CN103785422B - The preparation method of cauliflower-shaped CdS Nano microsphere photochemical catalyst and application thereof - Google Patents
The preparation method of cauliflower-shaped CdS Nano microsphere photochemical catalyst and application thereof Download PDFInfo
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Abstract
本发明涉及菜花状CdS纳米微球光催化剂的制备方法及其应用，属于环境材料制备技术领域。本发明包括菜花状CdS纳米微球光催化剂的制备，是在离子水中加入氯化镉和稳定剂，充分搅拌后用氢氧化钠调节溶液的pH值后通氮气除氧，再取适量硫化钠溶于水。然后将上述制备的溶液通氮气除氧气，加入硫化钠待溶液由无色变成橙黄色后，将溶液倒入到高压反应釜中加热、冷却、离心，洗涤并真空干燥，得到菜花状CdS纳米微球光催化剂。按照本发明所述的制备方法得到的菜花状CdS纳米微球光催化剂，能够有效利用可见光在抗生素废水中降解盐酸土霉素溶液。
The invention relates to a preparation method and application of a cauliflower-like CdS nanometer microsphere photocatalyst, belonging to the technical field of environmental material preparation. The invention includes the preparation of cauliflower-like CdS nano-microsphere photocatalyst, which is to add cadmium chloride and a stabilizer to ionized water, adjust the pH value of the solution with sodium hydroxide after sufficient stirring, pass nitrogen to remove oxygen, and then take an appropriate amount of sodium sulfide to dissolve in water. Then the solution prepared above was passed through nitrogen to remove oxygen, and sodium sulfide was added until the solution changed from colorless to orange-yellow. microsphere photocatalyst. The cauliflower-like CdS nanometer microsphere photocatalyst obtained according to the preparation method of the invention can effectively utilize visible light to degrade oxytetracycline hydrochloride solution in antibiotic wastewater.
Description
技术领域 technical field
本发明属于环境材料制备技术领域，涉及水热法合成菜花状CdS纳米微球光催化剂及其应用。 The invention belongs to the technical field of environmental material preparation, and relates to the hydrothermal synthesis of cauliflower-like CdS nanometer microsphere photocatalyst and its application.
背景技术 Background technique
抗生素（Antibiotics）是由某些微生物或动植物产生的化学物质，能抑制微生物和其他细胞增殖的物质，广泛用于治疗各种细菌感染或抑制致病微生物感染的药物。由于抗生素药物的不合理利用，对环境产生了较大的危害，以盐酸土霉素为例，许多研究报告表明抗生素已广泛存在土壤、地表水、地下水、沉积物、城市污水以及动物***物氧化塘中。因此，消除环境中抗生素残留带来的环境污染和食物链产品安全等问题已是科研工作者迫切需要解决的重大问题。目前废水处理的手段主要有物理法、化学法、生物化学法等，但众多废水处理技术或存在运行成本高、或带有二次污染等缺点，使得处理效果不能令人满意。 Antibiotics are chemical substances produced by certain microorganisms, animals and plants, substances that can inhibit the proliferation of microorganisms and other cells, and are widely used as drugs for treating various bacterial infections or inhibiting pathogenic microbial infections. Due to the irrational use of antibiotics, it has caused great harm to the environment. Taking oxytetracycline hydrochloride as an example, many research reports have shown that antibiotics have been widely oxidized in soil, surface water, groundwater, sediment, urban sewage and animal excreta. In the pond. Therefore, the elimination of environmental pollution caused by antibiotic residues in the environment and the safety of food chain products have become major issues that researchers urgently need to solve. At present, the means of wastewater treatment mainly include physical methods, chemical methods, biochemical methods, etc., but many wastewater treatment technologies have disadvantages such as high operating costs or secondary pollution, which makes the treatment effect unsatisfactory.
半导体光催化降解技术是一种高级氧化技术，是一种最有可能利用自然界太阳光实现清洁去污的环境友好技术，目前已成为人们关注较多的废水处理方法。在众多光催化用半导体材料中TiO2光催化剂具有低廉、无二次污染、等优点被誉为环境友好的污染处理材料，在环保和节能的应用前景受到广泛的关注，其主要应用于废水、废气处理及抗菌、自清洁产品的开发等领域。但是TiO2本身也存在局限性，如其光吸收阈值局限在紫外光区、光量子效率比较低、光催化降解缺乏选择性等。因此，近年来具有可见光响应能力强、光催化活性高、有选择性降解能力的新型光催化剂的开发成为研究的热点。 Semiconductor photocatalytic degradation technology is an advanced oxidation technology and an environmentally friendly technology that is most likely to use natural sunlight to achieve cleaning and decontamination. It has become a wastewater treatment method that people pay more attention to. Among many semiconductor materials for photocatalysis, TiO2 photocatalyst has the advantages of low cost, no secondary pollution, and is known as an environmentally friendly pollution treatment material. It has received extensive attention in the application prospects of environmental protection and energy saving. It is mainly used in wastewater, Waste gas treatment and antibacterial, self-cleaning product development and other fields. However, TiO 2 itself also has limitations, such as its light absorption threshold is limited in the ultraviolet region, the photon quantum efficiency is relatively low, and the photocatalytic degradation lacks selectivity. Therefore, in recent years, the development of new photocatalysts with strong visible light response ability, high photocatalytic activity and selective degradation ability has become a research hotspot.
硫化镉(CdS)是一种较典型的Ⅱ–Ⅵ族压电半导体和半导体光敏材料，具有较大的带隙宽度(约2.45eV)，也是一种良好的太阳能电池窗口材料和非线性光学材料。因其具有优良的光学、电学性质，被广泛应用于各种发光器件、光伏器件、光学探测器、光敏传感器以及光催化等领域，然而CdS本身具有的光腐蚀性限制了其应用。本发明中制得的CdS催化剂，方法操作简单，有效的减小了光腐蚀性，并对盐酸土霉素有较好的降解效果同时提高了催化剂稳定性。 Cadmium sulfide (CdS) is a typical II-VI piezoelectric semiconductor and semiconductor photosensitive material with a large bandgap width (about 2.45eV), and is also a good solar cell window material and nonlinear optical material. . Because of its excellent optical and electrical properties, it is widely used in various light-emitting devices, photovoltaic devices, optical detectors, photosensitive sensors, and photocatalysis. However, the photocorrosion of CdS itself limits its application. The CdS catalyst prepared in the present invention has simple method and operation, effectively reduces photocorrosion, has better degradation effect on oxytetracycline hydrochloride and improves catalyst stability at the same time.
发明内容 Contents of the invention
本发明以水热法为技术手段，制备出菜花状CdS纳米微球光催化剂 The present invention uses hydrothermal method as technical means to prepare cauliflower-like CdS nano-microsphere photocatalyst
本发明按以下步骤进行； The present invention is carried out according to the following steps;
在小烧杯中加入适量去离子水，通氮气除氧气后加入一定量的氯化镉(CdCl2·2.5H2O)，搅拌至完全溶解后，用1mol/L的NaOH溶液调节溶液的pH=7（所得到的光催化剂在pH=7时具有良好的菜花状形貌）。然后将一定量硫化钠（Na2S·9H2O）加入到上述溶液中，继续通入氮气除去氧气15min，倒入高压反应釜中加热，取出自然冷却，将冷却后的溶液离心得沉淀物，洗涤后放入真空干燥箱中烘干，得到菜花状CdS微球光催化剂。 Add an appropriate amount of deionized water into a small beaker, pass nitrogen to remove oxygen, add a certain amount of cadmium chloride (CdCl 2 2.5H 2 O), stir until completely dissolved, and adjust the pH of the solution with 1mol/L NaOH solution = 7 (the obtained photocatalyst has a good cauliflower-like morphology at pH = 7). Then add a certain amount of sodium sulfide (Na 2 S 9H 2 O) to the above solution, continue to pass nitrogen gas to remove oxygen for 15 minutes, pour it into a high-pressure reactor for heating, take it out and let it cool naturally, and centrifuge the cooled solution to obtain a precipitate , and put it into a vacuum drying oven to dry after washing to obtain a cauliflower-like CdS microsphere photocatalyst.
上述技术方案中所述去离子水的用量为能使固体完全溶解即可； The consumption of deionized water described in the above-mentioned technical scheme can make solid dissolve completely;
其中，所述的加入其中镉源硫源的摩尔质量比为1:0.5-3； Wherein, the molar mass ratio of adding the cadmium source to the sulfur source is 1:0.5-3;
所述的高压反应釜中加热为180oC加热1-3h； The heating in the high-pressure reactor is 180 o C for 1-3h;
所述的洗涤为分别用去离子水和无水乙醇洗涤两次； Described washing is to wash twice with deionized water and absolute ethanol respectively;
所述烘干为50℃烘干6h。 The drying is at 50° C. for 6 hours.
按照本发明所述的制备方法得到的菜花状CdS微球光催化剂，在抗生素废水中降解盐酸土霉素抗生素的应用。 The application of the cauliflower-like CdS microsphere photocatalyst obtained according to the preparation method of the invention in degrading oxytetracycline hydrochloride antibiotic in antibiotic waste water.
本发明中所用氯化镉，硫化钠均为分析纯，购于国药化学试剂有限公司；盐酸土霉素抗生素为标品，购于上海顺勃生物工程有限公司。 The cadmium chloride and sodium sulfide used in the present invention are analytically pure, purchased from Sinopharm Chemical Reagent Co., Ltd.; the oxytetracycline hydrochloride antibiotic is a standard product, purchased from Shanghai Shunbo Bioengineering Co., Ltd.
本发明的有益效果： Beneficial effects of the present invention:
本发明实现了以半导体花状CdS微球为催化剂降解抗生素废水的目的。半导体材料作为光催化剂，可见光作为激发，通过与污染物分子的界面相互作用实现特殊的催化或转化效应，使周围的氧气及水分子激发成极具氧化力的自由负离子，从而达到降解环境中有害有机物质的目的，该方法不会造成资源浪费与附加污染的形成，且操作简便，是一种绿色环保的高效处理技术。 The invention realizes the purpose of degrading antibiotic waste water by using the semiconductor flower-like CdS microsphere as a catalyst. Semiconductor materials are used as photocatalysts, and visible light is used as excitation to achieve special catalytic or conversion effects through the interface interaction with pollutant molecules, so that the surrounding oxygen and water molecules are excited into free negative ions with great oxidative power, so as to achieve the degradation of harmful substances in the environment. For the purpose of organic matter, this method will not cause waste of resources and the formation of additional pollution, and is easy to operate, which is a green and efficient treatment technology.
附图说明 Description of drawings
图1为菜花状CdS微球光催化剂的XRD图，图中很清楚的展现了CdS的特征峰。 Figure 1 is the XRD pattern of the cauliflower-like CdS microsphere photocatalyst, which clearly shows the characteristic peaks of CdS.
图2为菜花状CdS微球光催化剂的SEM及EDS图。 Figure 2 is the SEM and EDS images of the cauliflower-like CdS microsphere photocatalyst.
图3为菜花状CdS微球光催化剂对盐酸土霉素降解行为谱图。 Fig. 3 is a spectrogram of the degradation behavior of oxytetracycline hydrochloride by cauliflower-like CdS microsphere photocatalyst.
具体实施方式 detailed description
光催化活性评价：在DW-01型光化学反应仪（购自扬州大学教学仪器厂）中进行，可见光灯照射，将100mL盐酸土霉素模拟废水加入反应器中并测定其初始值，然后加入复合光催化剂，磁力搅拌并开启曝气装置通入空气保持催化剂处于悬浮或飘浮状态，光照过程中间隔10min取样分析，离心分离后取上层清液在分光光度计λmax=257nm处测定吸光度，并通过公式： Evaluation of photocatalytic activity: carried out in DW-01 photochemical reaction instrument (purchased from Yangzhou University Teaching Instrument Factory), irradiated by visible light, adding 100mL oxytetracycline hydrochloride simulated wastewater into the reactor and measuring its initial value, and then adding compound For photocatalysts, magnetically stir and open the aeration device to feed air to keep the catalyst in a suspended or floating state. Sampling and analysis are carried out at intervals of 10 minutes during the illumination process. formula:
DR=[（A0-Ai）/A0]×100%算出降解率，其中A0为达到吸附平衡时盐酸土霉素溶液的吸光度，Ai为定时取样测定的盐酸土霉素溶液的吸光度。 DR=[(A 0 -A i )/A 0 ]×100% to calculate the degradation rate, where A 0 is the absorbance of oxytetracycline hydrochloride solution when adsorption equilibrium is reached, and A i is the absorbance of oxytetracycline hydrochloride solution measured by regular sampling. Absorbance.
下面结合具体实施实例对本发明做进一步说明。 The present invention will be further described below in conjunction with specific implementation examples.
实施例1：Example 1:
(1)菜花状CdS微球光催化剂的制备： (1) Preparation of cauliflower-like CdS microsphere photocatalyst:
在小烧杯中加入去离子水，通氮气除氧气后加入氯化镉1.542g，搅拌至完全溶解后，充分搅拌后用1mol/L的氢氧化钠溶液调节溶液的pH=7，然后将1.248g硫化钠加入到上述溶液中，继续通入氮气除去氧气15min，倒入50mL高压反应釜中加热2h，取出自然冷却，将冷却后的溶液离心，洗涤并放入真空干燥箱中于50℃中6h烘干，得到镉源硫源摩尔质量比为1.29:1的菜花状CdS微球光催化剂光催化剂。 Add deionized water into a small beaker, add cadmium chloride 1.542g after purging nitrogen to remove oxygen, stir until it is completely dissolved, adjust the pH of the solution to 7 with 1mol/L sodium hydroxide solution after stirring fully, and then dissolve 1.248g Sodium sulfide was added to the above solution, continue to pass nitrogen gas to remove oxygen for 15 minutes, pour it into a 50mL autoclave and heat for 2 hours, take it out and let it cool naturally, centrifuge the cooled solution, wash it and put it in a vacuum drying oven at 50°C for 6 hours drying to obtain a cauliflower-like CdS microsphere photocatalyst photocatalyst with a molar mass ratio of cadmium source to sulfur source of 1.29:1.
(2)取(1)中样品0.05g在光化学反应仪中进行光催化降解试验，测得该光催化剂对15mg/L盐酸土霉素抗生素的降解率在60min内达到56.26%。 (2) Take 0.05 g of the sample in (1) and conduct a photocatalytic degradation test in a photochemical reaction apparatus. It is measured that the degradation rate of the photocatalyst to 15 mg/L oxytetracycline hydrochloride antibiotic reaches 56.26% within 60 min.
实施例2：Example 2:
(1)在小烧杯中加入去离子水，通氮气除氧气后加入1.542g氯化镉，搅拌至完全溶解后，充分搅拌后用1mol/L的氢氧化钠溶液调节溶液的pH=7，然后将0.811g硫化钠加入到上述溶液中保持镉源硫源摩尔质量比为1:0.5，继续通入氮气除去氧气15min，倒入50mL高压反应釜中加热2h，取出自然冷却，将冷却后的溶液离心，洗涤并放入真空干燥箱中于50℃中6h烘干，得到镉源硫源摩尔质量比为1:0.5的菜花状CdS微球光催化剂光催化剂。 (1) Add deionized water in a small beaker, add 1.542g of cadmium chloride after purging nitrogen to remove oxygen, stir until completely dissolved, after fully stirring, adjust the pH=7 of the solution with 1mol/L sodium hydroxide solution, then Add 0.811g of sodium sulfide to the above solution to keep the molar mass ratio of cadmium source and sulfur source at 1:0.5, continue to feed nitrogen to remove oxygen for 15 minutes, pour it into a 50mL autoclave and heat for 2 hours, take it out and let it cool naturally, and put the cooled solution Centrifuge, wash and dry in a vacuum drying oven at 50°C for 6 hours to obtain a cauliflower-shaped CdS microsphere photocatalyst with a molar mass ratio of cadmium source to sulfur source of 1:0.5.
(2)取(1)中样品在0.05g光化学反应仪中进行光催化降解试验，测得该光催化剂对15mg/L盐酸土霉素抗生素的降解率在60min内达到36.31%。 (2) Take the sample in (1) and carry out the photocatalytic degradation test in a 0.05g photochemical reaction apparatus. It is measured that the degradation rate of the photocatalyst to 15mg/L oxytetracycline hydrochloride antibiotic reaches 36.31% within 60min.
实施例3：Example 3:
按实施例1中的步骤，不同的是(1)中选取镉源硫源比为1:3制备催化剂，其中氯化镉1.542g、硫化钠4.865g。反应结束后取出自然冷却，将冷却后的溶液离心，洗涤并放入真空干燥箱中烘干，得到光催化剂。 According to the steps in Example 1, the difference is that the ratio of cadmium source to sulfur source in (1) is 1:3 to prepare the catalyst, wherein 1.542g of cadmium chloride and 4.865g of sodium sulfide. After the reaction is finished, take it out to cool naturally, centrifuge the cooled solution, wash it and put it into a vacuum drying oven to dry to obtain a photocatalyst.
(2)取(1)中样品0.05g在光化学反应仪中进行光催化降解试验，测得制得的光催化对15mg/L盐酸土霉素抗生素的降解率在60min内达到30.22%, (2) Get 0.05g of the sample in (1) and carry out the photocatalytic degradation test in the photochemical reaction instrument, and the photocatalytic degradation rate of 15mg/L oxytetracycline hydrochloride antibiotics obtained reaches 30.22% within 60min,
实施例4：Example 4:
按实施例1中的步骤，不同的是(1)中选取不同加热时间（1h,2h,3h）制备催化剂，取出自然冷却，将冷却后的溶液离心，洗涤并放入真空干燥箱中烘干，得到光催化剂。 According to the steps in Example 1, the difference is that (1) selects different heating times (1h, 2h, 3h) to prepare the catalyst, take it out and cool it naturally, centrifuge the cooled solution, wash it and put it in a vacuum drying oven to dry , to obtain a photocatalyst.
(2)取(1)中样品0.05g在光化学反应仪中进行光催化降解试验，测得反应时间为2h制得的光催化对15mg/L盐酸土霉素抗生素的降解率最高，而且在60min内达到56.26%,。 (2) Get 0.05g of the sample in (1) and carry out the photocatalytic degradation test in the photochemical reaction instrument. The photocatalytic degradation rate of 15mg/L oxytetracycline hydrochloride antibiotic is the highest for the photocatalysis made in 2h, and the reaction time is 60min Reached 56.26%, within.
实施例5：Example 5:
按实施例1中的步骤，不同的是(2)中抗生素浓度5mg/L,10mg/L,15mg/L,20mg/L，光催化合成以及别的条件未改变。 According to the steps in Example 1, the difference is that the antibiotic concentration in (2) is 5mg/L, 10mg/L, 15mg/L, 20mg/L, photocatalytic synthesis and other conditions remain unchanged.
(2)取(1)中样品0.05g在光化学反应仪中进行光催化降解试验，测得该光催化剂对对15mg/L盐酸土霉素抗生素的降解率最高，在60min内达到56.26%。 (2) Take 0.05 g of the sample in (1) and conduct a photocatalytic degradation test in a photochemical reaction apparatus. It is measured that the photocatalyst has the highest degradation rate to 15 mg/L oxytetracycline hydrochloride antibiotic, reaching 56.26% within 60 minutes.
实施例6：Embodiment 6:
按实施例1中的步骤，不同的是(2)将光催化降解中的催化剂用量改变为0.01g,0.05g,0.07g,0.1g. By the steps in Example 1, the difference is (2) the catalyst consumption in the photocatalytic degradation is changed to 0.01g, 0.05g, 0.07g, 0.1g.
(2)取(1)中样品在光化学反应仪中进行光催化降解试验，测得该当光催化剂用量为0.1g时对盐酸土霉素抗生素的降解率在60min内达到73.42%。 (2) Take the sample in (1) and carry out the photocatalytic degradation test in the photochemical reaction instrument. It is measured that when the photocatalyst dosage is 0.1g, the degradation rate of oxytetracycline hydrochloride antibiotic reaches 73.42% within 60min.
实施例7：Embodiment 7:
按实施例1中的步骤，不同的是(2)中溶液环境改变，依次将溶液pH改变为3.1,7,10。 According to the steps in Example 1, the difference is that the environment of the solution in (2) is changed, and the pH of the solution is changed to 3.1, 7, and 10 in sequence.
(2)取(1)中样品0.1g在光化学反应仪中进行光催化降解试验，测得该光催化剂在碱性、中性环境中降解效率较好，而且在中性溶液环境中(pH=7)达到最高73.42%。 (2) Take 0.1g of the sample in (1) and carry out the photocatalytic degradation test in the photochemical reaction instrument. 7) Reached the highest 73.42%.
图1为菜花状CdS微球光催化剂的XRD图，图中很清楚的展现了CdS的特征峰。由图1可知，所得到的CdS的特征峰十分明显呈现立方晶相，峰尖锐并无任何杂峰说明产品结晶度和纯度都较高。 Figure 1 is the XRD pattern of the cauliflower-like CdS microsphere photocatalyst, which clearly shows the characteristic peaks of CdS. It can be seen from Figure 1 that the characteristic peaks of the obtained CdS are very obvious in the cubic crystal phase, and the peaks are sharp without any miscellaneous peaks, indicating that the crystallinity and purity of the product are relatively high.
图2为菜花状CdS微球光催化剂的SEM及EDS图，从图中可以看出CdS的具体形貌。由图2中a中可看出CdS微球分散均匀，粒径大小均一。而且从高倍放大图像b、c可知CdS微球形貌规则呈菜花状，但微球表面粗糙。从图2中的能谱EDS图中可以看出，CdS微球的主要构成元素为Cd和S，而其中C可能来自于空气中的CO2而C含量对CdS微球的整体性能影响不大。 Figure 2 is the SEM and EDS images of the cauliflower-like CdS microsphere photocatalyst, from which the specific morphology of CdS can be seen. It can be seen from a in Figure 2 that the CdS microspheres are uniformly dispersed and the particle size is uniform. Moreover, from the high-magnification images b and c, it can be seen that the morphology of the CdS microspheres is cauliflower-like, but the surface of the microspheres is rough. From the energy spectrum EDS diagram in Figure 2, it can be seen that the main constituent elements of CdS microspheres are Cd and S, and the C may come from CO2 in the air, and the C content has little effect on the overall performance of CdS microspheres .
图3为菜花状CdS微球光催化剂对盐酸土霉素降解行为谱图。从图中可以看出，盐酸土霉素在波长=257nm处有较强的吸收峰。并且随着反应时间的进行，盐酸土霉素溶液浓度逐渐降低，逐渐被光催化剂所降解。 Fig. 3 is a spectrogram of the degradation behavior of oxytetracycline hydrochloride by cauliflower-like CdS microsphere photocatalyst. It can be seen from the figure that oxytetracycline hydrochloride has a strong absorption peak at wavelength = 257nm. And as the reaction time goes on, the concentration of oxytetracycline hydrochloride solution gradually decreases, and it is gradually degraded by the photocatalyst.
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