技术领域technical field
本发明属于污水处理技术领域，具体涉及水中新兴有机污染物和难降解有机污染物的处理方法，尤其涉及一种基于铁掺杂有序介孔四氧化三钴激活单过硫酸盐降解水中抗菌药物的方法。The invention belongs to the technical field of sewage treatment, and specifically relates to a treatment method for emerging organic pollutants and refractory organic pollutants in water, in particular to a method for degrading antibacterial drugs in water based on iron-doped ordered mesoporous cobalt tetroxide activating monopersulfate.
背景技术Background technique
近年来，药物及个人护理用品（Pharmaceuticals and Personal Care Products,PPCPs）已成为一种新兴的环境污染物，在地下水、地表水、土壤等环境介质中均被检测到，且被证明对环境及人类健康造成一定的危害。环丙沙星（Ciprofloxacin, CIP）属于喹诺酮类抗菌药物，广泛用于人类及动物疾病的治疗。残留的环丙沙星进入人体后，会对人体产生毒副作用，并大大增强人体病原菌的耐药性。另一方面，动物摄入了大量环丙沙星后，随粪尿排出体外，进入到自然环境中，对生态系统构成了潜在的危害。环丙沙星作为一种人畜共用药，药物残留通过食物链对人体健康危害更大。有研究指出，环丙沙星较难被微生物降解，且不能被常规水处理工艺有效去除。因此，亟需寻找有效方法解决环境中环丙沙星的污染问题。In recent years, Pharmaceuticals and Personal Care Products (PPCPs) have become an emerging environmental pollutant, which has been detected in groundwater, surface water, soil and other environmental media, and has been proved to be harmful to the environment and human beings. Health hazards. Ciprofloxacin (CIP) is a quinolone antibacterial drug widely used in the treatment of human and animal diseases. After the residual ciprofloxacin enters the human body, it will cause toxic and side effects to the human body and greatly enhance the drug resistance of human pathogenic bacteria. On the other hand, after animals ingest a large amount of ciprofloxacin, it is excreted with feces and urine and enters the natural environment, posing a potential hazard to the ecosystem. Ciprofloxacin is a drug shared by humans and animals, and drug residues are more harmful to human health through the food chain. Studies have pointed out that ciprofloxacin is difficult to be degraded by microorganisms and cannot be effectively removed by conventional water treatment processes. Therefore, it is urgent to find an effective method to solve the pollution problem of ciprofloxacin in the environment.
近年来，基于硫酸根自由基（SO4-·）的高级氧化技术受到了研究学者的广泛关注。其中过渡金属离子激活单过硫酸盐（Peroxymonosufate, PMS）体系产生强氧化活性的SO4-·在室温下即可高效率的进行，无需外加能量（超声、热源和光源），具有广阔的应用前景。但均相单过硫酸盐催化体系存在催化剂回收困难以及易造成生环境二次污染等问题。In recent years, the advanced oxidation technology based on sulfate radical (SO4- ·) has attracted extensive attention of researchers. Among them, the transition metal ion activates the monopersulfate (Peroxymonosufate, PMS) system to produce SO4- with strong oxidation activity. It can be carried out efficiently at room temperature without external energy (ultrasound, heat source and light source), and has broad application prospects. . However, the homogeneous monopersulfate catalyst system has problems such as difficulty in catalyst recovery and easy to cause secondary pollution to the living environment.
发明内容Contents of the invention
本发明提供了一种基于铁掺杂有序介孔四氧化三钴形成磁性TOM-Co3O4/CoFe2O4激活单过硫酸盐降解水中抗菌药物的方法，旨在解决均相单过硫酸盐激活体系中催化剂（过渡金属离子）回收困难且易造成环境二次污染的问题；解决目前所采用的非均相尖晶石型催化剂比表面积小，催化能力较低的问题；以及非均相TOM-Co3O4激活单过硫酸盐体系中催化剂回收操作复杂的问题。The invention provides a method based on iron-doped ordered mesoporous cobalt tetroxide to form magnetic TOM-Co3 O4 /CoFe2 O4 to activate monopersulfate to degrade antibacterial drugs in water, aiming to solve the problem of homogeneous monopersulfate activation It is difficult to recover the catalyst (transition metal ion) in the system and it is easy to cause secondary pollution to the environment; solve the problem of small specific surface area and low catalytic ability of the currently used heterogeneous spinel catalyst; and heterogeneous TOM- Co3 O4 activates the complex problem of catalyst recovery operation in monopersulfate system.
一种基于铁掺杂有序介孔四氧化三钴激活单过硫酸盐降解水中抗菌药物的方法，按以下步骤进行：A method for activating monopersulfate to degrade antibacterial drugs in water based on iron-doped ordered mesoporous cobalt tetroxide, carried out according to the following steps:
一、制备TOM-Co3O4：1. Preparation of TOM-Co3 O4 :
将模板KIT-6充分研磨后投加到Co(NO3)2·6H2O的乙醇溶液中，在室温条件下搅拌1h得溶液A； Thoroughly grind the template KIT-6, add it to the ethanol solution of Co(NO3 )2 6H2 O, and stir at room temperature for 1 hour to obtain solution A;
将步骤一所得溶液A于60 ℃条件下鼓风干燥得到粉红色固体粉末，将此固体粉末转移至坩埚内，并将其放置在马弗炉内于200 ℃条件下培烧5 h，所述马弗炉的升温速度为2 ℃/min； will step one The obtained solution A was air-dried at 60°C to obtain a pink solid powder, which was transferred to a crucible, and placed in a muffle furnace for 5 h at 200°C. The muffle furnace The heating rate is 2 ℃/min;
将步骤一中培烧后的褐色固体粉末充分研磨后投加到Co(NO3)2·6H2O的乙醇溶液中，在室温条件下搅拌1 h得溶液B； will step one The brown solid powder after medium sintering was fully ground, then added to the ethanol solution of Co(NO3 )2 6H2 O, and stirred at room temperature for 1 h to obtain solution B;
将步骤一所得溶液B于60 ℃条件下鼓风干燥得到黑色固体，将此固体转移至坩埚内，并将其放置在马弗炉内于450 ℃条件下培烧5 h，所述马弗炉的升温速度为2℃/min； will step one The resulting solution B was air-dried at 60°C to obtain a black solid, which was transferred to a crucible, placed in a muffle furnace and fired at 450°C for 5 h, and the heating rate of the muffle furnace was 2°C/min;
将步骤一中培烧的黑色固体粉末冷却至室温，经充分研磨之后投加至盛有2mol/L NaOH溶液的圆底烧瓶内，于60 ℃水浴条件下搅拌12 h，将搅拌后的溶液静置30 min倒去上清液，以上步骤重复三次； will step one The medium-fired black solid powder was cooled to room temperature, and after being fully ground, it was added to a round-bottomed flask filled with 2mol/L NaOH solution, stirred for 12 h in a water bath at 60 °C, and the stirred solution was left to stand for 30 min Pour off the supernatant, and repeat the above steps three times;
将步骤一所得产品分别用去超纯水和乙醇反复清洗至pH=7之后，60 ℃条件下真空干燥后再经充分研磨得TOM-Co3O4； will step one The obtained product was repeatedly washed with ultrapure water and ethanol to pH = 7, then vacuum-dried at 60°C and then fully ground to obtain TOM-Co3 O4 ;
二、制备磁性TOM-Co3O4/CoFe2O4：2. Preparation of magnetic TOM-Co3 O4 /CoFe2 O4 :
将TOM-Co3O4投加到Fe(NO3)3·9H2O-乙醇溶液中，在室温条件下搅拌1 h； Add TOM-Co3 O4 into Fe(NO3 )3 ·9H2 O-ethanol solution, and stir at room temperature for 1 h;
作为优选，步骤二中所述的TOM-Co3O4、Fe(NO3)3·9H2O的摩尔比为1:1；Preferably, step two The molar ratio of TOM-Co3 O4 , Fe(NO3 )3 ·9H2 O described in is 1:1;
作为优选，步骤二中所述的Fe(NO3)3·9H2O-乙醇溶液的摩尔浓度为0.4 mol/L；Preferably, step two The molar concentration of Fe(NO3 )3 ·9H2 O-ethanol solution described in is 0.4 mol/L;
将步骤二搅拌后的溶液于60 ℃条件下鼓风干燥得到黑色固体粉末，将此固体粉末转移至坩埚内，并将其放置在马弗炉内于450 ℃条件下培烧5 h，所述马弗炉的升温速度为2℃/min； will step two The stirred solution was air-dried at 60°C to obtain a black solid powder, which was transferred to a crucible, placed in a muffle furnace and fired at 450°C for 5 h, the muffle furnace The heating rate is 2°C/min;
将步骤二中培烧后的黑色固体粉末充分研磨得TOM-Co3O4/CoFe2O4，待用； will step two The black solid powder after medium sintering is fully ground to obtain TOM-Co3 O4 /CoFe2 O4 , which is ready for use;
三、将磁性TOM-Co3O4/CoFe2O4与含环丙沙星水溶液充分混合，转移至棕色摇瓶中；3. Fully mix the magnetic TOM-Co3 O4 /CoFe2 O4 with the aqueous solution containing ciprofloxacin, and transfer it to a brown shaker flask;
四、将单过硫酸盐投加至步骤三中的棕色摇瓶，于20~50 ℃下水浴振荡反应30~120min；4. Add monopersulfate to the brown shaker flask in step 3, and shake it in a water bath at 20-50 ℃ for 30-120 minutes;
五、通过外加磁场分离磁性TOM-Co3O4/CoFe2O4，回收的TOM-Co3O4/CoFe2O4用乙醇和去离子水进行反复清洗并于60 ℃条件下真空干燥，得到回收的TOM-Co3O4/CoFe2O4。5. The magnetic TOM-Co3 O4 /CoFe2 O4 is separated by an external magnetic field, and the recovered TOM-Co3 O4 /CoFe2 O4 is washed repeatedly with ethanol and deionized water and dried under vacuum at 60 °C. Recovered TOM-Co3 O4 /CoFe2 O4 is obtained.
作为优选，步骤一中所述的模板KIT-6、Co(NO3)2·6H2O的摩尔比为1:1。Preferably, step one The molar ratio of template KIT-6, Co(NO3 )2 ·6H2 O as described in is 1:1.
作为优选，步骤一中所述的Co(NO3)2·6H2O溶液的摩尔浓度为0.8 mol/L。Preferably, step one The molar concentration of the Co(NO3 )2 ·6H2 O solution described in is 0.8 mol/L.
作为优选，步骤一中所述的黑色固体与NaOH溶液的质量比为1:100~200。Preferably, step one The mass ratio of black solid and NaOH solution described in is 1:100~200.
作为优选，步骤二中所述的TOM-Co3O4、Fe(NO3)3·9H2O的摩尔比为1:1。Preferably, step two The molar ratio of TOM-Co3 O4 , Fe(NO3 )3 ·9H2 O described in is 1:1.
作为优选，步骤二中所述的Fe(NO3)3·9H2O-乙醇溶液的摩尔浓度为0.4 mol/L。Preferably, step two The molar concentration of the Fe(NO3 )3 ·9H2 O-ethanol solution described in is 0.4 mol/L.
作为优选，步骤三中所述的TOM-Co3O4/CoFe2O4的投加量为每升含环丙沙星水溶液中投放10~200 mg。Preferably, the dosage of TOM-Co3 O4 /CoFe2 O4 described in step 3 is 10-200 mg per liter of ciprofloxacin-containing aqueous solution.
作为优选，步骤三中所述的含环丙沙星水溶液浓度为1~20 mg/L。Preferably, the concentration of the ciprofloxacin-containing aqueous solution described in step three is 1-20 mg/L.
作为优选，步骤四中所述的单过硫酸盐为单过硫酸钾、单过硫酸铵、单过硫酸钠和单过硫酸钙中的至少一种；所述的单过硫酸盐与水溶液中环丙沙星的摩尔比为66:1。As preferably, the monopersulfate described in step 4 is at least one of potassium monopersulfate, ammonium monopersulfate, sodium monopersulfate and calcium monopersulfate; The molar ratio of sand star is 66:1.
本发明的意义是解决均相单过硫酸盐激活体系中催化剂（过渡金属离子）回收困难且易造成环境二次污染的问题；解决目前所采用的非均相尖晶石型催化剂比表面积小，催化能力较低的问题；解决非均相TOM-Co3O4激活单过硫酸盐体系中催化剂回收操作复杂的问题。本发明采用的磁性TOM-Co3O4/CoFe2O4具备很大的比表面积和丰富的孔道结构，能够吸附目标有机物的同时，表面大量的含氧官能团会进一步激活单过硫酸盐，生成SO4-·能够加快目标污染物的氧化降解。在TOM-Co3O4/CoFe2O4的使用过程中，金属离子M2+/M3+的价态转变和单过硫酸盐分解之间的平衡保证了催化剂发挥持续高效的催化性能；TOM-Co3O4/CoFe2O4具有良好的磁性和回用性，操作简便，降低了运行成本。The significance of the present invention is to solve the problem that the catalyst (transition metal ion) in the homogeneous monopersulfate activation system is difficult to recover and easily cause secondary environmental pollution; to solve the problem that the heterogeneous spinel catalyst currently used has a small specific surface area, The problem of low catalytic ability; solve the problem of complex catalyst recovery operation in the heterogeneous TOM-Co3 O4 activated monopersulfate system. The magnetic TOM-Co3 O4 /CoFe2 O4 used in the present invention has a large specific surface area and rich pore structure, which can adsorb target organic matter, and at the same time, a large number of oxygen-containing functional groups on the surface will further activate monopersulfate and generate SO4- ·It can accelerate the oxidative degradation of target pollutants. During the use of TOM-Co3 O4 /CoFe2 O4 , the balance between the valence transition of metal ions M2+ /M3+ and the decomposition of monopersulfate ensures the continuous and efficient catalytic performance of the catalyst; TOM-Co3 O4 /CoFe2 O4 has good magnetic properties and reusability, and is easy to operate, reducing operating costs.
本发明有益效果如下：The beneficial effects of the present invention are as follows:
1．TOM-Co3O4/CoFe2O4在催化单过硫酸盐的过程中，金属离子溶出很低，减少了环境的二次污染。1. In the process of TOM-Co3 O4 /CoFe2 O4 catalyzing monopersulfate, the dissolution of metal ions is very low, which reduces the secondary pollution of the environment.
2．TOM-Co3O4/CoFe2O4可以高效激活单过硫酸盐产生SO4-·，操作方便，节约能耗，无需对体系进行紫外辐照、超声空化、加热等。2. TOM-Co3 O4 /CoFe2 O4 can efficiently activate monopersulfate to generate SO4- ·, is convenient to operate, saves energy consumption, and does not need to irradiate the system with ultraviolet radiation, ultrasonic cavitation, heating, etc.
3．TOM-Co3O4/CoFe2O4具有很大的比表面积和丰富的孔道结构，可以更容易与单过硫酸盐和有机污染物接触，极大地提高催化效率。3. TOM-Co3 O4 /CoFe2 O4 has a large specific surface area and rich pore structure, which can be more easily contacted with monopersulfate and organic pollutants, greatly improving the catalytic efficiency.
4．TOM-Co3O4/CoFe2O4表面含有丰富的含氧官能团可以高效催化单过硫酸盐产生SO4-·氧化降解有机物，去除率超过95 %。4. The surface of TOM-Co3 O4 /CoFe2 O4 is rich in oxygen-containing functional groups, which can efficiently catalyze monopersulfate to produce SO4- ·oxidative degradation of organic matter, and the removal rate exceeds 95%.
5．TOM-Co3O4/CoFe2O4可通过外加磁场的方式进行回收重复利用，降低运行成本。5. TOM-Co3 O4 /CoFe2 O4 can be recycled and reused by applying an external magnetic field to reduce operating costs.
附图说明Description of drawings
图1为在不同工况条件下环丙沙星浓度百分比随时间的关系图。Fig. 1 is the relationship diagram of the concentration percentage of ciprofloxacin with time under different working conditions.
图2为回用次数对TOM-Co3O4/CoFe2O4激活单过硫酸盐降解环丙沙星的影响图。Fig. 2 is a diagram showing the effect of reuse times on the activation of monopersulfate to degrade ciprofloxacin by TOM-Co3 O4 /CoFe2 O4 .
图3为TOM-Co3O4/CoFe2O4经过经磁铁吸附前后的效果图，其中左图为未经磁铁吸附的效果图，右图为经磁铁吸附的效果图。Figure 3 is the effect diagram of TOM-Co3 O4 /CoFe2 O4 before and after magnet adsorption, in which the left image is the effect image without magnet adsorption, and the right image is the effect image after magnet adsorption.
具体实施方式detailed description
本发明技术方案不局限于以下例举的具体实施方法，还包括各具体实施方式间的任意组合。The technical solution of the present invention is not limited to the specific implementation methods exemplified below, but also includes any combination of various specific implementation modes.
实施例1Example 1
一、制备TOM-Co3O4：1. Preparation of TOM-Co3 O4 :
将模板KIT-6充分研磨后投加到Co(NO3)2·6H2O溶液中，在室温条件下搅拌1 h得溶液A； After fully grinding the template KIT-6, add it to the Co(NO3 )2 6H2 O solution, and stir at room temperature for 1 h to obtain solution A;
步骤一中所述的模板KIT-6、Co(NO3)2·6H2O的摩尔比为1:1；step one The molar ratio of the template KIT-6, Co(NO3 )2 ·6H2 O described in is 1:1;
步骤一中所述的溶液以乙醇为溶剂；step one The solution described in takes ethanol as solvent;
步骤一中所述的Co(NO3)2·6H2O溶液的摩尔浓度为0.8 mol/L；step one The molar concentration of the Co(NO3 )2 ·6H2 O solution described in is 0.8 mol/L;
将步骤一所得溶液A于60 ℃条件下鼓风干燥得到粉红色固体粉末，将此固体粉末转移至坩埚内，并将其放置在马弗炉内于200 ℃条件下培烧5 h，所述马弗炉的升温速度为2 ℃/min； will step one The obtained solution A was air-dried at 60°C to obtain a pink solid powder, which was transferred to a crucible, and placed in a muffle furnace for 5 h at 200°C. The muffle furnace The heating rate is 2 ℃/min;
将步骤一中培烧后的褐色固体粉末充分研磨后投加到Co(NO3)2·6H2O溶液中，在室温条件下搅拌1 h得溶液B； will step one The brown solid powder after medium sintering was fully ground and added to the Co(NO3 )2 6H2 O solution, and stirred at room temperature for 1 h to obtain solution B;
步骤一中所述的溶液以乙醇为溶剂；step one The solution described in takes ethanol as solvent;
步骤一中所述的Co(NO3)2·6H2O溶液的摩尔浓度为0.8 mol/L；step one The molar concentration of the Co(NO3 )2 ·6H2 O solution described in is 0.8 mol/L;
将步骤一所得溶液B于60 ℃条件下鼓风干燥得到黑色固体，将此固体转移至坩埚内，并将其放置在马弗炉内于450 ℃条件下培烧5 h； will step one The obtained solution B was air-dried at 60°C to obtain a black solid, which was transferred to a crucible, and placed in a muffle furnace for 5 h at 450°C;
步骤一中所述的将黑色固体粉末于450℃条件下培烧5 h，马弗炉的升温速度为2℃/min；step one Burn the black solid powder at 450°C for 5 hours, and the temperature rise rate of the muffle furnace is 2°C/min;
将步骤一中培烧的黑色固体粉末冷却至室温，经充分研磨之后投加至盛有2mol/L NaOH溶液的圆底烧瓶内，于60 ℃水浴条件下搅拌12 h，将搅拌后的溶液静置30 min倒去上清液，以上步骤重复三次； will step one The medium-fired black solid powder was cooled to room temperature, and after being fully ground, it was added to a round-bottomed flask filled with 2mol/L NaOH solution, stirred for 12 h in a water bath at 60 °C, and the stirred solution was left to stand for 30 min Pour off the supernatant, and repeat the above steps three times;
步骤一中所述的黑色固体与2 mol/L NaOH溶液的质量比为1:(100~200)；step one The mass ratio of black solid described in and 2 mol/L NaOH solution is 1:(100～200);
将步骤一中得到的材料分别用去超纯水和乙醇洗涤至pH=7之后，60 ℃真空干燥得到黑色固体，将此固体充分研磨之后储存备用。 will step one The material obtained in the above was washed with ultrapure water and ethanol to pH = 7, and then vacuum-dried at 60 °C to obtain a black solid, which was fully ground and stored for later use.
二、制备磁性TOM-Co3O4/CoFe2O4：2. Preparation of magnetic TOM-Co3 O4 /CoFe2 O4 :
将TOM-Co3O4投加到Fe(NO3)3·9H2O溶液中，在室温条件下搅拌1 h； Add TOM-Co3 O4 into Fe(NO3 )3 9H2 O solution, and stir at room temperature for 1 h;
步骤一中所述的TOM-Co3O4、Fe(NO3)3·9H2O的摩尔比为1:1；step one The molar ratio of TOM-Co3 O4 , Fe(NO3 )3 ·9H2 O described in is 1:1;
步骤一中所述的溶液以乙醇为溶剂；step one The solution described in takes ethanol as solvent;
步骤一中所述的Fe(NO3)3·9H2O溶液的摩尔浓度为0.4 mol/L；step one The molar concentration of the Fe(NO3 )3 9H2 O solution described in is 0.4 mol/L;
将步骤二搅拌后的溶液于60 ℃条件下鼓风干燥得到黑色固体粉末，将此固体粉末转移至坩埚内，并将其放置在马弗炉内于450 ℃条件下培烧5 h； will step two The stirred solution was air-dried at 60 °C to obtain a black solid powder, which was transferred to a crucible and placed in a muffle furnace for 5 h at 450 °C;
步骤二中所述的将黑色固体粉末于450 ℃条件下培烧5 h，马弗炉的升温速度为2℃/min；step two Burn the black solid powder at 450 °C for 5 h, and the heating rate of the muffle furnace is 2 °C/min;
将步骤二中培烧后的黑色固体粉末充分研磨后备用。 will step two The black solid powder after medium-baking is fully ground and ready for use.
三、将磁性TOM-Co3O4/CoFe2O4与含环丙沙星水溶液充分混合，转移至棕色摇瓶中；3. Fully mix the magnetic TOM-Co3 O4 /CoFe2 O4 with the aqueous solution containing ciprofloxacin, and transfer it to a brown shaker flask;
步骤三中所述的TOM-Co3O4/CoFe2O4的投加量为10~50 mg/L;The dosage of TOM-Co3 O4 /CoFe2 O4 described in step 3 is 10-50 mg/L;
步骤三中所述的含环丙沙星水溶液浓度为1~5 mg/L； The ciprofloxacin-containing aqueous solution concentration described in step 3 is 1 ~ 5 mg/L;
步骤三中所述的转移至棕色摇瓶中混合溶液体积为100 mL。 The volume of the mixed solution transferred to the brown shaker flask described in step 3 is 100 mL.
四、投加单过硫酸盐：将单过硫酸盐投加至步骤三中的棕色摇瓶中进行环丙沙星的降解反应；4. Add monopersulfate: add monopersulfate to the brown shake flask in step 3 to carry out the degradation reaction of ciprofloxacin;
保持反应液温度为20~30 ℃条件下水浴振荡反应30~60 min，可实现水中环丙沙星的高效去除，并得到含有TOM-Co3O4/CoFe2O4的混合溶液；Keeping the temperature of the reaction solution at 20-30 ℃ and shaking the reaction in a water bath for 30-60 min, the efficient removal of ciprofloxacin in water can be achieved, and a mixed solution containing TOM-Co3 O4 /CoFe2 O4 can be obtained;
步骤四中所述的单过硫酸盐为单过硫酸钾、单过硫酸铵、单过硫酸钠和单过硫酸钙中的一种或其中几种的混合物；The monopersulfate described in step 4 is one or a mixture of potassium monopersulfate, ammonium monopersulfate, sodium monopersulfate and calcium monopersulfate;
步骤四中所述的单过硫酸盐与水溶液中环丙沙星的摩尔比为(10~50):1。The molar ratio of monopersulfate described in step 4 to ciprofloxacin in the aqueous solution is (10～50):1.
五、通过外加磁场分离磁性TOM-Co3O4/CoFe2O4：通过外加磁场分离磁性TOM-Co3O4/CoFe2O4，回收的TOM-Co3O4/CoFe2O4用乙醇和去离子水进行反复清洗并于60 ℃条件下真空干燥，得到回收的TOM-Co3O4/CoFe2O4；5. Separation of magnetic TOM-Co3 O4 /CoFe2 O4 by external magnetic field: Separation of magnetic TOM-Co3 O4 /CoFe2 O4 by external magnetic field, the recovered TOM-Co3 O4 /CoFe2 O4 is used Repeated washing with ethanol and deionized water and vacuum drying at 60 °C to obtain recovered TOM-Co3 O4 /CoFe2 O4 ;
步骤五中所述的TOM-Co3O4/CoFe2O4用乙醇和去离子水进行反复清洗，清洗次数不少于5次。The TOM-Co3 O4 /CoFe2 O4 described in step 5 is repeatedly washed with ethanol and deionized water, and the washing times are not less than 5 times.
测试环丙沙星浓度百分比随时间的变化情况，变化曲线见附图1。Test the change of ciprofloxacin concentration percentage with time, and the change curve is shown in Figure 1.
实施例2：Example 2:
本实施方式与实施例1不同的是步骤三中目标污染物环丙沙星的浓度为5~10 mg/L，其他步骤及参数与实施例1相同。The difference between this embodiment and Example 1 is that the concentration of the target pollutant ciprofloxacin in Step 3 is 5-10 mg/L, and other steps and parameters are the same as in Example 1.
实施例3：Example 3:
本实施方式与实施例1不同的是步骤三中目标污染物环丙沙星的浓度为10~20 mg/L，其他步骤及参数与实施例1相同。The difference between this embodiment and Example 1 is that the concentration of the target pollutant ciprofloxacin in Step 3 is 10-20 mg/L, and other steps and parameters are the same as in Example 1.
实施例4：Example 4:
本实施方式与实施例1不同的是步骤三中TOM-Co3O4/CoFe2O4的投加量为50~100 mg/L，其他步骤及参数与实施例1相同。The difference between this embodiment and Example 1 is that the dosage of TOM-Co3 O4 /CoFe2 O4 in Step 3 is 50-100 mg/L, and other steps and parameters are the same as in Example 1.
实施例5：Example 5:
本实施方式与实施例1不同的是步骤三中TOM-Co3O4/CoFe2O4的投加量为100~200 mg/L，其他步骤及参数与实施例1相同。The difference between this embodiment and Example 1 is that the dosage of TOM-Co3 O4 /CoFe2 O4 in Step 3 is 100-200 mg/L, and other steps and parameters are the same as in Example 1.
实施例6：Embodiment 6:
本实施方式与实施例1不同的是步骤四中单过硫酸盐与目标污染物的摩尔比为(50~100):1，其他步骤及参数与实施例1相同。The difference between this embodiment and Example 1 is that the molar ratio of monopersulfate to target pollutant in Step 4 is (50-100):1, and other steps and parameters are the same as in Example 1.
实施例7：Embodiment 7:
本实施方式与实施例1不同的是步骤四中单过硫酸盐与含环丙沙星的摩尔比为(100~200):1，其他步骤及参数与实施例1相同。The difference between this embodiment and Example 1 is that the molar ratio of monopersulfate to ciprofloxacin in step 4 is (100-200): 1, and other steps and parameters are the same as in Example 1.
实施例8：Embodiment 8:
本实施方式与实施例1不同的是步骤四中反应体系温度为30 ~50 ℃，其他步骤及参数与实施例1相同。The difference between this embodiment and Example 1 is that the temperature of the reaction system in Step 4 is 30-50 °C, and other steps and parameters are the same as in Example 1.
实施例9：Embodiment 9:
本实施方式与实施例1不同的是步骤三中投加的TOM-Co3O4/CoFe2O4为步骤五中通过外加磁场回收的TOM-Co3O4/CoFe2O4，其他步骤及参数与实施例1相同。The difference between this embodiment and Example 1 is that the TOM-Co 3 O4 /CoFe2 O4 added in thethird step is the TOM-Co3 O4 /CoFe2 O4 recovered by the external magnetic field in the fifth step, and the other steps And parameter is identical with embodiment 1.
实施例10：多次回用催化剂（TOM-Co3O4/CoFe2O4）激活PMS对环丙沙星降解实验按以下方法进行：Example 10: The catalyst (TOM-Co3 O4 /CoFe2 O4 ) was used multiple times to activate PMS to degrade ciprofloxacin by the following method:
将磁性TOM-Co3O4/CoFe2O4与含环丙沙星水溶液充分混合，转移至棕色摇瓶中；Fully mix the magnetic TOM-Co3 O4 /CoFe2 O4 with the aqueous solution containing ciprofloxacin, and transfer it to a brown shaker flask;
步骤三中所述的TOM-Co3O4/CoFe2O4为步骤五中通过外加磁场回收的材料；The TOM-Co3 O4 /CoFe2 O4 described in the step 3 is the material recovered by the external magnetic field in the step 5;
步骤三中所述的TOM-Co3O4/CoFe2O4的投加量为100 mg/L；The dosage of TOM-Co3 O4 /CoFe2 O4 described in step 3 is 100 mg/L;
步骤三中所述的含环丙沙星水溶液浓度为5 mg/L； The ciprofloxacin-containing aqueous solution concentration described in step 3 is 5 mg/L;
步骤三中所述的转移至棕色摇瓶中混合溶液体积为100 mL。 The volume of the mixed solution transferred to the brown shaker flask described in step 3 is 100 mL.
二、投加单过硫酸盐：将单过硫酸盐投加至步骤三中的棕色摇瓶中进行环丙沙星的降解反应；2. Add monopersulfate: add monopersulfate to the brown shake flask in step 3 to carry out the degradation reaction of ciprofloxacin;
保持反应液温度为25±1 ℃条件下水浴振荡反应60 min，可实现水中环丙沙星的高效去除，并得到含有TOM-Co3O4/CoFe2O4的混合溶液；Keeping the temperature of the reaction solution at 25±1 ℃ and shaking the reaction in a water bath for 60 minutes, the efficient removal of ciprofloxacin in water can be achieved, and a mixed solution containing TOM-Co3 O4 /CoFe2 O4 can be obtained;
步骤四中所述的单过硫酸盐为单过硫酸钾、单过硫酸铵、单过硫酸钠和单过硫酸钙中的一种或其中几种的混合物；The monopersulfate described in step 4 is one or a mixture of potassium monopersulfate, ammonium monopersulfate, sodium monopersulfate and calcium monopersulfate;
步骤四中所述的单过硫酸盐与水溶液中环丙沙星的摩尔比为66:1。The molar ratio of monopersulfate described in step 4 to ciprofloxacin in the aqueous solution is 66:1.
三、通过外加磁场分离磁性TOM-Co3O4/CoFe2O4：通过外加磁场分离磁性TOM-Co3O4/CoFe2O4，回收的TOM-Co3O4/CoFe2O4用乙醇和去离子水进行反复清洗并于60 ℃条件下真空干燥，得到回收的TOM-Co3O4/CoFe2O4；3. Separation of magnetic TOM-Co3 O4 /CoFe2 O4 by external magnetic field: Separation of magnetic TOM-Co3 O4 /CoFe2 O4 by external magnetic field, the recovered TOM-Co3 O4 /CoFe2 O4 is used Repeated washing with ethanol and deionized water and vacuum drying at 60 °C to obtain recovered TOM-Co3 O4 /CoFe2 O4 ;
步骤五中所述的TOM-Co3O4/CoFe2O4用乙醇和去离子水进行反复清洗，清洗次数不少于5次。The TOM-Co3 O4 /CoFe2 O4 described in step 5 is repeatedly washed with ethanol and deionized water, and the washing times are not less than 5 times.
回用次数不同的TOM-Co3O4/CoFe2O4与过硫酸盐协同吸附环丙沙星实验时，环丙沙星剩余浓度与时间的关系图见附图2。When using different times of TOM-Co3 O4 /CoFe2 O4 and persulfate for synergistic adsorption of ciprofloxacin, the relationship between the remaining concentration of ciprofloxacin and time is shown in Figure 2.
从附图2中可以看到多次回收后TOM-Co3O4/CoFe2O4仍然保持很高催化性能，第五次回收的TOM-Co3O4/CoFe2O4和单过硫酸盐共存的条件下，60 min内环丙沙星的去除率仍高达90 %以上。由此可见， TOM-Co3O4/CoFe2O4具备良好的回用性。It can be seen from Figure 2 that TOM-Co3 O4 /CoFe2 O4 still maintains high catalytic performance after multiple recovery, and the fifth recovery of TOM-Co3 O4 /CoFe2 O4 and monopersulfuric acid Under the condition of salt coexistence, the removal rate of ciprofloxacin was still as high as 90% within 60 min. It can be seen that TOM-Co3 O4 /CoFe2 O4 has good reusability.
比较例1单独投加TOM-Co3O4/CoFe2O4对环丙沙星的吸附实验按以下方法进行：Comparative Example 1 Adding TOM-Co3 O4 /CoFe2 O4 alone to the adsorption experiment of ciprofloxacin is carried out as follows:
一、制备TOM-Co3O4：与实施例1步骤一相同；1. Preparation of TOM-Co3 O4 : same as Step 1 of Example 1;
二、制备磁性TOM-Co3O4/CoFe2O4：与实施例1步骤二相同；2. Preparation of magnetic TOM-Co3 O4 /CoFe2 O4 : same as Step 2 of Example 1;
三、将磁性TOM-Co3O4/CoFe2O4与含环丙沙星水溶液充分混合，转移至棕色摇瓶中，保持反应液温度为25±1 ℃条件下水浴振荡反应60 min，并得到含有TOM-Co3O4/CoFe2O4的混合溶液；3. Fully mix the magnetic TOM-Co3 O4 /CoFe2 O4 with the aqueous solution containing ciprofloxacin, transfer it to a brown shaker flask, keep the temperature of the reaction solution at 25±1°C and shake it in a water bath for 60 minutes, and A mixed solution containing TOM-Co3 O4 /CoFe2 O4 is obtained;
步骤三中所述的TOM-Co3O4/CoFe2O4的投加量为100 mg/L；The dosage of TOM-Co3 O4 /CoFe2 O4 described in step 3 is 100 mg/L;
步骤三中所述的含环丙沙星水溶液浓度为5 mg/L；The ciprofloxacin-containing aqueous solution concentration described in step 3 is 5 mg/L;
步骤三中所述的转移至棕色摇瓶中混合溶液体积为100 mL。The volume of the mixed solution transferred to the brown shaker flask described in step 3 is 100 mL.
四、通过外加磁场分离磁性TOM-Co3O4/CoFe2O4：通过外加磁场分离磁性TOM-Co3O4/CoFe2O4，回收的TOM-Co3O4/CoFe2O4用乙醇和去离子水反复清洗后并于于60 ℃条件下条件下真空干燥，得到回收的TOM-Co3O4/CoFe2O4，则完成了单独投加TOM-Co3O4/CoFe2O4对环丙沙星的吸附实验；4. Separation of magnetic TOM-Co3 O4 /CoFe2 O4 by external magnetic field: Separation of magnetic TOM-Co3 O4 /CoFe2 O4 by external magnetic field, recovery of TOM-Co3 O4 /CoFe2 O4 After repeated washing with ethanol and deionized water and vacuum drying at 60 °C, the recovered TOM-Co3 O4 /CoFe2 O4 was obtained, and the separate dosing of TOM-Co3 O4 /CoFe2 was completed. OThe adsorption experiment of ciprofloxacin;
步骤四中所述的TOM-Co3O4/CoFe2O4用乙醇和去离子水反复清洗，清洗次数不少于5次。The TOM-Co3 O4 /CoFe2 O4 described in Step 4 is repeatedly washed with ethanol and deionized water, and the washing frequency is not less than 5 times.
测试环丙沙星浓度百分比随时间的变化情况，变化曲线见附图1。Test the change of ciprofloxacin concentration percentage with time, and the change curve is shown in Figure 1.
比较例2单独投加单过硫酸盐对环丙沙星的氧化实验按以下方法进行：Comparative example 2 adds monopersulfate separately to the oxidation experiment of ciprofloxacin and carries out as follows:
一、配制环丙沙星水溶液：配置一定浓度的环丙沙星水溶液并转移至棕色摇瓶中；1. Preparation of ciprofloxacin aqueous solution: prepare a certain concentration of ciprofloxacin aqueous solution and transfer it to a brown shaker flask;
步骤一中所述的含环丙沙星水溶液浓度为5 mg/L；The ciprofloxacin-containing aqueous solution concentration described in step 1 is 5 mg/L;
步骤一中所述的转移至棕色摇瓶中混合溶液体积为100 mL。The volume of the mixed solution transferred to the brown shaker flask described in step 1 was 100 mL.
二、投加单过硫酸盐：将单过硫酸盐投加至步骤一中的棕色摇瓶中保持反应液温度为25±1 ℃条件下水浴振荡反应60 min，可实现单独投加单过硫酸盐对环丙沙星的氧化实验；2. Dosing monopersulfate: Add monopersulfate to the brown shaker flask in step 1. Keep the temperature of the reaction solution at 25±1 ℃ and shake the reaction in a water bath for 60 minutes, which can realize the single addition of monopersulfuric acid Oxidation experiment of ciprofloxacin by salt;
步骤四中所述的单过硫酸盐为过硫酸氢钾；The monopersulfate described in step 4 is potassium hydrogen persulfate;
步骤四中所述的单过硫酸盐与水溶液中环丙沙星的摩尔比为66:1。The molar ratio of monopersulfate described in step 4 to ciprofloxacin in the aqueous solution is 66:1.
通过对比实施例1、比较例1和比较例2，可以发现：采用本发明所述的TOM-Co3O4/CoFe2O4协同单过硫酸盐吸附水溶液中环丙沙星比二者单独使用时，具有更好的吸附效果。By comparing Example 1, Comparative Example 1 and Comparative Example 2, it can be found that: TOM-Co3 O4 /CoFe2 O4 of the present invention is used in coordination with monopersulfate adsorption in the aqueous solution of ciprofloxacin than the two used alone , it has a better adsorption effect.
以上仅列举了本发明的优选实施方案，本发明的保护范围并不限制于此，本领域技术人员在本发明权利要求范围内所作的任何改变均落入本发明保护范围内。The above only lists preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereto. Any changes made by those skilled in the art within the scope of the claims of the present invention all fall within the protection scope of the present invention.
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| CN201610685175.XACN106430516B (en) | 2016-08-18 | 2016-08-18 | A method for degrading antibacterial drugs in water based on iron-doped ordered mesoporous cobalt tetroxide-activated monopersulfate |
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| CN201610685175.XACN106430516B (en) | 2016-08-18 | 2016-08-18 | A method for degrading antibacterial drugs in water based on iron-doped ordered mesoporous cobalt tetroxide-activated monopersulfate |
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| CN201610685175.XAActiveCN106430516B (en) | 2016-08-18 | 2016-08-18 | A method for degrading antibacterial drugs in water based on iron-doped ordered mesoporous cobalt tetroxide-activated monopersulfate |
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