CN106607063B - Float type visible-light photocatalyst and preparation method and application - Google Patents
Float type visible-light photocatalyst and preparation method and application Download PDFInfo
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- CN106607063B CN106607063B CN201510704430.6A CN201510704430A CN106607063B CN 106607063 B CN106607063 B CN 106607063B CN 201510704430 A CN201510704430 A CN 201510704430A CN 106607063 B CN106607063 B CN 106607063B
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011324 bead Substances 0.000 claims abstract description 58
- 239000010881 fly ash Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 15
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- 239000000463 material Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
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- 230000000593 degrading effect Effects 0.000 abstract description 8
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- JMWHLOJMXZVRMC-UHFFFAOYSA-L disodium;4,7-dichloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [Na+].[Na+].O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 JMWHLOJMXZVRMC-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明公开了一种对水体中有机污染物降解的漂浮型可见光光催化剂，所述光催化剂以粉煤灰漂珠为载体，粉煤灰漂珠表面覆盖有BiOBr或/和BiOI材料，覆盖率为50﹪～100﹪；所述粉煤灰漂珠为中空球形颗粒，直径为20μm～200μm，比重为0.3g/cm3～0.5g/cm3；其制备方法通过中和水解和低温保温处理两步法，将BiOBr或/和BiOI负载到粉煤灰漂珠的表面，避免了高温处理的能耗和对漂珠结构的破坏，操作时间短且可控，更容易实施和工业化利用；制备的可见光光催化剂成本低廉，可重复使用，可漂浮于水体表面，40min可以使玫瑰红B的去除率达到100﹪，在地表水体污染治理特别是对于有表面漂浮有机物污染物的水体治理有较大的应用前景。
The invention discloses a floating visible light photocatalyst for degrading organic pollutants in a water body. The photocatalyst uses fly ash floating beads as a carrier, and the surface of the fly ash floating beads is covered with BiOBr or/and BiOI materials. 50% to 100%; the fly ash floating beads are hollow spherical particles with a diameter of 20 μm to 200 μm and a specific gravity of 0.3g/cm 3 to 0.5g/cm 3 ; the preparation method is through neutralization, hydrolysis and low temperature heat preservation Two-step method, loading BiOBr or/and BiOI on the surface of fly ash floating beads, avoiding the energy consumption of high-temperature treatment and damage to the structure of floating beads, the operation time is short and controllable, and it is easier to implement and industrially utilize; preparation The visible light photocatalyst is low in cost, reusable, and can float on the surface of the water body. The removal rate of rose bengal B can reach 100% in 40 minutes. It has great potential in surface water pollution control, especially for water bodies with surface floating organic pollutants. application prospects.
Description
技术领域technical field
本发明涉及一种可见光光催化剂，具体地说是一种漂浮型可见光光催化剂及制备方法和应用，特别是涉及一种对水体中有机污染物降解的漂浮型可见光光催化剂及制备方法和应用。The invention relates to a visible light photocatalyst, in particular to a floating visible light photocatalyst and its preparation method and application, in particular to a floating visible light photocatalyst for degrading organic pollutants in water, its preparation method and application.
背景技术Background technique
随着社会经济的发展，能源危机和环境问题是当今全球社会普遍关注的问题，而半导体光催化表现出了强氧化性、污染物矿化完全、成本低、高效、不产生二次污染等优点，能够彻底矿化有机污染物质，并且可以直接以太阳光为能源的特点，有望同时解决能源和环境问题，所以一直得到人们的关注。目前，关注得最多的光催化剂为TiO2，主要是其具有无毒、物化性质稳定、廉价易得的特点。但是，由于TiO2禁带宽度较宽（为3.2eV），只能被紫外光激发，只能利用太阳光中约4﹪的能量；而太阳光谱中占绝大多数（约96﹪）的可见光部分则不能被有效地利用，由此限制了其实际的工业应用。因此，如何高效地利用太阳光进行光催化反应，人们把目光转移到了能开发能被可见光激发的光催化剂的开发上。With the development of social economy, energy crisis and environmental problems are the common concerns of the global society today, and semiconductor photocatalysis shows the advantages of strong oxidation, complete mineralization of pollutants, low cost, high efficiency, and no secondary pollution. , can completely mineralize organic pollutants, and can directly use sunlight as an energy source, which is expected to solve energy and environmental problems at the same time, so it has always attracted people's attention. At present, TiO 2 is the most concerned photocatalyst, mainly because it is non-toxic, stable in physical and chemical properties, cheap and easy to obtain. However, due to the wide band gap of TiO 2 (3.2eV), it can only be excited by ultraviolet light, and can only use about 4% of the energy in sunlight; while the visible light that accounts for the vast majority (about 96%) of the solar spectrum Some of them cannot be effectively utilized, thereby limiting their practical industrial applications. Therefore, how to efficiently use sunlight to carry out photocatalytic reactions, people have shifted their attention to the development of photocatalysts that can be excited by visible light.
漂珠是一种能浮于水面的粉煤灰空心球，为燃煤电厂的一般工业固体废弃物，主要是由硅铝酸盐组成的一种陶瓷微球，呈灰白色，壁薄中空，重量很轻，容重为720kg/m3（重质），418.8kg/m3（轻质），粒径约0.1毫米，表面封闭而光滑，热导率小，耐火度≥1610℃，是优良的保温耐火材料，广泛用于轻质浇注料的生产和石油钻井方面。漂珠的化学成份以二氧化硅和三氧化二铝为主，具有颗粒细、中空、质轻、高强度、耐磨、耐高温、保温绝缘、绝缘阻燃等多种特性。由于具有无毒、廉价、物化性质稳定、导热系数低和中空结构的特点，可作为光催化剂的载体。特别是负载光催化剂后能够长时间稳定的漂浮在地表水体的表面，既可以是负载的可见光光催化剂充分接收阳光照射以提高太阳能的利用率，又方便在地表水体污染物氧化分解后回收重复使用，可以大幅度降低地表水体污染修复成本。此外，漂珠良好的吸附性能也可以提高光催化剂的降解效能。同传统的TiO2 光催化剂相比，优势不言而喻。Floating beads are a kind of fly ash hollow balls that can float on the water surface. They are general industrial solid wastes in coal-fired power plants. They are mainly ceramic microspheres composed of aluminosilicate. Very light, the bulk density is 720kg/m 3 (heavy), 418.8kg/m 3 (light), the particle size is about 0.1 mm, the surface is closed and smooth, the thermal conductivity is small, and the refractoriness is ≥ 1610 ° C. It is an excellent thermal insulation Refractory materials are widely used in the production of lightweight castables and oil drilling. The chemical composition of floating beads is mainly silicon dioxide and aluminum oxide, which has many characteristics such as fine particles, hollow, light weight, high strength, wear resistance, high temperature resistance, heat preservation and insulation, insulation and flame retardancy. Due to its non-toxic, cheap, stable physical and chemical properties, low thermal conductivity and hollow structure, it can be used as a carrier for photocatalysts. In particular, the loaded photocatalyst can float stably on the surface of surface water for a long time. It can not only fully receive sunlight to improve the utilization rate of solar energy, but also facilitate the recycling and reuse of surface water pollutants after oxidation and decomposition. , can greatly reduce the cost of surface water pollution remediation. In addition, the good adsorption performance of floating beads can also improve the degradation efficiency of photocatalysts. Compared with the traditional TiO 2 photocatalyst, the advantages are self-evident.
铋系光催化剂以其独特的电子结构、优良的可见光吸收能力和较高的有机物降解能力，引起了研究者们的极大兴趣。如钒酸铋（化学式BiVO4）因其较窄的带隙（2.4eV 左右）、较高的光化学稳定性、较强的氧化还原能力及无毒、成本低等优点而被越来越多的应用于可见光光催化研究。卤氧化铋BiOX ( X＝Cl，Br，I)具有沿c 轴方向，双X离子层和Bi2O2层交替排列构成的层状晶体结构，是一类重要的层状结构半导体。这种具有开放式和间接跃迁的层状晶体结构有利于光生电子空穴对的有效分离和电荷转移，可以直接被可见光激发而作为可见光光催化剂。Bismuth-based photocatalysts have aroused great interest of researchers due to their unique electronic structure, excellent visible light absorption ability and high organic degradation ability. For example, bismuth vanadate (chemical formula BiVO 4 ) is being used more and more because of its narrow band gap (about 2.4eV), high photochemical stability, strong redox ability, non-toxicity, and low cost. Applied to visible light photocatalysis research. Bismuth oxyhalide BiOX (X=Cl, Br, I) has a layered crystal structure consisting of double X ion layers and Bi 2 O 2 layers alternately arranged along the c-axis direction, and is an important type of layered semiconductor. This layered crystal structure with open and indirect transitions is beneficial to the efficient separation and charge transfer of photogenerated electron-hole pairs, and can be directly excited by visible light as a visible light photocatalyst.
文献1：申请号：03158740.2，申请日：2003-09-22，发明名称：具有可见光响应的光催化剂及其制备方法和应用的专利公开了一种金属氧化物颗粒、非金属元素、半导体纳米粒子组成的催化剂，所述金属氧化物为氧化铁、氧化铷、氧化镍、氧化钴、氧化镉、氧化铜、氧化银、氧化铟、氧化铋等物质。非金属元素为氮、碳、硫、硼、磷等。半导体纳米粒子为二氧化钛(TiO2)、二氧化锡(SnO2)、氧化锌(ZnO)、硫化镉(CdS)、三氧化钨(WO3)等具有光催化活性的物质。该催化剂除可用于空气、废水、地表水及饮用水中有机污染物、重金属离子等的光催化处理外,还可用于光催化合成、光催化固氮等光催化反应。Document 1: Application No.: 03158740.2, Application Date: 2003-09-22, Invention Name: A photocatalyst with visible light response and its preparation method and application patent discloses a metal oxide particle, a non-metal element, and a semiconductor nanoparticle The catalyst composed of metal oxides is iron oxide, rubidium oxide, nickel oxide, cobalt oxide, cadmium oxide, copper oxide, silver oxide, indium oxide, bismuth oxide and the like. Non-metallic elements are nitrogen, carbon, sulfur, boron, phosphorus, etc. Semiconductor nanoparticles are substances having photocatalytic activity such as titanium dioxide (TiO 2 ), tin dioxide (SnO 2 ), zinc oxide (ZnO), cadmium sulfide (CdS), and tungsten trioxide (WO 3 ). The catalyst can be used not only for photocatalytic treatment of organic pollutants and heavy metal ions in air, waste water, surface water and drinking water, but also for photocatalytic reactions such as photocatalytic synthesis and photocatalytic nitrogen fixation.
文献2：申请号：201410730696.3，申请日：2014-12-05，发明名称：一种卤氧化铋/氧化铋可见光光催化剂的制备方法的专利公开了将硝酸铋溶解在硝酸溶液中，用碱液调节pH，搅拌，过滤，洗涤，干燥，高温300-600℃煅烧3-10小时，制得黄色氧化铋；制得的氧化铋加入适量一定浓度的盐酸、氢溴酸或者氢碘酸，超声反应后离心分离，之后在恒温50-100℃下干燥4-10小时即为卤氧化铋/氧化铋光催化剂。制备的卤氧化铋/氧化铋可见光光催化剂有效的解决了光生电子和载流子复合率高的问题，大大的提高了光催化性能。Document 2: Application No.: 201410730696.3, Application Date: 2014-12-05, Invention Name: A patent for the preparation method of bismuth oxyhalide/bismuth oxide visible light photocatalyst discloses dissolving bismuth nitrate in nitric acid solution, using lye Adjust the pH, stir, filter, wash, dry, and calcine at a high temperature of 300-600°C for 3-10 hours to produce yellow bismuth oxide; add an appropriate amount of hydrochloric acid, hydrobromic acid or hydroiodic acid to the prepared bismuth oxide, and ultrasonically react After centrifugation, drying at a constant temperature of 50-100°C for 4-10 hours is the bismuth oxyhalide/bismuth oxide photocatalyst. The prepared bismuth oxyhalide/bismuth oxide visible light photocatalyst effectively solves the problem of high recombination rate of photogenerated electrons and carriers, and greatly improves the photocatalytic performance.
文献1、文献2中所述的光催化剂是不能漂浮的，如用于水体处理，将沉入水体，不能有效接受表面阳光照射，不利于水体表面污染物的光催化去除，同时，也存在回收困难，容易造成资源的浪费；而且制备过程繁琐，需要经过煅烧先制备氧化铋，然后通过酸性条件下的离子交换过程。The photocatalysts described in Document 1 and Document 2 cannot float. If they are used for water treatment, they will sink into the water and cannot effectively receive surface sunlight, which is not conducive to the photocatalytic removal of pollutants on the surface of the water. At the same time, there are also recycling Difficult, easy to cause waste of resources; and the preparation process is cumbersome, it needs to be calcined to prepare bismuth oxide first, and then through the ion exchange process under acidic conditions.
为此，文献3：申请号：201210301463.2，申请日：2012-08-23，发明名称：一种漂浮型BiVO4/漂珠复合光催化剂、其制备方法及应用的专利公开了以漂珠为载体，在漂珠表面负载BiVO4颗粒薄膜。其制备步骤是：室温下，将异丙氧基氧化钒的乙酰丙酮溶液与硝酸铋的冰乙酸溶液混合，剧烈搅拌，形成墨绿色的溶胶，然后加入粉煤灰漂珠搅拌进行负载，浸渍，水浴蒸干，煅烧，即得到该复合光催化剂。经试验表明，该光催化剂在200-550nm波长范围均有吸收，是一种可见光响应型光催化剂，同常用的TiO2光催化剂相比，BiVO4/漂珠能提高对太阳光能的利用率；此外，相比于TiO2/漂珠，BiVO4/漂珠在可见光下能够显著提高降解亚甲基蓝的效率。For this reason, document 3: application number: 201210301463.2, application date: 2012-08-23, invention name: a kind of floating type BiVO 4 /floating bead composite photocatalyst, its preparation method and application patent discloses using floating bead as carrier , supporting BiVO particle films on the surface of floating beads. The preparation steps are as follows: at room temperature, mix the acetylacetone solution of isopropoxy vanadium oxide and the glacial acetic acid solution of bismuth nitrate, stir vigorously to form a dark green sol, then add fly ash floating beads and stir for loading, impregnation, The composite photocatalyst is obtained by evaporating to dryness in a water bath and calcining. Tests have shown that the photocatalyst has absorption in the wavelength range of 200-550nm, and is a visible light responsive photocatalyst. Compared with the commonly used TiO 2 photocatalyst, BiVO 4 /floating beads can improve the utilization rate of solar energy ; In addition, compared with TiO 2 /floating beads, BiVO 4 /floating beads can significantly improve the efficiency of methylene blue degradation under visible light.
但是，文献3在采用漂珠负载光催化剂的过程中，采用高温煅烧的方法，该方法在煅烧的过程中需要较高的能耗，对设备有较高的要求，并且，在高温中容易造成漂珠的结构破裂而失去漂浮性能。However, Document 3 adopts a high-temperature calcination method in the process of using floating beads to support photocatalysts. This method requires high energy consumption during the calcination process and has high requirements for equipment, and it is easy to cause The structure of the floating beads is broken and loses the floating performance.
发明内容Contents of the invention
本发明的目的是提供一种对水体中有机污染物降解的漂浮型可见光光催化剂及制备方法和应用。The object of the present invention is to provide a floating visible light photocatalyst for degrading organic pollutants in water, a preparation method and application thereof.
卤氧化铋BiOX ( X＝Cl，Br，I)具有沿c 轴方向，双X离子层和Bi2O2层交替排列构成的层状晶体结构，是一类重要的层状结构半导体。这种具有开放式和间接跃迁的层状晶体结构有利于光生电子空穴对的有效分离和电荷转移，可以直接被可见光激发而作为可见光光催化剂，其中BiOBr和BiOI禁带宽度较窄可以直接被可见光激发而作为可见光光催化剂，两者组成复合体系具有更优的光催化活性，但BiOBr和BiOI及其复合物粉体在实际应用中容易沉到水体以下，一方面不容易接收太阳光照，另一方面回收不易。Bismuth oxyhalide BiOX (X=Cl, Br, I) has a layered crystal structure consisting of double X ion layers and Bi 2 O 2 layers alternately arranged along the c-axis direction, and is an important type of layered semiconductor. This layered crystal structure with open and indirect transitions is conducive to the effective separation and charge transfer of photogenerated electron-hole pairs, and can be directly excited by visible light as a visible light photocatalyst, in which BiOBr and BiOI have narrow band gaps and can be directly excited Excited by visible light as a visible light photocatalyst, the composite system of the two has better photocatalytic activity, but BiOBr and BiOI and their composite powders tend to sink below the water body in practical applications. On the one hand, it is not easy to receive sunlight, and on the other hand On the one hand, recycling is not easy.
本发明是采用如下技术方案实现其发明目的的，一种漂浮型可见光光催化剂，所述光催化剂以粉煤灰漂珠为载体，粉煤灰漂珠表面覆盖有BiOBr或/和BiOI材料，覆盖率为50﹪～100﹪；所述粉煤灰漂珠为中空球形颗粒，直径为20μm～200μm，比重为0.3g/cm3～0.5g/cm3。The present invention realizes the object of the invention by adopting the following technical scheme, a floating visible light photocatalyst, the photocatalyst uses fly ash floating beads as a carrier, and the surface of the fly ash floating beads is covered with BiOBr or/and BiOI materials, covering The ratio is 50% to 100%; the fly ash floating beads are hollow spherical particles with a diameter of 20 μm to 200 μm and a specific gravity of 0.3 g/cm 3 to 0.5 g/cm 3 .
一种漂浮型可见光光催化剂制备方法，它包括下列步骤：A method for preparing a floating visible light photocatalyst, comprising the following steps:
⑴漂珠预处理，将粉煤灰漂珠加入蒸馏水中，室温下清洗1h～2h，过滤，101℃干燥；(1) Pretreatment of floating beads, adding fly ash floating beads to distilled water, washing at room temperature for 1h-2h, filtering, and drying at 101°C;
⑵将Bi(NO3)3•5H2O溶解于乙二醇，Bi(NO3)3•5H2O与乙二醇的质量比为1:5～40，待固体全部溶解后，加入KBr 或/和KI，充分搅拌溶解成透明的混合溶液；溶液中KBr与Bi(NO3)3•5H2O的摩尔比为0～1:1，KI与Bi(NO3)3•5H2O的摩尔比为0～1:1，KBr和KI的总摩尔数与Bi(NO3)3•5H2O的摩尔比为1:1；(2) Dissolve Bi(NO 3 ) 3 •5H 2 O in ethylene glycol, the mass ratio of Bi(NO 3 ) 3 •5H 2 O to ethylene glycol is 1:5~40, after all the solids are dissolved, add KBr Or/and KI, fully stirred and dissolved into a transparent mixed solution; the molar ratio of KBr and Bi(NO 3 ) 3 •5H 2 O in the solution is 0~1:1, KI and Bi(NO 3 ) 3 •5H 2 O The molar ratio of KBr and KI to Bi(NO 3 ) 3 •5H 2 O is 1:1;
⑶往步骤⑵的混合溶液中加入步骤⑴制备的粉煤灰漂珠，充分搅拌20min～60min，Bi(NO3)3•5H2O与漂珠的质量比为0.5～1:1，在室温持续搅拌状态下，再向混合溶液中缓慢加入35.0 wt﹪ NH3•H2O,调整体系的pH值为5.0～12.0，即制得乳状悬浊液；(3) Add the fly ash floating beads prepared in step (1) to the mixed solution in step (2), and stir thoroughly for 20 to 60 minutes. The mass ratio of Bi(NO 3 ) 3 •5H 2 O to floating beads is 0.5 to 1:1. Under continuous stirring, slowly add 35.0 wt﹪ NH 3 ·H 2 O to the mixed solution, adjust the pH of the system to 5.0-12.0, and obtain a milky suspension;
⑷将步骤⑶制备的乳状悬浊液真空过滤，得到的滤饼在烘箱中100℃～200℃下保温0.5h～12h，然后，将得到的粉末样品用去离子水洗涤，最后，在干燥箱中90℃干燥1h～6h，即制得粉煤灰漂珠负载BiOBr或/和BiOI的可见光光催化剂。(4) Vacuum filter the emulsion suspension prepared in step (3), and heat the obtained filter cake in an oven at 100°C to 200°C for 0.5h to 12h, then wash the obtained powder sample with deionized water, and finally, dry it in a drying oven Dry at 90°C for 1h to 6h to prepare a visible light photocatalyst of fly ash floating beads supporting BiOBr or/and BiOI.
本发明在步骤⑵中，Bi(NO3)3•5H2O与乙二醇的质量比较优选为1:15～30。In step (2) of the present invention, the mass ratio of Bi(NO 3 ) 3 •5H 2 O to ethylene glycol is preferably 1:15-30.
本发明在步骤⑵中，Bi(NO3)3•5H2O与乙二醇的质量比优选为1:20～25。In step (2) of the present invention, the mass ratio of Bi(NO 3 ) 3 •5H 2 O to ethylene glycol is preferably 1:20-25.
本发明在步骤⑶中，NH3•H2O调整体系的pH值优选为8.0～10.0。In step (3) of the present invention, the pH value of the NH 3 •H 2 O adjustment system is preferably 8.0-10.0.
本发明上述漂浮型可见光光催化剂，在可见光照射下，对水体中有机污染物降解过程中的应用。The above-mentioned floating visible light photocatalyst of the present invention is used in the process of degrading organic pollutants in water bodies under the irradiation of visible light.
本发明上述漂浮型可见光光催化剂，在可见光照射下，对水体中有机污染物玫瑰红B降解过程中的应用。The above-mentioned floating visible light photocatalyst of the present invention is used in the process of degrading the organic pollutant Rose Bengal B in the water body under the irradiation of visible light.
由于采用上述技术方案，本发明较好的实现了发明目的，通过中和水解和低温保温处理两步法，将BiOBr或/和BiOI负载到粉煤灰漂珠的表面，避免了高温处理的能耗和对漂珠结构的破坏，同时可以降低能耗；同时，中和水解和低温保温处理两个步骤都适合在大的装置中进行，操作时间短且可控，更容易实施和工业化利用；制备的BiOBr或/和BiOI可见光光催化剂成本低廉，可重复使用，可漂浮于水体表面，40min可以使玫瑰红B 的去除率达到100﹪，光催化效率远高于P25 TiO2粉体，且重复使用后活性没有明显下降，在地表水体污染治理特别是对于有表面漂浮有机物污染物的水体治理有较大的应用前景。Due to the adoption of the above-mentioned technical scheme, the present invention better realizes the purpose of the invention, and BiOBr or/and BiOI are loaded on the surface of the fly ash floating beads through the two-step method of neutralization, hydrolysis and low-temperature heat preservation treatment, avoiding the energy of high-temperature treatment. consumption and damage to the structure of floating beads, and can reduce energy consumption; at the same time, the two steps of neutralization, hydrolysis and low-temperature heat preservation are suitable for large devices, and the operation time is short and controllable, and it is easier to implement and industrialize; The prepared BiOBr or/and BiOI visible light photocatalysts are low in cost, reusable, and can float on the surface of water bodies. The removal rate of rose bengal B can reach 100% in 40 minutes, and the photocatalytic efficiency is much higher than that of P25 TiO 2 powder. After use, the activity does not decrease significantly, and it has great application prospects in the treatment of surface water pollution, especially for the treatment of water bodies with surface floating organic pollutants.
附图说明Description of drawings
图1是本发明制备的粉煤灰漂珠表面覆盖有BiOBr或/和BiOI可见光光催化剂XRD图谱；Fig. 1 is that the surface of the fly ash floating beads prepared by the present invention is covered with BiOBr or/and BiOI visible light photocatalyst XRD spectrum;
图2是本发明制备的粉煤灰漂珠表面覆盖有BiOBr或/和BiOI可见光光催化剂降解玫瑰红B的效果图；Fig. 2 is the effect figure that the surface of the fly ash floating beads prepared by the present invention is covered with BiOBr or/and BiOI visible light photocatalyst degrading Rose Bengal B;
图3是本发明制备的粉煤灰漂珠表面覆盖有BiOBr或/和BiOI可见光光催化剂扫描电镜（SEM）图；Figure 3 is a scanning electron microscope (SEM) image of the surface of the fly ash floating beads prepared by the present invention covered with BiOBr or/and BiOI visible light photocatalyst;
图4是本发明在不同pH值下制备的粉煤灰漂珠表面覆盖有BiOBr或/和BiOI可见光光催化剂的紫外可见漫反射光谱（DRS）图谱。Fig. 4 is an ultraviolet-visible diffuse reflectance spectrum (DRS) spectrum of fly ash floating beads prepared at different pH values covered with BiOBr or/and BiOI visible light photocatalyst.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步说明。The present invention will be further described below in conjunction with embodiment.
实施例1：Example 1:
一种漂浮型可见光光催化剂制备方法，它包括下列步骤：A method for preparing a floating visible light photocatalyst, comprising the following steps:
⑴漂珠预处理，将粉煤灰漂珠加入蒸馏水中，室温下清洗1h～2h，过滤，101℃干燥；(1) Pretreatment of floating beads, adding fly ash floating beads to distilled water, washing at room temperature for 1h-2h, filtering, and drying at 101°C;
⑵将Bi(NO3)3•5H2O溶解于乙二醇，Bi(NO3)3•5H2O与乙二醇的质量比为1:5～40，待固体全部溶解后，加入KBr 或/和KI，充分搅拌溶解成透明的混合溶液；溶液中KBr与Bi(NO3)3•5H2O的摩尔比为0～1:1，KI与Bi(NO3)3•5H2O的摩尔比为0～1:1，KBr和KI的总摩尔数与Bi(NO3)3•5H2O的摩尔比为1:1；(2) Dissolve Bi(NO 3 ) 3 •5H 2 O in ethylene glycol, the mass ratio of Bi(NO 3 ) 3 •5H 2 O to ethylene glycol is 1:5~40, after all the solids are dissolved, add KBr Or/and KI, fully stirred and dissolved into a transparent mixed solution; the molar ratio of KBr and Bi(NO 3 ) 3 •5H 2 O in the solution is 0~1:1, KI and Bi(NO 3 ) 3 •5H 2 O The molar ratio of KBr and KI to Bi(NO 3 ) 3 •5H 2 O is 1:1;
本发明在步骤⑵中，Bi(NO3)3•5H2O与乙二醇的质量比较优选为1:15～30。In step (2) of the present invention, the mass ratio of Bi(NO 3 ) 3 •5H 2 O to ethylene glycol is preferably 1:15-30.
本发明在步骤⑵中，Bi(NO3)3•5H2O与乙二醇的质量比优选为1:20～25。In step (2) of the present invention, the mass ratio of Bi(NO 3 ) 3 •5H 2 O to ethylene glycol is preferably 1:20-25.
⑶往步骤⑵的混合溶液中加入步骤⑴制备的粉煤灰漂珠，充分搅拌20min～60min，Bi(NO3)3•5H2O与漂珠的质量比为0.5～1:1，在室温持续搅拌状态下，再向混合溶液中缓慢加入35.0 wt﹪ NH3•H2O,调整体系的pH值为5.0～12.0，即制得乳状悬浊液；(3) Add the fly ash floating beads prepared in step (1) to the mixed solution in step (2), and stir thoroughly for 20 to 60 minutes. The mass ratio of Bi(NO 3 ) 3 •5H 2 O to floating beads is 0.5 to 1:1. Under continuous stirring, slowly add 35.0 wt﹪ NH 3 ·H 2 O to the mixed solution, adjust the pH of the system to 5.0-12.0, and obtain a milky suspension;
本发明在步骤⑶中，NH3•H2O调整体系的pH值优选为8.0～10.0。In step (3) of the present invention, the pH value of the NH 3 •H 2 O adjustment system is preferably 8.0-10.0.
⑷将步骤⑶制备的乳状悬浊液真空过滤，得到的滤饼在烘箱中100℃～200℃下保温0.5h～12h，然后，将得到的粉末样品用去离子水洗涤，最后，在干燥箱中90℃干燥1h～6h，即制得粉煤灰漂珠负载BiOBr或/和BiOI的可见光光催化剂。(4) Vacuum filter the emulsion suspension prepared in step (3), and heat the obtained filter cake in an oven at 100°C to 200°C for 0.5h to 12h, then wash the obtained powder sample with deionized water, and finally, dry it in a drying oven Dry at 90°C for 1h to 6h to prepare a visible light photocatalyst of fly ash floating beads supporting BiOBr or/and BiOI.
一种漂浮型可见光光催化剂，所述光催化剂以粉煤灰漂珠为载体，粉煤灰漂珠表面覆盖有BiOBr或/和BiOI材料，覆盖率为50﹪～100﹪；所述粉煤灰漂珠为中空球形颗粒，直径为20μm～200μm，比重为0.3g/cm3～0.5g/cm3。A floating visible light photocatalyst, the photocatalyst uses fly ash floating beads as a carrier, and the surface of the fly ash floating beads is covered with BiOBr or/and BiOI materials, with a coverage rate of 50% to 100%; the fly ash The floating beads are hollow spherical particles with a diameter of 20μm-200μm and a specific gravity of 0.3g/cm 3 -0.5g/cm 3 .
本发明上述漂浮型可见光光催化剂，在可见光照射下，对水体中有机污染物降解过程中的应用。The above-mentioned floating visible light photocatalyst of the present invention is used in the process of degrading organic pollutants in water bodies under the irradiation of visible light.
本发明上述漂浮型可见光光催化剂，在可见光照射下，对水体中有机污染物玫瑰红B降解过程中的应用。The above-mentioned floating visible light photocatalyst of the present invention is used in the process of degrading the organic pollutant Rose Bengal B in the water body under the irradiation of visible light.
本实施例将粉煤灰漂珠（直径为20μm～200μm，比重为0.3g/cm3～0.5g/cm3）加入蒸馏水中，室温下清洗1～2h，过滤，101℃干燥；称取2.8 mmol的Bi(NO3)3•5H2O溶解于20mL乙二醇，待固体全部溶解后，再加2.8 mmol KBr，使得KBr与Bi(NO3)3•5H2O摩尔比为1:1，充分搅拌溶解成透明的混合溶液；向上述混合溶液中加入2.0g烘干后的粉煤灰漂珠，充分搅拌60min，再在室温持续搅拌状态下，向上述混合液体缓慢加入35.0 wt﹪ NH3•H2O调整体系的pH值为9，即可得到白色的混合物；将上述步骤得到的乳状的悬浊液真空过滤，得到的滤饼在烘箱中160℃下保温6h，然后将得到的灰色的粉末样品用去离子水洗涤数次，最后在干燥箱中90℃干燥1h得到粉煤灰漂珠负载BiOBr的可见光光催化剂。In this example, fly ash floating beads (with a diameter of 20 μm to 200 μm and a specific gravity of 0.3 g/cm 3 to 0.5 g/cm 3 ) were added to distilled water, washed at room temperature for 1 to 2 hours, filtered, and dried at 101°C; weighed 2.8 Dissolve 1 mmol of Bi(NO 3 ) 3 •5H 2 O in 20 mL of ethylene glycol. After all the solids are dissolved, add 2.8 mmol of KBr so that the molar ratio of KBr to Bi(NO 3 ) 3 •5H 2 O is 1:1. , stir fully to dissolve into a transparent mixed solution; add 2.0 g of dried fly ash floating beads to the above mixed solution, stir fully for 60 minutes, and then slowly add 35.0 wt﹪ NH 3 • Adjust the pH value of the system to 9 with H 2 O to obtain a white mixture; vacuum filter the milky suspension obtained in the above steps, and keep the obtained filter cake in an oven at 160°C for 6 hours, and then the obtained The gray powder sample was washed several times with deionized water, and finally dried in a drying oven at 90 °C for 1 h to obtain a visible light photocatalyst of fly ash floating beads loaded with BiOBr.
实施例2：Example 2:
本实施例将粉煤灰漂珠（直径为20μm～200μm，比重为0.3g/cm3～0.5g/cm3）加入蒸馏水中，室温下清洗1～2h，过滤，101℃干燥；称取2.8 mmo的Bi(NO3)3•5H2O溶解于20mL乙二醇，待固体全部溶解后，再加2.8 mmol KI，使得KI与Bi(NO3)3•5H2O摩尔比为1:1，充分搅拌溶解成透明的混合溶液；向上述混合溶液中加入2.0g烘干后的粉煤灰漂珠，充分搅拌60min，再在室温持续搅拌状态下，向上述混合液体缓慢加入35.0 wt﹪ NH3•H2O调整体系的pH值为9，即可得到白色的混合物；将上述步骤得到的乳状的悬浊液真空过滤，得到的滤饼在烘箱中160℃下保温6h，然后将得到的黄棕色的粉末样品用去离子水洗涤数次，最后在干燥箱中90℃干燥1h得到粉煤灰漂珠负载BiOI的可见光光催化剂。In this example, fly ash floating beads (with a diameter of 20 μm to 200 μm and a specific gravity of 0.3 g/cm 3 to 0.5 g/cm 3 ) were added to distilled water, washed at room temperature for 1 to 2 hours, filtered, and dried at 101°C; weighed 2.8 mmo of Bi(NO 3 ) 3 •5H 2 O was dissolved in 20mL of ethylene glycol, and after the solid was completely dissolved, 2.8 mmol of KI was added to make the molar ratio of KI to Bi(NO 3 ) 3 •5H 2 O 1:1 , stir fully to dissolve into a transparent mixed solution; add 2.0 g of dried fly ash floating beads to the above mixed solution, stir fully for 60 minutes, and then slowly add 35.0 wt﹪ NH 3 • Adjust the pH value of the system to 9 with H 2 O to obtain a white mixture; vacuum filter the milky suspension obtained in the above steps, and keep the obtained filter cake in an oven at 160°C for 6 hours, and then the obtained The yellow-brown powder sample was washed several times with deionized water, and finally dried in a drying oven at 90 °C for 1 h to obtain a visible light photocatalyst of fly ash floating beads loaded with BiOI.
实施例3：Example 3:
本实施例将粉煤灰漂珠（直径为20μm～200μm，比重为0.3g/cm3～0.5g/cm3）加入蒸馏水中，室温下清洗1～2h，过滤，101℃干燥；称取2.8 mmo的Bi(NO3)3•5H2O溶解于20mL乙二醇，待固体全部溶解后，再加入1.4 mmol KBr 和1.4 mmol KI，使得KBr与Bi(NO3)3•5H2O摩尔比为0.5:1，同时KI与Bi(NO3)3•5H2O摩尔比为0.5:1，NaBr和KI总摩尔数与Bi(NO3)3•5H2O摩尔比为1:1，充分搅拌溶解成透明的混合溶液；向上述混合溶液中加入2.0g烘干后的中空微球载体，充分搅拌60min。再在室温持续搅拌状态下，向上述混合液体缓慢加入35.0 wt﹪NH3•H2O调整体系的pH值为9，即可得到白色的混合物；将上述步骤得到的乳状的悬浊液真空过滤，得到的滤饼在烘箱中160℃下保温6h，然后将得到的黄绿色的粉末样品用去离子水洗涤数次，最后在干燥箱中90℃干燥1 h得到粉煤灰漂珠负载BiOBr和BiOI的可见光光催化剂。In this example, fly ash floating beads (with a diameter of 20 μm to 200 μm and a specific gravity of 0.3 g/cm 3 to 0.5 g/cm 3 ) were added to distilled water, washed at room temperature for 1 to 2 hours, filtered, and dried at 101°C; weighed 2.8 mmo of Bi(NO 3 ) 3 •5H 2 O was dissolved in 20 mL of ethylene glycol, and after all the solids were dissolved, 1.4 mmol of KBr and 1.4 mmol of KI were added to make the molar ratio of KBr to Bi(NO 3 ) 3 •5H 2 O is 0.5:1, while the molar ratio of KI to Bi(NO 3 ) 3 •5H 2 O is 0.5:1, the total molar ratio of NaBr and KI to Bi(NO 3 ) 3 •5H 2 O is 1:1, fully Stir to dissolve into a transparent mixed solution; add 2.0 g of dried hollow microsphere carrier to the above mixed solution, and fully stir for 60 minutes. Then, under continuous stirring at room temperature, slowly add 35.0 wt% NH 3 •H 2 O to the above mixed liquid to adjust the pH value of the system to 9, and a white mixture can be obtained; vacuum filter the milky suspension obtained in the above steps , the obtained filter cake was kept in an oven at 160 °C for 6 h, then the obtained yellow-green powder sample was washed several times with deionized water, and finally dried in a drying oven at 90 °C for 1 h to obtain fly ash floating beads loaded BiOBr and Visible light photocatalyst of BiOI.
由图1可知，实施例1、实施例2和实施例3制备得到的粉煤灰漂珠负载BiOBr、负载BiOI、负载BiOBr和BiOI的可见光光催化剂能够较好的漂浮于水体表面，经X-射线衍射（XRD）物相分析，可以得知实施例1、实施例2和实施例3的粉煤灰漂珠表面分别负载了四方相的BiOBr、BiOI、BiOBr和BiOI。As can be seen from Figure 1, the fly ash floating beads prepared in Example 1, Example 2 and Example 3 are loaded with BiOBr, loaded BiOI, and the visible light photocatalysts loaded with BiOBr and BiOI can float on the surface of the water body well, and the X- XRD phase analysis shows that the surfaces of the fly ash floating beads in Example 1, Example 2 and Example 3 are loaded with tetragonal BiOBr, BiOI, BiOBr and BiOI respectively.
可见光光催化活性评价采用50 W LED蓝光灯作为光源，该光源的主波长为450nm为可见光，光源距离反应池液面5cm，活性实验中采用玫瑰红B作为目标物质。所有的光催化实验反应初始条件为：50 mL玫瑰红B溶液，加入100 mg制备得到的粉煤灰漂珠负载BiOBr、负载BiOI、负载BiOBr和BiOI的可见光光催化剂，光照反应之前，将悬浮体系置于暗处磁力搅拌30min，确保有机物分子在光催化材料表面达到吸附和脱附平衡。然后打开光源，每隔一定的时间间隔取2 mL的悬浮液过滤去除固体后，将过滤得到的液体用可见紫外分光光度计(UV-1800，Shimadzu，日本)上测定其浓度，同时计算玫瑰红B的降解效率。图2为实施例1、实施例2和实施例3制备得到的粉煤灰漂珠负载BiOBr、负载BiOI、负载BiOBr和BiOI的可见光光催化剂的光催化活性评价比较图，由图2可知，粉煤灰漂珠负载BiOBr和BiOI的可见光光催化剂具有最高的可见光光催化活性，可见光照40min后的玫瑰红B去除率达到100﹪，远优于P25 TiO2悬浮体系。Visible light photocatalytic activity evaluation uses 50 W LED blue light as the light source, the main wavelength of the light source is 450nm as visible light, and the light source is 5 cm away from the liquid surface of the reaction pool. Rose Bengal B is used as the target substance in the activity experiment. The initial conditions of all photocatalytic experiments were as follows: 50 mL rose bengal B solution, 100 mg of prepared fly ash floating beads loaded BiOBr, loaded BiOI, loaded BiOBr and BiOI visible light photocatalyst, before the light reaction, the suspension system Place in the dark and stir magnetically for 30 minutes to ensure that the organic molecules reach an equilibrium of adsorption and desorption on the surface of the photocatalytic material. Then turn on the light source, take 2 mL of the suspension at regular time intervals and filter to remove the solids, measure the concentration of the filtered liquid with a visible ultraviolet spectrophotometer (UV-1800, Shimadzu, Japan), and calculate the concentration of rose bengal at the same time. The degradation efficiency of B. Fig. 2 is the comparison chart of the photocatalytic activity evaluation of the visible light photocatalyst of the fly ash floating bead loaded BiOBr, loaded BiOI, loaded BiOBr and BiOI prepared in embodiment 1, embodiment 2 and embodiment 3, as can be seen from Fig. 2, powder The visible light photocatalyst loaded with BiOBr and BiOI on coal ash floating beads has the highest visible light photocatalytic activity, and the removal rate of rose bengal B reaches 100% after 40 min of visible light, which is far better than that of P25 TiO 2 suspension system.
由图3可知，实施例3制备得到的粉煤灰漂珠负载BiOBr和BiOI的可见光光催化剂在圆形的粉煤灰漂珠表面负载了不规则的BiOBr和BiOI膜状物质，形成的粗糙表面有利于有机物在表面的吸附。It can be seen from Fig. 3 that the visible light photocatalyst of the fly ash floating beads loaded with BiOBr and BiOI prepared in Example 3 is loaded with irregular BiOBr and BiOI film-like substances on the surface of the circular fly ash floating beads, forming a rough surface Facilitate the adsorption of organic matter on the surface.
实施例4：Example 4:
本实施例在步骤⑶中，调整体系的pH值为5。In the present embodiment, in step (3), the pH value of the adjustment system is 5.
余同实施例3。The rest are the same as embodiment 3.
实施例5：Example 5:
本实施例在步骤⑶中，调整体系的pH值为7。In the present embodiment, in step (3), the pH value of the adjustment system is 7.
余同实施例3。The rest are the same as embodiment 3.
实施例6：Embodiment 6:
本实施例在步骤⑶中，调整体系的pH值为11。In the present embodiment, in step (3), the pH value of the adjustment system is 11.
余同实施例3。The rest are the same as embodiment 3.
由图4可知，实施例4、实施例5和实施例6制备得到的粉煤灰漂珠负载BiOBr和BiOI的可见光光催化剂样品在波长200 nm～550nm 具有良好吸收，说明粉煤灰漂珠负载BiOBr和BiOI的可见光光催化剂为可见光光催化剂，随着制备过程中，调整体系的pH值越高，光催化剂吸收可见光的能力越强。It can be seen from Figure 4 that the visible light photocatalyst samples loaded with BiOBr and BiOI on fly ash floating beads prepared in Example 4, Example 5 and Example 6 have good absorption at a wavelength of 200 nm to 550 nm, indicating that the fly ash floating beads loaded The visible light photocatalysts of BiOBr and BiOI are visible light photocatalysts. During the preparation process, the higher the pH value of the adjustment system, the stronger the ability of the photocatalyst to absorb visible light.
实施例7：Embodiment 7:
本实施例在步骤⑵中，称取2.8 mmol的Bi(NO3)3•5H2O溶解于10mL乙二醇。In step (2) of this embodiment, 2.8 mmol of Bi(NO 3 ) 3 •5H 2 O was weighed and dissolved in 10 mL of ethylene glycol.
余同实施例3。The rest are the same as embodiment 3.
实施例8：Embodiment 8:
本实施例在步骤⑵中，称取2.8 mmol的Bi(NO3)3•5H2O溶解于30mL乙二醇。In step (2) of this embodiment, 2.8 mmol of Bi(NO 3 ) 3 •5H 2 O was weighed and dissolved in 30 mL of ethylene glycol.
余同实施例3。The rest are the same as embodiment 3.
实施例9：Embodiment 9:
本实施例在步骤⑵中，称取2.8 mmol的Bi(NO3)3•5H2O溶解于35mL乙二醇。In step (2) of this embodiment, 2.8 mmol of Bi(NO 3 ) 3 •5H 2 O was weighed and dissolved in 35 mL of ethylene glycol.
余同实施例3。The rest are the same as embodiment 3.
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