CN104826623B - Bismuth oxide photocatalyst, preparation method and applications thereof - Google Patents
Bismuth oxide photocatalyst, preparation method and applications thereof Download PDFInfo
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- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 48
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract 2
- 238000001035 drying Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000002244 precipitate Substances 0.000 abstract description 9
- 229960001230 asparagine Drugs 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000005693 optoelectronics Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 15
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- RBMGJIZCEWRQES-DKWTVANSSA-N (2s)-2,4-diamino-4-oxobutanoic acid;hydrate Chemical compound O.OC(=O)[C@@H](N)CC(N)=O RBMGJIZCEWRQES-DKWTVANSSA-N 0.000 description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域：Technical field:
本发明属于新型半导体光催化材料领域，具体涉及一种氧化铋光催化剂及其制备方法和应用。The invention belongs to the field of novel semiconductor photocatalytic materials, and in particular relates to a bismuth oxide photocatalyst and its preparation method and application.
背景技术：Background technique:
半导体光催化剂可以在紫外光或可见光的照射下可对有机污染物进行光催化降解，使其分解成小分子化合物，最后矿化生成水和二氧化碳；具有效率高、成本低、低能耗、操作方便等优点，因此受到环境、材料、能源等领域专家学者的广泛关注和重视。常用的光催化剂为纳米二氧化钛，但其存在着光量子效率低，太阳能利用率低，仅在紫外光区有响应等缺点，严重制约了光催化技术在实际工业和生活上的大规模运用。解决这一问题的主要途径包括对二氧化钛的结构和组成进行改性，或者开发非二氧化钛的新型光催化剂。Semiconductor photocatalysts can photocatalytically degrade organic pollutants under the irradiation of ultraviolet light or visible light, decompose them into small molecular compounds, and finally mineralize them to generate water and carbon dioxide; they have high efficiency, low cost, low energy consumption, and easy operation Therefore, it has been widely concerned and valued by experts and scholars in the fields of environment, materials, energy and so on. The commonly used photocatalyst is nano-titanium dioxide, but it has the disadvantages of low photon quantum efficiency, low solar energy utilization rate, and only responds in the ultraviolet region, which seriously restricts the large-scale application of photocatalytic technology in actual industry and life. The main ways to solve this problem include modifying the structure and composition of titania, or developing new photocatalysts other than titania.
铋基化合物具有带隙小、活性高、无毒和价廉等优点，近年来逐渐成为新型光催化剂开发领域的一个研究热点。在含铋半导体材料中，氧化铋因结构简单、对可见光具有良好的吸收、光生载流子不易复合、具有高的氧化能力以及无毒性等优点而受到广泛关注。目前国内外制备氧化铋纳米颗粒的方法主要是水热法，需要高温高压的反应条件，为其规模化生产带来了较大的困难和危险性，大大制约了氧化铋纳米材料在工业上的应用。而且，这些方法所需要的温度大都在150℃以上，反应时间通常为12小时以上，是一种能耗极高的合成途径。此外，水热合成过程中通常会加入表面活性剂或者通过酸碱调节体系pH值来控制材料的形貌，这样不仅导致生产成本的提高，而且排出的废水也可能引起环境污染。Bismuth-based compounds have the advantages of small band gap, high activity, non-toxicity and low cost, and have gradually become a research hotspot in the field of new photocatalyst development in recent years. Among bismuth-containing semiconductor materials, bismuth oxide has attracted extensive attention due to its simple structure, good absorption of visible light, difficult recombination of photogenerated carriers, high oxidation ability, and non-toxicity. At present, the method of preparing bismuth oxide nanoparticles at home and abroad is mainly the hydrothermal method, which requires high temperature and high pressure reaction conditions, which brings great difficulties and dangers to its large-scale production, and greatly restricts the industrial application of bismuth oxide nanomaterials. application. Moreover, the temperature required by these methods is mostly above 150° C., and the reaction time is usually above 12 hours, which is a very high energy-consuming synthesis route. In addition, during the hydrothermal synthesis process, surfactants are usually added or the pH value of the system is adjusted by acid and alkali to control the morphology of the material, which not only leads to an increase in production costs, but also causes environmental pollution in the discharged wastewater.
公开号为CN103861580A的中国专利“一种纳米球状氧化铋光催化剂的制备方法及应用”是将含铋化合物和葡萄糖酸钠溶于水中，调节pH至10～13,得到混合溶液，再将混合溶液放入高压反应釜中，密封后在120～180℃保持18～24小时，冷却至室温，将高压反应釜内的溶液分离，取出沉淀，干燥后在400～600℃焙烧，得到纳米球状α相氧化铋光催化剂。公开号为CN102320657A的中国专利“一种γ相氧化铋的制备方法”是以α相或β相氧化铋为原料，溶剂为去离子水，在加入去离子水后，α相或β相氧化铋原料浓度为0.01～3M，将所述的原料在去离子水中分散均匀后，加入浓度为1～10M的pH调节剂，调节pH值至12.5～14，装入带聚四氟乙烯内衬的反应釜中，将反应釜放入烘箱，在120℃～220℃的温度范围内保温1～48小时，冷却至室温，洗涤后，得到γ相Bi2O3。The Chinese patent with the publication number CN103861580A "Preparation method and application of a nano-spherical bismuth oxide photocatalyst" is to dissolve a bismuth-containing compound and sodium gluconate in water, adjust the pH to 10-13 to obtain a mixed solution, and then mix the mixed solution Put it into a high-pressure reactor, seal it and keep it at 120-180°C for 18-24 hours, cool to room temperature, separate the solution in the high-pressure reactor, take out the precipitate, dry it and roast it at 400-600°C to obtain a nano-spherical α phase Bismuth oxide photocatalyst. The Chinese patent with the publication number CN102320657A "a preparation method of γ-phase bismuth oxide" uses α-phase or β-phase bismuth oxide as raw material, and the solvent is deionized water. After adding deionized water, the α-phase or β-phase bismuth oxide The concentration of the raw material is 0.01-3M. After the raw material is uniformly dispersed in deionized water, a pH regulator with a concentration of 1-10M is added to adjust the pH value to 12.5-14, and the reactor with a polytetrafluoroethylene lining is loaded. Put the reaction kettle into an oven, keep it warm at a temperature range of 120°C to 220°C for 1 to 48 hours, cool to room temperature, and wash to obtain γ-phase Bi 2 O 3 .
上述两个专利虽然都成功运用水热法制备出氧化铋纳米材料，但是如何在温和的常压和低温条件下大规模制备出性能优越、纯度高的纳米级β相氧化铋尚未见诸报道。Although the above two patents have successfully used the hydrothermal method to prepare bismuth oxide nanomaterials, how to prepare nano-scale β-phase bismuth oxide with superior performance and high purity on a large scale under mild atmospheric pressure and low temperature conditions has not yet been reported.
发明内容：Invention content:
本发明的目的是提供一种能够在温和的常压和低温条件下大规模制备出性能优越、纯度高的纳米级β相氧化铋的氧化铋光催化剂及其制备方法。The purpose of the present invention is to provide a bismuth oxide photocatalyst capable of preparing nano-scale β-phase bismuth oxide with superior performance and high purity on a large scale under mild normal pressure and low temperature conditions and a preparation method thereof.
本发明的氧化铋光催化剂是通过以下方法制备的，其特征在于，将含铋化合物和L-天冬酰胺溶解在水中，得到均匀溶液，然后在80～160℃下保温4～8小时，冷却后将沉淀取出洗涤干燥，在320～440℃焙烧1～4小时，得到氧化铋光催化剂。The bismuth oxide photocatalyst of the present invention is prepared by the following method, which is characterized in that the bismuth-containing compound and L-asparagine are dissolved in water to obtain a uniform solution, and then kept at 80-160° C. for 4-8 hours, cooled Afterwards, the precipitate is taken out, washed and dried, and calcined at 320-440° C. for 1-4 hours to obtain a bismuth oxide photocatalyst.
所述的含铋化合物优选为硝酸铋。The bismuth-containing compound is preferably bismuth nitrate.
优选，所述的含铋化合物和L-天冬酰胺是按照物质的量之比1:(2～9)溶解在水中。Preferably, the bismuth-containing compound and L-asparagine are dissolved in water according to the ratio of the amount of substances 1: (2-9).
所述的洗涤是先用水洗涤，再用乙醇洗涤。The washing is firstly washed with water, and then washed with ethanol.
本发明还提供了上述氧化铋光催化剂在可见光下催化降解有机污染物中的应用。The present invention also provides the application of the above-mentioned bismuth oxide photocatalyst in catalytic degradation of organic pollutants under visible light.
本发明利用含铋化合物和L-天冬酰胺在常压和低温的条件下反应生成二者的配合物前驱体，通过焙烧后，前驱体作为自牺牲模板分解和转化为纳米花状β相氧化铋可见光催化剂。该纳米花状β相氧化铋具有更高的均匀性、粒度较细、颗粒尺寸分布窄、且具有一定形貌，所制备的氧化铋平均晶粒尺寸约为50纳米，再由这些晶粒构成的纳米三维花状结构平均直径是300～600纳米。The present invention uses bismuth-containing compounds and L-asparagine to react under normal pressure and low temperature conditions to generate the complex precursors of the two. After roasting, the precursors are decomposed as self-sacrificing templates and converted into nano-flower-like β-phase oxidation Bismuth visible photocatalyst. The nanoflower-like β-phase bismuth oxide has higher uniformity, finer particle size, narrow particle size distribution, and has a certain shape. The average grain size of the prepared bismuth oxide is about 50 nanometers, and then composed of these grains The average diameter of the nanometer three-dimensional flower-like structure is 300-600 nanometers.
本发明的制备方法非常简单，实验条件要求很低，最终产品纳米花状β相氧化铋，其纯度高，产率高，节约成本和能源。本发明解决了运用水热法无法大规模生产氧化铋的缺点，解决了以前不能在常压条件下制备和不能在较宽烘烧温度范围获得纯β相的难题，为氧化铋在环境治理方面的广泛应用提供了一种新的方法。同时，本发明所得产物的产率较高，节约原料和生产成本。另外，原料L-天冬酰胺是一种氨基酸，对人体和其它生物无毒害作用，在生产和使用过程中不会对环境产生二次污染。本发明的纳米花状β相氧化铋是纳米级，颗粒尺寸均一，太阳能利用率较高，量子效率较高，因此，具有较高的可见光催化活性，可以广泛应用于有机污染物的催化降解，并可以在其它光电设备和工业催化剂等领域进行使用。The preparation method of the present invention is very simple, and the requirements for experimental conditions are very low, and the final product is nano-flower-shaped β-phase bismuth oxide, which has high purity and high yield, and saves cost and energy. The invention solves the disadvantage that bismuth oxide cannot be produced on a large scale by using the hydrothermal method, and solves the previous problems that it cannot be prepared under normal pressure conditions and cannot obtain pure β phase in a wide range of firing temperatures, and it is a great contribution to the environmental management of bismuth oxide. Wide application provides a new method. Simultaneously, the yield of the product obtained in the present invention is relatively high, which saves raw materials and production costs. In addition, the raw material L-asparagine is an amino acid, which is non-toxic to the human body and other organisms, and will not cause secondary pollution to the environment during production and use. The nano-flower-like β-phase bismuth oxide of the present invention is nanoscale, has uniform particle size, high solar energy utilization rate, and high quantum efficiency. Therefore, it has high visible light catalytic activity and can be widely used in the catalytic degradation of organic pollutants. And it can be used in other photoelectric equipment, industrial catalyst and other fields.
附图说明：Description of drawings:
图1是实施例1的氧化铋的X射线衍射图；Fig. 1 is the X-ray diffraction figure of the bismuth oxide of embodiment 1;
图2是实施例1的氧化铋的扫描电镜形貌图。FIG. 2 is a scanning electron microscope topography diagram of the bismuth oxide of Example 1. FIG.
图3是应用实施例1的污染物去除率和总有机碳去除率图。Fig. 3 is the graph of pollutant removal rate and total organic carbon removal rate of Application Example 1.
具体实施方式：detailed description:
以下实施例是对本发明的进一步说明，而不是对本发明的限制。The following examples are to further illustrate the present invention, rather than limit the present invention.
实施例1Example 1
将1克五水硝酸铋和1.5克一水合L-天冬酰胺加入50mL蒸馏水中，充分搅拌溶解，再将混合后的溶液转移到150mL圆底烧瓶中，在100℃油浴下充分反应4小时；待反应冷却下来至室温后，将反应所得的反应物进行离心洗涤，沉淀分别使用去离子水和乙醇洗涤3遍，得到白色固体，将产物置于烘箱中，60℃下干燥12小时；然后将白色固体充分研磨，置于陶瓷坩埚内，使用马福炉在340℃下煅烧2小时，得到淡黄色固体粉末，即纳米花状β相氧化铋光催化剂。该纳米花状β相氧化铋光催化剂的X射线衍射图和扫描电镜形貌图如图1和图2所示。将此纳米花状β相氧化铋光催化剂按照下述应用实施例1中的方法进行处理，结果表明，光反应1小时可以完全降解目标污染物对羟基联苯，如图3所示。Add 1 g of bismuth nitrate pentahydrate and 1.5 g of L-asparagine monohydrate into 50 mL of distilled water, stir and dissolve thoroughly, then transfer the mixed solution to a 150 mL round bottom flask, and fully react for 4 hours in an oil bath at 100°C ; After the reaction is cooled down to room temperature, the reactant obtained from the reaction is centrifuged and washed, and the precipitate is washed 3 times with deionized water and ethanol respectively to obtain a white solid, which is placed in an oven and dried at 60°C for 12 hours; then The white solid was thoroughly ground, placed in a ceramic crucible, and calcined at 340° C. for 2 hours using a muffle furnace to obtain a light yellow solid powder, which is the nanoflower-shaped β-phase bismuth oxide photocatalyst. The X-ray diffraction pattern and scanning electron microscope topography of the nanoflower-like β-phase bismuth oxide photocatalyst are shown in Fig. 1 and Fig. 2 . The nano-flower-like β-phase bismuth oxide photocatalyst was treated according to the method in Application Example 1 below, and the results showed that the target pollutant p-hydroxybiphenyl could be completely degraded by photoreaction for 1 hour, as shown in FIG. 3 .
实施例2Example 2
将1克五水硝酸铋和2.0克一水合L-天冬酰胺加入50mL蒸馏水中，充分搅拌溶解，再将混合后的溶液转移到150mL圆底烧瓶中，在120℃油浴下充分反应6小时；待反应冷却至室温后，将反应所得的反应物进行离心洗涤，沉淀分别使用去离子水和乙醇洗涤3遍，得到白色固体，将产物置于烘箱中，60℃下干燥12小时；然后将白色固体充分研磨，置于陶瓷坩埚内，使用马福炉在380℃下煅烧2小时，得到淡黄色固体粉末，即纳米花状β相氧化铋光催化剂。将此纳米花状β相氧化铋光催化剂按照下述应用实施例1中的方法进行处理，结果表明，光反应1小时可以完全降解目标污染物对羟基联苯。Add 1 g of bismuth nitrate pentahydrate and 2.0 g of L-asparagine monohydrate into 50 mL of distilled water, stir to dissolve, then transfer the mixed solution to a 150 mL round bottom flask, and fully react in an oil bath at 120°C for 6 hours ; After the reaction is cooled to room temperature, the reactant obtained from the reaction is centrifuged and washed, and the precipitate is washed 3 times with deionized water and ethanol respectively to obtain a white solid, which is placed in an oven and dried at 60°C for 12 hours; then The white solid was thoroughly ground, placed in a ceramic crucible, and calcined at 380° C. for 2 hours using a muffle furnace to obtain a light yellow solid powder, which is the nanoflower-shaped β-phase bismuth oxide photocatalyst. The nano-flower-like β-phase bismuth oxide photocatalyst was treated according to the method in Application Example 1 below, and the results showed that the target pollutant p-hydroxybiphenyl could be completely degraded by photoreaction for 1 hour.
实施例3Example 3
将2克五水硝酸铋和4.5克一水合L-天冬酰胺加入100mL蒸馏水中，充分搅拌溶解，再将混合后的溶液转移到250mL圆底烧瓶中，在140℃油浴下充分反应8小时；待反应冷却至室温后，将反应所得的反应物进行离心洗涤，沉淀分别使用去离子水和乙醇洗涤3遍，得到白色固体，将产物置于烘箱中，60℃下干燥12小时；然后将白色固体充分研磨，置于陶瓷坩埚内，使用马福炉在400℃下煅烧2小时，得到淡黄色固体粉末，即纳米花状β相氧化铋光催化剂。将此纳米花状β相氧化铋光催化剂按照下述应用实施例1中的方法进行处理，结果表明，光反应1小时可以完全降解目标污染物对羟基联苯。Add 2 grams of bismuth nitrate pentahydrate and 4.5 grams of L-asparagine monohydrate into 100 mL of distilled water, stir and dissolve, then transfer the mixed solution to a 250 mL round bottom flask, and fully react in an oil bath at 140°C for 8 hours ; After the reaction is cooled to room temperature, the reactant obtained from the reaction is centrifuged and washed, and the precipitate is washed 3 times with deionized water and ethanol respectively to obtain a white solid, which is placed in an oven and dried at 60°C for 12 hours; then The white solid was thoroughly ground, placed in a ceramic crucible, and calcined at 400° C. for 2 hours in a muffle furnace to obtain a light yellow solid powder, which is the nanoflower-shaped β-phase bismuth oxide photocatalyst. The nano-flower-like β-phase bismuth oxide photocatalyst was treated according to the method in Application Example 1 below, and the results showed that the target pollutant p-hydroxybiphenyl could be completely degraded by photoreaction for 1 hour.
实施例4Example 4
将4.85克五水硝酸铋和3克一水合L-天冬酰胺加入200mL蒸馏水中，充分搅拌溶解，再将混合后的溶液转移到250mL圆底烧瓶中，在160℃油浴下充分反应4小时；待反应冷却至室温后，将反应所得的反应物进行离心洗涤，沉淀分别使用去离子水和乙醇洗涤3遍，得到白色固体，将产物置于烘箱中，60℃下干燥12小时；然后将白色固体充分研磨，置于陶瓷坩埚内，使用马福炉在420℃下煅烧1小时，得到淡黄色固体粉末，即纳米花状β相氧化铋光催化剂。将此纳米花状β相氧化铋光催化剂按照下述应用实施例1中的方法进行处理，结果表明，光反应1小时可以完全降解目标污染物对羟基联苯。Add 4.85 grams of bismuth nitrate pentahydrate and 3 grams of L-asparagine monohydrate into 200 mL of distilled water, fully stir to dissolve, then transfer the mixed solution to a 250 mL round bottom flask, and fully react for 4 hours in an oil bath at 160 °C ; After the reaction is cooled to room temperature, the reactant obtained from the reaction is centrifuged and washed, and the precipitate is washed 3 times with deionized water and ethanol respectively to obtain a white solid, which is placed in an oven and dried at 60°C for 12 hours; then The white solid was thoroughly ground, placed in a ceramic crucible, and calcined at 420° C. for 1 hour using a muffle furnace to obtain a light yellow solid powder, which is the nanoflower-shaped β-phase bismuth oxide photocatalyst. The nano-flower-like β-phase bismuth oxide photocatalyst was treated according to the method in Application Example 1 below, and the results showed that the target pollutant p-hydroxybiphenyl could be completely degraded by photoreaction for 1 hour.
实施例5Example 5
将4.85克五水硝酸铋和13.5克一水合L-天冬酰胺加入300mL蒸馏水中，充分搅拌溶解，再将混合后的溶液转移到500mL圆底烧瓶中，在80℃油浴下充分反应8小时；待反应冷却至室温后，将反应所得的反应物进行离心洗涤，沉淀分别使用去离子水和乙醇洗涤3遍，得到白色固体，将产物置于烘箱中，60℃下干燥12小时；然后将白色固体充分研磨，置于陶瓷坩埚内，使用马福炉在440℃下煅烧4小时，得到淡黄色固体粉末，即纳米花状β相氧化铋光催化剂。将此纳米花状β相氧化铋光催化剂按照下述应用实施例1中的方法进行处理，结果表明，光反应1小时可以完全降解目标污染物对羟基联苯。Add 4.85 grams of bismuth nitrate pentahydrate and 13.5 grams of L-asparagine monohydrate into 300 mL of distilled water, fully stir to dissolve, then transfer the mixed solution to a 500 mL round bottom flask, and fully react in an oil bath at 80 °C for 8 hours ; After the reaction is cooled to room temperature, the reactant obtained from the reaction is centrifuged and washed, and the precipitate is washed 3 times with deionized water and ethanol respectively to obtain a white solid, which is placed in an oven and dried at 60°C for 12 hours; then The white solid was thoroughly ground, placed in a ceramic crucible, and calcined at 440° C. for 4 hours in a muffle furnace to obtain a light yellow solid powder, which is the nanoflower-shaped β-phase bismuth oxide photocatalyst. The nano-flower-like β-phase bismuth oxide photocatalyst was treated according to the method in Application Example 1 below, and the results showed that the target pollutant p-hydroxybiphenyl could be completely degraded by photoreaction for 1 hour.
应用实施例1Application Example 1
称取50mg材料1(实施例1制备的纳米花状β相氧化铋)，置于50mL浓度为20ppm的对羟基联苯水溶液中，首先避光暗吸附60min，接着在可见光(1000W氙灯，配420nm滤光片)照射下进行反应1小时，期间每隔一定时间取样品一次，将滤液运用紫外可见光分光光度计进行测量，将所得结果进行数据处理，结果表明(见图3)可见光反应1小时可以完全降解目标污染物对羟基联苯，同时体系中总有机碳去除率(矿化率)达到95％以上，说明污染物及其降解中间物被彻底的去除，不会产生二次污染。Weigh 50mg of material 1 (the nano-flower-like β-phase bismuth oxide prepared in Example 1), place 50mL concentration of 20ppm in p-hydroxybiphenyl aqueous solution, first avoid light and dark adsorption for 60min, then in visible light (1000W xenon lamp, with 420nm filter) to react for 1 hour, during which samples are taken at regular intervals, the filtrate is measured by a UV-visible spectrophotometer, and the results obtained are processed. The results show (see Figure 3) that the visible light reaction can The target pollutant p-hydroxybiphenyl is completely degraded, and the total organic carbon removal rate (mineralization rate) in the system reaches more than 95%, indicating that the pollutants and their degradation intermediates are completely removed without secondary pollution.
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