CN111111673B - Prussian blue modified CeO 2 Novel high-efficiency heterogeneous Fenton catalyst - Google Patents
Prussian blue modified CeO 2 Novel high-efficiency heterogeneous Fenton catalyst Download PDFInfo
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- CN111111673B CN111111673B CN202010015551.0A CN202010015551A CN111111673B CN 111111673 B CN111111673 B CN 111111673B CN 202010015551 A CN202010015551 A CN 202010015551A CN 111111673 B CN111111673 B CN 111111673B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses Prussian blue modified CeO 2 The novel high-efficiency heterogeneous Fenton catalyst has the catalyst carrier of cerium dioxide and the iron source of Prussian blue. Accordingly, the inventors have also established a process for the preparation of the catalyst. Experiments show that the obtained novel efficient heterogeneous Fenton catalyst has higher Fenton catalytic oxidation capacity and stability on norfloxacin in water within the pH range of 2-9. The novel efficient heterogeneous Fenton catalyst disclosed by the invention is simple and easy to prepare, has the characteristics of high catalytic efficiency, low iron ion elution amount, good stability and wide pH range (2-9), not only improves the catalytic efficiency of the catalyst, but also widens the application range of reaction pH, has long service life, and can be used for advanced oxidation of water treatment, such as degradation of organic pollutants such as antibiotics and the like.
Description
Technical Field
The invention belongs to the technical field of Fenton catalysts, and particularly relates to Prussian blue modified CeO 2 The novel high-efficiency heterogeneous Fenton catalyst.
Background
The Fenton reaction has received wide attention from environmental workers due to the advantages of high treatment efficiency, easy operation, simple equipment and the like. However, the traditional homogeneous Fenton reaction has the problems of low reaction pH, iron mud generated after the reaction and the like, and the application of the traditional homogeneous Fenton reaction in wastewater treatment is limited. The heterogeneous Fenton reaction system, namely the catalyst exists in a solid state, has the advantages of wide pH application range, good stability and the like, can be separated from the wastewater, greatly simplifies the treatment process, and solves the problem of the homogeneous Fenton reaction in the operation process. Therefore, the preparation of the heterogeneous Fenton catalyst which has wide pH application range, high efficiency and stability is of great significance.
CeO 2 Belongs to lanthanide series oxide, has cubic fluorite structure and higher oxygen vacancy, and has CeO under the condition of oxidation reduction 2 Can pass through Ce 3+ /Ce 4+ The oxygen is stored and released by interconversion, and the oxygen storage material has wide application in the field of catalysis, namely being used as a carrier, a catalyst and an auxiliary agent. CeO (CeO) 2 Oxygen vacancies in the molecular structure may directly donate H 2 O 2 Reduction to OH improves the catalytic effect, and researches show that H is caused by the existence of oxygen holes 2 O 2 Is more easily coated with CeO 2 And adsorption is favorable for Fenton reaction. At CeO 2 In the catalytic process, ce 3+ Is oxidized to Ce 4+ The process of (2) is extremely easy to occur. In contrast, ce 4+ Reduction to Ce 3+ The process of (a) is much more difficult. The doping of metal or metal oxide can greatly improve CeO 2 Thereby increasing the reducibility of CeO 2 /H 2 O 2 Catalytic activity of the system.
As typical homogeneous and heterogeneous Fenton catalysts, iron and its oxides have a wide range of applications and research backgrounds. Prussian blue is an inorganic substance, has multiple valence Fe and redox capability, has the property of peroxide mimic enzyme, and can catalyze hydrogen peroxide to oxidize organic substances.
Currently prussian blue modified CeO 2 The literature of the novel high-efficiency heterogeneous Fenton catalyst is rarely reported.
Disclosure of Invention
The invention aims to solve the technical problem of providing Prussian blue modified CeO which is simple and easy to prepare, strong in catalytic oxidation capacity and good in stability 2 The novel high-efficiency heterogeneous Fenton catalyst.
In order to solve the technical problem, the invention adopts the following technical scheme:
prussian blue modified CeO 2 The novel high-efficiency heterogeneous Fenton catalyst has the catalyst carrier of cerium dioxide and the iron source of Prussian blue.
The catalyst consists of a catalyst carrier CeO 2 And iron-containing compound (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O and K 3 Fe(CN) 6 And (4) preparing.
The preparation method of the novel high-efficiency heterogeneous Fenton catalyst is well configured (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, adding K first 3 Fe(CN) 6 Stirring uniformly; then, ceO was added 2 Powder is evenly stirred; and then carrying out suction filtration, drying the solid obtained by filtration, and grinding the solid into powder to obtain the physical supported catalyst.
CeO 2 In such an amount that Prussian Blue (PB) and cerium oxide (CeO) 2 ) The mass ratio of the substances is PB to CeO 2 ＝1:10。
The preparation method is to prepare (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, first adding K 3 Fe(CN) 6 Stirring for 1h in a water bath kettle at 25 ℃; then, ceO was added 2 Stirring the powder for 24 hours at 25 ℃; and then, carrying out suction filtration, putting the filtered solid into an oven, drying for 12h at the temperature of 100 ℃, and fully grinding to obtain the physical supported catalyst.
The preparation method of the novel high-efficiency heterogeneous Fenton catalyst is well configured (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, adding CeO 2 Pulverizing, stirring to obtain (NH) 4 ) 2 Fe(SO 4 ) 2 -CeO 2 Suspending liquid; then, K is added to the suspension 3 Fe(CN) 6 Stirring uniformly; and then carrying out suction filtration, washing, drying the solid obtained by filtration, and grinding the solid into powder to obtain the chemical type supported catalyst.
CeO 2 The powder is added in such an amount that [ (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O]:[CeO 2 ]1, 100, 1, 20 or 1; k 3 Fe(CN) 6 In such an amount that [ (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O]:[K 3 Fe(CN) 6 ]＝3:2。
The preparation method is to prepare (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, adding CeO 2 Stirring the powder in water bath at 25 deg.C for 1 hr to obtain (NH) 4 ) 2 Fe(SO 4 ) 2 -CeO 2 Suspending liquid; subsequently, K is added to the suspension 3 Fe(CN) 6 Stirring for 24 hours; and then carrying out suction filtration, washing, putting the solid obtained by filtration into a drying oven, drying for 12 hours at the temperature of 100 ℃, and fully grinding to obtain the chemical supported catalyst.
The novel efficient heterogeneous Fenton catalyst is applied to catalytic degradation of organic pollutants.
The catalytic degradation is carried out in the pH range of 2-9, and the organic pollutant is norfloxacin.
Taking into account Prussian blue and CeO 2 The Fenton catalytic effect is achieved, and the coupling of the two can enhance the Ce 3+ /Ce 4+ With Fe 3+ /Fe 2+ The electron transfer efficiency is improved synergistically 2 The catalytic efficiency of (a). Accordingly, the inventor develops Prussian blue modified CeO 2 The novel high-efficiency heterogeneous Fenton catalyst has the catalyst carrier of cerium dioxide and the iron source of Prussian blue. Accordingly, the inventors have also established a process for the preparation of the catalyst. Experiments show that the obtained novel efficient heterogeneous Fenton catalyst has higher Fenton catalytic oxidation capacity and stability on norfloxacin in water within the pH range of 2-9. Because of CeO 2 Has a special cubic fluorite structure and higher oxygen vacancy (superior oxygen storage and release functions), ce 3+ /Ce 4+ The mutual conversion of the two components, the properties of multi-valence state Fe in the Prussian blue, oxidation reduction capability and peroxide mimic enzyme thereof are coupled to cooperatively catalyze H 2 O 2 Thereby realizing the high-efficiency and stable degradation of organic matters.
Compared with the problems of low reaction pH (2-3), iron mud generated after the reaction and the like existing in the traditional homogeneous Fenton reaction, the Prussian blue modified CeO of the invention 2 The novel high-efficiency heterogeneous Fenton catalyst is simple and easy to prepare, has the characteristics of high catalytic efficiency, low iron ion elution amount, good stability and wide pH range (2-9), not only improves the catalytic efficiency of the catalyst, but also widens the application of reaction pHThe range is wide, the service life is long, and the catalyst can be used for water treatment advanced oxidation, such as degradation of organic pollutants such as antibiotics and the like.
Drawings
FIG. 1 shows Prussian blue modified CeO according to the present invention 2 The synthesis schematic diagram of the novel high-efficiency heterogeneous Fenton catalyst is shown.
Detailed Description
Example 1 preparation of physically Supported catalyst
Weighing 294mg (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 Adding 200mL of deionized water into the conical flask, and stirring and dissolving by using a glass rod; weighing 164mg K 3 Fe(CN) 6 Adding into a conical flask, and stirring for 1h in a water bath kettle at 25 ℃; adding weighed CeO 2 1480mg, stirred for 24h. And after stirring, carrying out suction filtration, and putting the filtered solid into an oven to be dried for 12 hours at the temperature of 100 ℃. After drying, grinding the mixture into powder by using a mortar to obtain the physical supported catalyst.
Example 2 preparation of chemically Supported catalyst
29.4mg, 73.5mg, 147mg, 294mg (NH) were weighed respectively 4 ) 2 Fe(SO 4 ) 2 ·6H 2 Putting O into different conical flasks, adding 200mL of deionized water respectively, stirring and dissolving by using a glass rod, and adding weighed CeO into each conical flask 2 1480mg, stirred in a 25 ℃ water bath for 1h; weighing 16.4mg, 41mg, 82mg and 164mg K 3 Fe(CN) 6 Respectively adding the mixture into the conical flasks, and stirring for 24 hours; and after stirring, carrying out suction filtration, and putting the filtered solid into an oven to be dried for 12 hours at the temperature of 100 ℃. Drying, grinding into powder with mortar to obtain PB: ceO 2 1, 100, 1.
Example 3 detection of catalytic degradation Capacity
200mL norfloxacin solution with the concentration of 20mg/L are put into a 250mL conical flask, and 0.6g L norfloxacin solution is added into the conical flask respectively -1 Equal amount of pure CeO 2 Powder and physical-supported Prussian blue modified CeO 2 Heterogeneous Fenton catalyst (PB + CeO) 2 ) Modified with chemically supported Prussian blueCeO 2 Heterogeneous Fenton catalyst (PB/CeO) 2 ) Adjusting pH =4, placing in a 30 deg.C constant temperature water bath oscillator, adsorbing and balancing for 1 hr, respectively adding 2ml of 6% H 2 O 2 The Fenton reaction was carried out for 1 hour. The result shows that the catalytic oxidative degradation efficiency of norfloxacin meets PB/CeO 2 (95.2％)>PB+CeO 2 (75.8％) >CeO 2 (8.6％)。
200mL of norfloxacin solution with the concentration of 20mg/L are taken and put into a 250mL conical flask, and 0.6g L of norfloxacin solution is added into the 250mL conical flask respectively -1 CeO (PB) of 2 1, 100, 1, 20, 1 2 Heterogeneous Fenton catalyst (PB/CeO) 2 ) Adjusting pH =4, placing in a 30 ℃ constant temperature water bath oscillator, adsorbing and balancing for 1 hour, and adding 2ml of 6% H 2 O 2 The Fenton reaction was carried out. The results show that norfloxacin is in PB: ceO 2 The degradation rates after 1 hour of reaction were 21.2%,45.7%, 72.5%, and 99.2% under catalysis of = 1.
200mL norfloxacin solution with concentration of 20mg/L is taken in a 250mL conical flask, and 0.6g L is added -1 Chemical load type catalyst (PB: ceO) 2 =1, 10), adjusting pH =2,3,4,5,6,7,8,9, placing in a 30 ℃ constant temperature water bath oscillator, after 1 hour of adsorption equilibrium, adding 2ml of 6% H concentration 2 O 2 The Fenton reaction was carried out. The results show that under the synergistic effect of heterogeneous Fenton catalytic oxidation and oxygen hole catalytic oxidation, the degradation rates of norfloxacin after reaction for 1 hour under the conditions of pH =2,3,4,5,6,7 and 8,9 are respectively 99.2%,96.7%, 92.5%, 93.8%, 94.1%, 95.2%, 95.8% and 96.1%, and the dissolution concentration of iron ions is less than 1mg L -1 The catalyst is recycled for 8 times, and the norfloxacin degradation efficiency is not obviously reduced.
The physical and chemical characteristics of the catalyst are characterized, and the result shows that the Prussian blue chemically modified CeO 2 Because of the addition of Prussian blue, the crystal lattice of cerium dioxide is distorted, the surface holes are increased, and the specific surface area is 2.7383m 2 Increase in g to24.3592m 2 /g。
Claims (8)
1. The high-efficiency heterogeneous Fenton catalyst is characterized by comprising a catalyst carrier CeO 2 And iron-containing compound (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O and K 3 Fe(CN) 6 Is prepared by disposing (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, adding K first 3 Fe(CN) 6 Stirring uniformly; then, ceO was added 2 Powder is evenly stirred; then, carrying out suction filtration, drying the solid obtained by filtering, and grinding the solid into powder to obtain the physical supported catalyst; the CeO 2 The powder is added in such an amount that [ (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O]:[CeO 2 ]1; said K 3 Fe(CN) 6 Is added in such an amount that [ (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O]:[K 3 Fe(CN) 6 ]＝3:2。
2. The method for preparing the high-efficiency heterogeneous Fenton catalyst according to claim 1, wherein: configuration (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, adding K first 3 Fe(CN) 6 Stirring uniformly; then, ceO was added 2 Powder is evenly stirred; then, carrying out suction filtration, drying the solid obtained by filtering, and grinding the solid into powder to obtain a physical supported catalyst; the CeO 2 The powder is added in such an amount that [ (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O]:[CeO 2 ]1.
3. The method of claim 2, wherein: the CeO 2 In such an amount that the ratio of the Prussian blue to the cerium dioxide substance is PB: ceO 2 ＝1:10。
4. The production method according to claim 3, characterized in that: fitting for mixingTo (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, first adding K 3 Fe(CN) 6 Stirring for 1h in a water bath kettle at 25 ℃; then, ceO was added 2 Stirring the powder for 24 hours at 25 ℃; and then, carrying out suction filtration, putting the filtered solid into an oven, drying for 12 hours at the temperature of 100 ℃, and fully grinding to obtain the physically-supported catalyst.
5. The method for preparing the high-efficiency heterogeneous Fenton catalyst according to claim 1, wherein: configuration (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, adding CeO 2 Pulverizing, stirring to obtain (NH) 4 ) 2 Fe(SO 4 ) 2 -CeO 2 Suspending liquid; subsequently, K is added to the suspension 3 Fe(CN) 6 Stirring uniformly; and then carrying out suction filtration, washing, drying and grinding the solid obtained by filtration into powder to obtain the chemical type supported catalyst.
6. The production method according to claim 5, characterized in that: configuration (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution, adding CeO 2 Stirring the powder in water bath at 25 deg.C for 1 hr to obtain (NH) 4 ) 2 Fe(SO 4 ) 2 -CeO 2 Suspending liquid; then, K is added to the suspension 3 Fe(CN) 6 Stirring for 24 hours; and then, carrying out suction filtration, washing, putting the solid obtained by filtration into an oven, drying for 12h at the temperature of 100 ℃, and fully grinding to obtain the chemical type supported catalyst.
7. The high-efficiency heterogeneous Fenton catalyst of claim 1 is applied to catalytic degradation of organic pollutants.
8. Use according to claim 7, characterized in that: the catalytic degradation is carried out in the pH range of 2-9, and the organic pollutant is norfloxacin.
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| CN112958108B (en) * | 2021-02-23 | 2023-12-29 | 华侨大学 | Preparation method and application of magnetic oxygen-deficient nano cage-shaped iron-manganese composite catalyst |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102327773A (en) * | 2011-06-13 | 2012-01-25 | 清华大学 | Preparation method of nano Fe3O4/CeO2 composite material and application thereof |
| CN102962063A (en) * | 2011-09-01 | 2013-03-13 | 苏州科技学院 | Preparation of Prussian blue photo-Fenton catalyst and method for degrading organic pollutant |
| CN107321355A (en) * | 2017-07-25 | 2017-11-07 | 广州润方环保科技有限公司 | A kind of preparation method and application of tetracycline pollution waters restoration material |
| CN110252316A (en) * | 2019-07-04 | 2019-09-20 | 华南理工大学 | Hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst and the preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102327773A (en) * | 2011-06-13 | 2012-01-25 | 清华大学 | Preparation method of nano Fe3O4/CeO2 composite material and application thereof |
| CN102962063A (en) * | 2011-09-01 | 2013-03-13 | 苏州科技学院 | Preparation of Prussian blue photo-Fenton catalyst and method for degrading organic pollutant |
| CN107321355A (en) * | 2017-07-25 | 2017-11-07 | 广州润方环保科技有限公司 | A kind of preparation method and application of tetracycline pollution waters restoration material |
| CN110252316A (en) * | 2019-07-04 | 2019-09-20 | 华南理工大学 | Hollow cerium dioxide micro-balloon load ferrihydrite multiphase-fenton fenton catalyst and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Surface Anchoring Approach for Growth of CeO2 Nanocrystals on Prussian Blue Capsules Enable Superior Lithium Storage;Kai Wang等;《ACS Appl. Mater. Interfaces》;20190816;第11卷;全文 * |
| 介孔CeO2的制备及其性能;赵旭 等;《南昌大学学报（理科版）》;20070430;第31卷(第2期);全文 * |
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