0.6) at formaldehyde elimination, which is much better than that of pure diatomite or BiOCl. The difference of optimum photocatalysts in liquid and gaseous phase systems can be attributed to the photoelectric performances of BiOCl/diatomite composite, which were characterized by DRS, PL, transient photocurrents and the electrochemical impedance spectroscopy technique.     

Size-controlled BiOCl–RGO composites having enhanced photodegradative properties

Visible light-active bismuth oxychloride–reduced graphene oxide (BiOCl–RGO) composite photocatalysts were synthesised using a hydrothermal method at low temperature, and at a low cost. This approach reduced the recombination of electron–hole pairs and thereby provided more efficient photocatalysts. The size of BiOCl structure was controlled by polyvinylpyrrolidone (PVP) addition. Furthermore, formation of nanosized BiOCl sheets and BiOCl–RGO composites were confirmed by X-ray diffraction, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. Fabricated BiOCl–RGO composite with PVP exhibited better photocatalytic activity than pure BiOCl grown with and without PVP towards degradation of Rhodamine B (RhB). It was found that the composite photocatalyst degrades RhB completely within 310 min as compared with several hours for pure BiOCl. The improved photocatalytic performance of BiOCl–RGO composite was attributed to its high specific surface area (22.074 m² g^?1 and existence of polar surfaces, compared with 9.831 m² g^?1 for pure BiOCl). The analyses indicated that RGO helped to reduce recombination losses and improve electron transport. It also showed that presence of polar surfaces improved photocatalytic activity of BiOCl. Hence, BiOCl–RGO composite is a promising catalyst for the degradation of organic pollutants under visible light and could be used in applications such as water purification devices.     

Oxygen vacancies facilitated photocatalytic detoxification of three typical contaminants over graphene oxide surface embellished BiOCl photocatalysts

A conventional solvothermal way was used to synthesize graphene oxide (GO)/BiOCl photocatalytic nanomaterials with enhanced photocatalytic performance. Due to the introduction of GO, there are intuitive changes in morphology, indicating that GO can guide the growth of GO/BiOCl catalysts. The results of X-ray photoelectron spectroscopy (XPS) and Raman show that a strong chemical interaction occurs around GO and BiOCl. The results of trapping experiments show that O₂^– is the major active species. XPS analysis confirms that the 0.75% GO/BiOCl produces the highest level of oxygen vacancies (OVs). All the GO/BiOCl photocatalysts possess better photocatalytic properties than the neat BiOCl, and 0.5% GO/BiOCl exhibits the highest photoactivity. The photocatalytic activity of 0.5% GO/BiOCl composite for detoxification of rhodamine B (RhB) and tetracycline (TC) under visible light illumination is 4.6 and 6.3 times of that on the reference BiOCl, separately, the photocatalytic activity of 0.5% GO/BiOCl for detoxication of perfluorooctanoic acid (PFOA) is 1.25 times of that of the single BiOCl under UV light illumination, which can be credited to the high separation rate of carriers and the strong interaction between GO and BiOCl. Combining with the results, a separation and transfer mechanism of carriers was revealed.     

Preparation and modification of hierarchical nanostructured Bi2WO6 with high visible light-induced photocatalytic activity

Hierarchical nanostructured Bi(2)WO(6) micro-clews were synthesized by a solvothermal process with mixed solvents and formaldehyde. The hierarchical Bi(2)WO(6) micro-clews, with an average diameter of ca. 1.0 μm, consisted of nano-sheets assembled in a special fashion and the formation process mainly went through an Ostwald ripening-anisotropic growth and self-assembling process. The Bi(2)WO(6) micro-clews were further modified by Bi(2)O(3) to fabricate heterojunction photocatalysts, where Bi(2)O(3) nanoparticles were uniformly assembled on the surface of Bi(2)WO(6) nano-sheets. Compared with pure Bi(2)WO(6) and Bi(2)O(3), the composite photocatalyst exhibits higher photocatalytic activity for the degradation of rhodamine B under visible light. On the basis of characterization by x-ray diffraction, photoluminescence and UV-vis diffuse reflectance spectroscopies, a mechanism was proposed to account for the enhanced photocatalytic activity of the Bi(2)O(3)/Bi(2)WO(6) heterojunction.     

高效碳量子点/BiOCl纳米复合材料用于光催化污染物降解

为了克服单纯BiOCl光谱吸收范围窄和载流子复合几率高的缺点, 本研究制备了一种具有高效光催化活性的碳量子点(CQDs)/BiOCl纳米复合材料。光催化降解罗丹明B染料实验表明CQDs/BiOCl纳米复合材料的光催化性能远优于单纯的BiOCl, 其光催化性能约为后者的3.4倍。当CQDs的复合量为7.1wt%时, 样品的光催化性能最佳, 能够在2 min之内将罗丹明B完全脱色, 而单纯的BiOCl在相同时间内对罗丹明B的降解率仅为29.5%。通过紫外-可见漫反射谱、光电化学测试以及自由基捕获实验揭示了CQDs/BiOCl纳米复合材料的光催化性能提升机理, 结果表明CQDs可以拓展BiOCl的可见光吸收范围, 这有利于增强其光捕获能力以及促进电子-空穴对的产生。除此之外, CQDs独特的上转换发光行为, 以及光诱导的电子转移能力提升了CQDs/BiOCl纳米复合材料光催化性能。     

简易合成Bi/Bi2MoO6/TiO2复合纳米纤维及其增强的可见光催化性能

以电纺TiO₂ 纳米纤维为基质, 葡萄糖为还原剂, 采用简单一步溶剂热法制备了等离子体Bi/Bi₂MoO₆/TiO₂复合纳米纤维。利用X射线衍射、场发射扫描电镜、透射电子显微镜、X射线光电子能谱、紫外-可见漫反射光谱和光致发光谱等对样品进行表征。以RhB和4-CP为模拟有机污染物, 评价材料的光催化性能。结果表明: 部分Bi ³⁺被葡萄糖还原成金属Bi纳米粒子, 原位沉积在Bi₂MoO₆纳米片上, 同时构筑在TiO₂纳米纤维表面。金属Bi的等离子体共振效应, 有效提高了样品的光催化活性。可见光照50 min, 样品对RhB的降解率为95.8%, 五次循环后仍保持在92%以上; 可见光照180 min, 样品对4-CP的降解率达68.8%。证实该材料具有良好的可见光催化活性和稳定性。     

Hydrothermal synthesis of sphere-like BiOCl using sodium lignosulphonate as surfactant and its application in visible light photocatalytic degradation of rodamine B

The BiOCl-SL was prepared by a simple hydrothermal reaction between Bi(NO₃)₃·5H₂O and KCl using sodium lignosulfonate (SL) as a structure-directing agent. The standard tetragonal structure of the BiOCl has been confirmed by X-ray powder diffraction. The scanning electron microscopy results revealed that a suitable amount of SL is favorable for the formation of hollow sphere-Like BiOCl. The fourier transform infrared spectroscopy (FT-IR) of the BiOCl-SL showed the BiOCl samples have been cleaned thoroughly, and the following photocatalytic experiment will not be affected by SL. In comparison with the pure BiOCl, the UV–Vis diffuse reflectance spectroscopy (UV–Vis-DRS) of the BiOCl-SL showed a red shift of absorption edge. The Brunauer–Emmett–Teller surface area measurement indicated that the surface area of BiOCl-SL is much bigger than that of pure BiOCl. The photocatalytic activity of BiOCl was tested on the degradation of Rodamine B (RhB) under visible light irradiation, and the result showed that the BiOCl-SL-0.3 had excellent photocatalytic activity for RhB after visible light irradiation for 2 h.