阅读说明：本技术 一种非金属改性镍铁尖晶石芬顿催化剂的制备方法 (Preparation method of nonmetal modified nickel-iron spinel Fenton catalyst ) 是由 余冠杰 鞠美庭 刘乐 钱恒力 赵莹 付学颖 王艳双 于 2021-01-12 设计创作，主要内容包括：本发明属于环保材料领域,公开了一种非金属改性镍铁尖晶石芬顿催化剂,包括以下步骤：a.制备热剥离聚合物氮化碳。b.取热剥离聚合物氮化碳分散在乙醇中超声处理,得到溶液A。c.取六水合硝酸镍和九水合硝酸铁溶于乙醇,得到溶液B。将溶液A缓慢加入B,得到混合溶液C。d.使用6mol/L的NaOH溶液调节C溶液的pH,得到溶液D。e.将步骤d中得到的溶液D放入聚四氟乙烯为内衬的水热釜中水热10～36h,温度为100～250℃,抽滤,真空干燥,得到非金属改性镍铁尖晶石芬顿催化剂。本发明提供的非金属改性镍铁尖晶石芬顿催化剂具有原料廉价易得、制备过程简单且适用范围广的优点。(The invention belongs to the field of environment-friendly materials, and discloses a nonmetal modified nickel-iron spinel Fenton catalyst, which comprises the following steps: a. preparing thermal stripping polymer carbon nitride. b. And dispersing the thermal release polymer carbon nitride in ethanol for ultrasonic treatment to obtain a solution A. c. And dissolving nickel nitrate hexahydrate and ferric nitrate nonahydrate in ethanol to obtain a solution B. And slowly adding the solution A into the solution B to obtain a mixed solution C. d. The pH of the solution C was adjusted using 6mol/L NaOH solution to obtain a solution D. e. And D, putting the solution D obtained in the step D into a hydrothermal kettle with polytetrafluoroethylene as a lining, and carrying out hydrothermal treatment for 10-36 h at the temperature of 100-250 ℃, carrying out suction filtration, and carrying out vacuum drying to obtain the nonmetal modified nickel-iron spinel Fenton catalyst. The nonmetal modified nickel-iron spinel Fenton catalyst provided by the invention has the advantages of cheap and easily-obtained raw materials, simple preparation process and wide application range.)

1. A preparation method of a nonmetal modified nickel-iron spinel Fenton catalyst is characterized by comprising the following steps:

a. preparing thermal stripping polymer carbon nitride.

b. And dispersing the thermal release polymer carbon nitride in ethanol for ultrasonic treatment to obtain a solution A.

c. And dissolving nickel nitrate hexahydrate and ferric nitrate nonahydrate in ethanol to obtain a solution B. And slowly adding the solution A into the solution B to obtain a mixed solution C.

d. The pH of the solution C was adjusted using 6mol/L NaOH solution to obtain a solution D.

e. And D, putting the solution D obtained in the step D into a hydrothermal kettle with polytetrafluoroethylene as a lining, and carrying out hydrothermal treatment for 10-36 h at the temperature of 100-250 ℃, carrying out suction filtration, and carrying out vacuum drying.

2. The preparation method of the nonmetal modified nickel ferrite Fenton catalyst according to claim 1, which is characterized by comprising the following steps: the preparation method of the thermal release polymer carbon nitride in the step a comprises the following steps: placing dicyandiamide into a crucible, placing the crucible into a muffle furnace, roasting for 2-6 h at 400-600 ℃, heating up at 2.3 ℃/min, grinding, dispersing in deionized water, performing ultrasonic treatment for 60min, performing suction filtration, and drying. And (3) roasting for 2-8 h at 400-600 ℃ for thermal etching, wherein the temperature rise program is 10 ℃/min, and the obtained product is thermal stripping polymer carbon nitride.

3. The preparation method of the nonmetal modified nickel ferrite Fenton catalyst according to claim 1, which is characterized by comprising the following steps: the molar ratio of the thermal stripping polymer carbon nitride to the ethanol in the step b is 1: 200-1000.

4. The preparation method of the nonmetal modified nickel ferrite Fenton catalyst according to claim 1, which is characterized by comprising the following steps: in the step c, the molar ratio of nickel nitrate to ethanol is 1: 200-400, and the molar ratio of ferric nitrate to ethanol is 1:50 to 200.

5. The preparation method of the nonmetal modified nickel hercynite fenton catalyst according to claim 1, is characterized in that: and d, adjusting the pH value of the solution C in the step d to be 11-13.

6. The preparation method of the nonmetal modified nickel ferrite Fenton catalyst according to claim 1, which is characterized by comprising the following steps: the water heating time in the step e is 15-30 hours, and the temperature is 120-200 ℃.

Technical Field

The invention belongs to the field of environment-friendly materials, and particularly relates to a preparation method of a nonmetal modified nickel-iron spinel Fenton catalyst.

Background

In the field of advanced oxidation technologies (AOPs), the homogeneous Fenton technology is one of the main technologies for treating industrial wastewater at present, and has already occupied an important position in the field of sewage treatment. However, the homogeneous Fenton method requires a large amount of Fenton reagents, mainly Fe, in the wastewater treatment process²⁺And H₂O₂And H is₂O₂Easy decomposition and high preparation, transportation and storage costs, and restricts the application of homogeneous Fenton. By Fe in a heterogeneous Fenton catalytic system²⁺And H₂O₂The generation of hydroxyl radicals by the reaction is the most central and efficient step in the whole pollutant degradation reaction process. However, in Fe²⁺During regeneration, a portion of H₂O₂Can act as an electron donor and eventually follow O₂And superoxide radical (O)₂ ^-) And the formation and decomposition of hydrogen peroxide reduce the utilization rate of hydrogen peroxide. Research proves that the ultraviolet light or visible light and the Fenton oxidation technology are combined to utilize light to excite the chemical reaction of the Fenton reagent so as to generate more hydroxyl radicals and increase H₂O₂Utilization ratio of (2) and Fe²⁺Thereby degrading the pollutants more effectively. However, photo-fenton, a new advanced oxidation technology, still has the outstanding problems of high running cost, poor catalyst stability, strong ultraviolet dependence, and the like. Therefore, the development of a high-efficiency and stable photo-Fenton catalyst is of great significance.

The invention content is as follows:

the invention aims to provide a preparation method of a nonmetal modified nickel-iron spinel Fenton catalyst with high catalytic activity and good stability, which is characterized by comprising the following steps:

a. preparing thermal stripping polymer carbon nitride.

b. And dispersing the thermal release polymer carbon nitride in ethanol for ultrasonic treatment to obtain a solution A.

c. And dissolving nickel nitrate hexahydrate and ferric nitrate nonahydrate in ethanol to obtain a solution B. And slowly adding the solution A into the solution B to obtain a mixed solution C.

d. The pH of the solution C was adjusted using 6mol/L NaOH solution to obtain a solution D.

e. And D, putting the solution D obtained in the step D into a hydrothermal kettle with polytetrafluoroethylene as a lining, and carrying out hydrothermal treatment for 10-36 h at the temperature of 100-250 ℃, carrying out suction filtration, and carrying out vacuum drying.

Further, the preparation method of the thermal release polymer carbon nitride in the step a comprises the following steps: placing dicyandiamide into a crucible, placing the crucible into a muffle furnace, roasting for 2-6 h at 400-600 ℃, heating up at 2.3 ℃/min, grinding, dispersing in deionized water, performing ultrasonic treatment for 60min, performing suction filtration, and drying. And (3) roasting for 2-8 h at 400-600 ℃ for thermal etching, wherein the temperature rise program is 10 ℃/min, and the obtained product is thermal stripping polymer carbon nitride.

Further, the molar ratio of the thermal stripping polymer carbon nitride to the ethanol in the step b is 1: 200-1000.

Furthermore, in the step c, the molar ratio of the nickel nitrate to the ethanol is 1: 200-400, and the molar ratio of the ferric nitrate to the ethanol is 1: 50-200.

Further, the pH value of the solution C in the step d is adjusted to 11-13

Furthermore, the water heating time in the step e is 15-30 hours, and the temperature is 120-200 ℃.

Detailed Description

The present invention is further described in the following examples, but the technical content described in the examples is illustrative and not restrictive, and the scope of the present invention should not be limited thereby.

Example 1

a. Placing 5.0g of dicyandiamide in a crucible, placing in a muffle furnace, roasting at 400 ℃ for 6h, heating at 2.3 ℃/min, grinding, dispersing in deionized water, performing ultrasonic treatment for 60min, performing suction filtration, and drying. And (3) roasting for 8 hours at 600 ℃ for thermal etching, wherein the temperature rise program is 10 ℃/min, and the obtained product is thermal stripping polymer carbon nitride.

b. 329.6mg of thermal release polymer carbon nitride is dispersed in 60mL of ethanol for ultrasonic treatment, and the molar ratio of the thermal release polymer carbon nitride to the ethanol is 1: 200. Solution a was obtained.

c. 247.0mg of nickel nitrate hexahydrate and 1373.6mg of ferric nitrate nonahydrate were dissolved in 60mL of ethanol to obtain a solution B. And slowly adding the solution A into the solution B to obtain a mixed solution C. Wherein the molar ratio of the nickel nitrate to the ethanol is 1:200, and the molar ratio of the ferric nitrate to the ethanol is 1: 50.

d. The pH of the solution C was adjusted to 11 using 6mol/L NaOH solution to give a solution D.

e. Putting the solution D into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 10 hours at the temperature of 250 ℃, carrying out suction filtration, and carrying out vacuum drying.

The performance of the nonmetal modified nickel-iron spinel Fenton catalyst is evaluated by adopting a PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofele company, 100ml of paracetamol (acetaminophen) aqueous solution with the concentration of 20mg/L is taken as a target pollutant, 50mg of the prepared catalyst and 0.5ml of 30% hydrogen peroxide are taken, and T90 (the time for the paracetamol conversion rate to be more than 90%) is 30min under the irradiation of the xenon lamp. The catalyst has better catalytic activity for catalyzing and degrading paracetamol.

Example 2

a. Placing 5.0g of dicyandiamide into a crucible, placing the crucible into a muffle furnace, roasting for 4h at 550 ℃, heating up at 2.3 ℃/min, grinding, dispersing in deionized water, performing ultrasonic treatment for 60min, performing suction filtration, and drying. And (3) roasting for 4h at 550 ℃ for thermal etching, wherein the temperature rise program is 10 ℃/min, and the obtained product is thermal stripping polymer carbon nitride.

b. 200mg of thermal release polymer carbon nitride is dispersed in 60mL of ethanol for ultrasonic treatment, and the molar ratio of the thermal release polymer carbon nitride to the ethanol is 1: 510. Solution a was obtained.

c. 145.4mg of nickel nitrate hexahydrate and 404.0mg of ferric nitrate nonahydrate were dissolved in 10mL of ethanol to obtain a solution B. And slowly adding the solution A into the solution B to obtain a mixed solution C. Wherein the molar ratio of the nickel nitrate to the ethanol is 1:340, and the molar ratio of the ferric nitrate to the ethanol is 1: 170.

d. The pH of the solution C was adjusted to 13 using 6mol/L NaOH solution to obtain a solution D.

e. And (3) putting the solution D into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 20 hours at the temperature of 180 ℃, performing suction filtration, and performing vacuum drying.

The performance of the nonmetal modified nickel-iron spinel Fenton catalyst is evaluated by adopting a PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofely company, 100ml of 20mg/L phenol aqueous solution is taken as a target pollutant, 50mg of the prepared catalyst and 0.5ml of 30% hydrogen peroxide are taken, and T90 (the time for the conversion rate of phenol to be more than 90%) is 30min under the irradiation of the xenon lamp. The catalyst has better catalytic activity for catalyzing and degrading phenol.

Example 3

a. Placing 5.0g of dicyandiamide into a crucible, placing the crucible into a muffle furnace, roasting for 3h at 500 ℃, heating up at the temperature of 2.3 ℃/min, grinding, dispersing in deionized water, performing ultrasonic treatment for 60min, performing suction filtration, and drying. And (3) roasting for 6h at 450 ℃ for thermal etching, wherein the temperature rise program is 10 ℃/min, and the obtained product is thermal stripping polymer carbon nitride.

b. 94.8mg of thermal release polymer carbon nitride is dispersed in 60mL of ethanol for ultrasonic treatment, and the molar ratio of the thermal release polymer carbon nitride to the ethanol is 1: 1000. Solution a was obtained.

c. 123.6mg of nickel nitrate hexahydrate and 343.4mg of ferric nitrate nonahydrate were dissolved in 10mL of ethanol to obtain a solution B. And slowly adding the solution A into the solution B to obtain a mixed solution C. Wherein the molar ratio of the nickel nitrate to the ethanol is 1:400, and the molar ratio of the ferric nitrate to the ethanol is 1: 200.

d. The pH of the solution C was adjusted to 12 using 6mol/L NaOH solution to give a solution D.

e. Putting the solution D into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 36 hours at the temperature of 120 ℃, performing suction filtration, and performing vacuum drying.

The performance of the nonmetal modified nickel-iron spinel Fenton catalyst is evaluated by adopting a PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofele company, 100ml of paracetamol (acetaminophen) aqueous solution with the concentration of 20mg/L is taken as a target pollutant, 50mg of the prepared catalyst and 0.5ml of 30% hydrogen peroxide are taken, and T90 (the time for the paracetamol conversion rate to be more than 90%) is 45min under the irradiation of the xenon lamp. The catalyst has better catalytic activity for catalyzing and degrading paracetamol.

Example 4

a. Placing 5.0g of dicyandiamide into a crucible, placing the crucible into a muffle furnace, roasting for 2h at 500 ℃, heating at the temperature of 2.3 ℃/min, grinding, dispersing in deionized water, performing ultrasonic treatment for 60min, performing suction filtration, and drying. And (3) roasting for 5h at 550 ℃ for thermal etching, wherein the temperature rise program is 10 ℃/min, and the obtained product is thermal stripping polymer carbon nitride.

b. 118.5mg of thermal release polymer carbon nitride is dispersed in 60mL of ethanol for ultrasonic treatment, and the molar ratio of the thermal release polymer carbon nitride to the ethanol is 1: 800. Solution a was obtained.

c. 183.1mg of nickel nitrate hexahydrate and 686.8mg of iron nitrate nonahydrate were dissolved in 60mL of ethanol to obtain a solution B. And slowly adding the solution A into the solution B to obtain a mixed solution C. Wherein the molar ratio of the nickel nitrate to the ethanol is 1:270, and the molar ratio of the ferric nitrate to the ethanol is 1: 100.

d. The pH of the solution C was adjusted to 13 using 6mol/L NaOH solution to obtain a solution D.

e. And (3) putting the solution D into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 20 hours at the temperature of 250 ℃, performing suction filtration, and performing vacuum drying.

The performance of the nonmetal modified nickel-iron spinel Fenton catalyst is evaluated by adopting a PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofele company, 100ml of paracetamol (acetaminophen) aqueous solution with the concentration of 20mg/L is taken as a target pollutant, 50mg of the prepared catalyst and 0.5ml of 30% hydrogen peroxide are taken, and T90 (the time for the paracetamol conversion rate to be more than 90%) is 60min under the irradiation of the xenon lamp. The catalyst has better catalytic activity for catalyzing and degrading paracetamol.

Example 5

a. Placing 5.0g of dicyandiamide into a crucible, placing the crucible into a muffle furnace, roasting for 4h at 550 ℃, heating up at 2.3 ℃/min, grinding, dispersing in deionized water, performing ultrasonic treatment for 60min, performing suction filtration, and drying. And (3) roasting for 5 hours at 600 ℃ for thermal etching, wherein the temperature rise program is 10 ℃/min, and the obtained product is thermal stripping polymer carbon nitride.

b. 236.9mg of thermal release polymer carbon nitride is dispersed in 60mL of ethanol for ultrasonic treatment, and the molar ratio of the thermal release polymer carbon nitride to the ethanol is 1: 400. Solution a was obtained.

c. 141.2mg of nickel nitrate hexahydrate and 457.9mg of ferric nitrate nonahydrate were dissolved in 10mL of ethanol to obtain solution B. And slowly adding the solution A into the solution B to obtain a mixed solution C. Wherein the molar ratio of the nickel nitrate to the ethanol is 1:350, and the molar ratio of the ferric nitrate to the ethanol is 1: 150.

d. The pH of the solution C was adjusted to 12 using 6mol/L NaOH solution to give a solution D.

e. Putting the solution D into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 18 hours at the temperature of 200 ℃, carrying out suction filtration, and carrying out vacuum drying.

The performance of the nonmetal modified nickel-iron spinel Fenton catalyst is evaluated by adopting a PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofele company, 100ml of paracetamol (acetaminophen) aqueous solution with the concentration of 20mg/L is taken as a target pollutant, 50mg of the prepared catalyst and 0.5ml of 30% hydrogen peroxide are taken, and T90 (the time for the paracetamol conversion rate to be more than 90%) is 35min under the irradiation of the xenon lamp. The catalyst has better catalytic activity for catalyzing and degrading paracetamol.