CN109513441A - A kind of preparation of the solid phase coated bimetallic catalyst applied to heterogeneous Fenton - Google Patents
A kind of preparation of the solid phase coated bimetallic catalyst applied to heterogeneous Fenton Download PDFInfo
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- CN109513441A CN109513441A CN201811340127.2A CN201811340127A CN109513441A CN 109513441 A CN109513441 A CN 109513441A CN 201811340127 A CN201811340127 A CN 201811340127A CN 109513441 A CN109513441 A CN 109513441A
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- active carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007790 solid phase Substances 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000002363 herbicidal effect Effects 0.000 claims description 2
- 239000004009 herbicide Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 238000002407 reforming Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 10
- 239000005510 Diuron Substances 0.000 description 10
- 238000002386 leaching Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/33—
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
A kind of preparation of the solid phase coated bimetallic catalyst applied to heterogeneous Fenton, belongs to wastewater treatment technology of advanced oxidation field.The present invention is using granular active carbon as carrier, by impregnating absorption in the mixed solution of molysite and mantoquita, bimetallic catalyst is prepared in calcining under a nitrogen atmosphere, and package processing is carried out to it using polytetrafluoroethylene (PTFE) at it, the catalyst of method preparation is high-efficient, it is easily recycled, there is lower iron ion dissolution rate relative to single-metal reforming catalyst.
Description
Technical field
The present invention relates to wastewater treatment technology of advanced oxidation fields, and in particular to a kind of preparation of coated bimetallic catalyst
Method.
Background technique
Traditional treating organic waste water by Fenton method needs to add Fe during the reaction2+And H2O2, reagent to add process multiple
It is miscellaneous, and due to H2O2With unstability, the risk that accident occurs in reaction process is increased.In addition, during Fenton's reaction
Fe2+Fe can be generated3+, and a large amount of iron containing sludge is generated under the conditions of slightly higher pH, secondary pollution is caused, subsequent processing is increased
Cost.
Heterogeneous electricity Fenton oxidation method overcomes Fenton reagent in traditional Fenton process and adds many and diverse, and applicable pH range is narrow, holds
The disadvantages of being also easy to produce iron containing sludge gradually becomes the research hotspot in high-level oxidation technology, utilizes heterogeneous electric Fenton oxidation method
Efficiently go the core of organic contamination in water removal first is that the stable catalyst of preparation high catalytic efficiency, performance.It is solid phase supported to urge
The preparation of agent and its constructed out-phase electricity Fenton oxidation system, have widened the scope of application of electric Fenton oxidation technology.
Active carbon particle is common material in sewage disposal process, and there is stable chemical property, gap abundant to tie
Structure and higher specific surface area.There are carrier of the present invention using active carbon particle as bimetallic catalyst raw material easily to obtain,
The advantages of being easy large scale preparation, can preferably realize the recycling of heterogeneous catalysis in actual use.It is heterogeneous to urge
Agent due to the leaching of active component and inactivation, substantially reduces the service life of heterogeneous catalysis in use.This
Invention is wrapped up using the heterogeneous fenton catalyst of bimetallic of the polytetrafluoroethylene (PTFE) to preparation, and the structure for improving catalyst is strong
Degree, limits the leaching of active component in use process, slows down the inactivation of the heterogeneous fenton catalyst of bimetallic, effectively extends
Its service life.
Summary of the invention
The purpose of the present invention is intended to study a kind of using active carbon as the efficient and cheap of carrier, performance stabilization, long service life
Heterogeneous bimetallic fenton catalyst, and by package processing reduce iron ion leaching rate
To achieve the above object, the present invention uses following technological means.
A kind of preparation of the solid phase coated bimetallic catalyst applied to heterogeneous Fenton, the specific steps are as follows:
(1) granular active carbon by partial size in 3-5mm is successively embathed with pure water and acetone, removes the organic matter of attachment；So
It is put into air dry oven and is dried for standby with the clean acetone of ultrapure water again afterwards；
(2) at room temperature, the active carbon after a certain amount of cleaning is weighed, ferric nitrate, copper nitrate and nitric acid are placed in
In mixed solution, 4-16h of soaking at room temperature, taking-up is put into air dry oven at 40 DEG C-60 DEG C dry；
(3) active carbon in step (2) is put into Muffle furnace under nitrogen protection, is calcined at 500 DEG C -700 DEG C
0.5h-2h；
(4) by the active carbon in step (3) be immersed in mass percent be 1%-20% (preferably 5%-20%) poly- four
In vinyl fluoride aqueous solution, 15min-60min is impregnated, separation of solid and liquid, which is placed in 60 DEG C -80 DEG C of vacuum oven, dries.It completes
The preparation of coated catalytic agent.
The molar ratio of ferric nitrate and copper nitrate is (4-12): 1, preferably 10:1 in step (2)；
The concentration of nitric acid is 0.1-4mol/L in mixed solution in step (2), and the concentration of ferric nitrate is 0.1-1.2mol/L.
Electrochemicial oxidation using solid phase coated bimetallic catalyst prepared by the present invention, for herbicide in water
With excellent performance.
Compared with prior art, the present invention has following excellent effect
1. the present invention is using active carbon as catalyst carrier, one side active carbon is cheap and easy to get, and absorption property is good, can make
A large amount of metal ion is adsorbed during standby, is widely used material in water process；On the other hand, the addition of copper ion promotes
Fe3+With Fe2+Mutually convert, Fenton's reaction can be catalyzed preferably and independently, improve the catalytic capability of catalyst.
2. carrying out package processing to bimetallic catalyst using polytetrafluoroethylene (PTFE), inactivation and the leaching of active component are slowed down
Process, while the addition of copper ion can further slow down the leaching of iron ion in catalyst.
Detailed description of the invention
Fig. 1 is the XPS result figure for the coated bimetallic catalyst that the preparation of embodiment 1 is completed.
Wherein a corresponds to Fe, and b corresponds to Cu.
Fig. 2 is the XRD result figure for the coated bimetallic catalyst that the preparation of embodiment 1 is completed.
Fig. 3 is the influence that the copper and iron element of different proportion of the embodiment of the present invention degrades to diuron, and ordinate is corresponding to be
The ratio of the relatively primitive diuron of diuron concentration in degradation process in solution.
Specific embodiment
It is illustrated in the following with reference to the drawings and specific embodiments, but the present invention is not limited to following embodiment.
Embodiment 1
(1) active carbon particle by partial size in 3-5mm is successively embathed with ultrapure water and acetone, removes the organic matter of attachment；
Then it is put into air dry oven and is dried for standby with the clean acetone of ultrapure water again.
(2) at room temperature, the active carbon after a certain amount of cleaning, ferric nitrate, the nitre of iron copper molar ratio 10:1 are weighed
The mixed solution (ferric nitrate, copper nitrate, concentration of nitric acid are 1mol/L, 0.1mol/L, 2mol/L) of sour copper and nitric acid, puts
Enter and impregnate 12h in thermostat water bath, taking-up is put into air dry oven dries at 40 DEG C.
(3) active carbon in step (2) is put into Muffle furnace in nitrogen protection down toward 600 DEG C of calcining at constant temperature 0.5h, certainly
It is taken out after being so cooled to room temperature.
(4) by the active carbon in step (3) in 10% polytetrafluoroethylsolution solution, 0.5h is impregnated, is separated by solid-liquid separation postposition
It is dried in 60 DEG C of vacuum oven.Complete coated catalytic agent preparation.
(5) the coated catalytic agent of above-mentioned preparation is applied in heterogeneous electric Fenton-like system, handles diuron waste water, answers
The catalyst degradation 300mL concentration prepared in fashion described above is the diuron waste water of 10mg/L, anhydrous sodium sulfate as electrolyte,
Concentration is 0.05M.Catalyst amounts are 2g, and constant-current supply provides electric current 100mA, and reaction solution is adjusted to pH=3.0,25min
When, diuron is up to degradable, and the iron ion the amount of dissolution in reaction solution is lower than 0.2mg/L after reaction.
Embodiment 2-5
With embodiment 1, but in step (4), iron copper molar ratio successively becomes 4:1,6:1,8:1,12 to specific preparation process:
1。
The coated bimetallic catalyst of above-mentioned preparation is applied in heterogeneous electric Fenton-like system, processing diuron is useless
Water, treatment conditions are with embodiment 1, and diuron is up to degradable, and the iron ion the amount of dissolution in reaction solution is successively after reaction
For 0.7,0.6,0.4,0.3mg/L.
Comparative example 1
(1) active carbon particle by partial size in 3-5mm is successively embathed with ultrapure water and acetone, removes the organic matter of attachment；
Then it is put into air dry oven and is dried for standby with the clean acetone of ultrapure water again.
(2) at room temperature, by the active carbon after cleaning, the mixing of the ferric nitrate and nitric acid of excessive 0.1mol/L
It in solution, is placed in thermostat water bath and impregnates 12h, taking-up is put into air dry oven dries at 40 DEG C.
(3) active carbon in step (2) is put into Muffle furnace under nitrogen protection in 600 DEG C of calcining at constant temperature 0.5h, certainly
It is taken out after being so cooled to room temperature.
(4) by the active carbon in step (3) in 10% polytetrafluoroethylsolution solution, 0.5h is impregnated, is separated by solid-liquid separation postposition
It is dried in 60 DEG C of vacuum oven.Complete the preparation of coated single-metal reforming catalyst.
(5) the coated single-metal reforming catalyst of above-mentioned preparation is applied in heterogeneous electric Fenton-like system, handles diuron
Waste water, treatment conditions with embodiment 1, diuron just can reach after the 30min that degrades it is degradable, after reaction in reaction solution
Iron ion the amount of dissolution be 0.8mg/L.
Claims (8)
1. a kind of preparation method of the solid phase coated bimetallic catalyst applied to heterogeneous Fenton, which is characterized in that including
Following steps:
(1) granular active carbon by partial size in 3-5mm is successively embathed with pure water and acetone, removes the organic matter of attachment；Then again
With the clean acetone of ultrapure water, it is put into air dry oven and is dried for standby；
(2) at room temperature, the active carbon after a certain amount of cleaning is weighed, the mixing of ferric nitrate, copper nitrate and nitric acid is placed in
In solution, 4-16h of soaking at room temperature, taking-up is put into air dry oven at 40 DEG C-60 DEG C dry；
(3) active carbon in step (2) is put into Muffle furnace under nitrogen protection, calcines 0.5h- at 500 DEG C -700 DEG C
2h；
(4) active carbon in step (3) is immersed in the polytetrafluoroethyl-ne aqueous solution that mass percent is 1%-20%, dipping
15min-60min, separation of solid and liquid, which is placed in 60 DEG C -80 DEG C of vacuum oven, dries.Complete the preparation of coated catalytic agent.
2. according to the method for claim 1, which is characterized in that the molar ratio of ferric nitrate and copper nitrate is (4- in step (2)
12):1。
3. according to the method for claim 1, which is characterized in that the molar ratio 10:1 of ferric nitrate and copper nitrate in step (2).
4. according to the method for claim 1, which is characterized in that the concentration of nitric acid is 0.1- in mixed solution in step (2)
4mol/L, the concentration of ferric nitrate are 0.1-1.2mol/L.
5. according to the method for claim 1, which is characterized in that the concentration of nitric acid is 2- in mixed solution in step (2)
4mol/L, the concentration of ferric nitrate are 0.4-1.2mol/L.
6. according to the method for claim 1, which is characterized in that polytetrafluoroethylene (PTFE) concentration is 5%-20% in step (4).
7. the solid phase coated bimetallic catalyst being prepared according to method described in any one of claims 1-6.
8. according to the application for the solid phase coated bimetallic catalyst that method described in any one of claims 1-6 is prepared,
Heterogeneous Fenton electrochemicial oxidation for herbicide in water.
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| CN201811340127.2A CN109513441A (en) | 2018-11-12 | 2018-11-12 | A kind of preparation of the solid phase coated bimetallic catalyst applied to heterogeneous Fenton |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811340127.2A CN109513441A (en) | 2018-11-12 | 2018-11-12 | A kind of preparation of the solid phase coated bimetallic catalyst applied to heterogeneous Fenton |
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| CN109513441A true CN109513441A (en) | 2019-03-26 |
Family
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| CN115518614A (en) * | 2022-07-12 | 2022-12-27 | 山东大学 | Iron-copper bimetal modified biochar material and preparation method and application thereof |
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| CN111054341A (en) * | 2020-01-10 | 2020-04-24 | 北京工业大学 | Preparation method and application of bimetal oxide loaded activated carbon fiber composite electrode |
| CN111097415A (en) * | 2020-01-10 | 2020-05-05 | 北京工业大学 | Preparation of activated carbon supported catalyst applied to heterogeneous electro-Fenton degradation of organic wastewater |
| CN111097415B (en) * | 2020-01-10 | 2022-09-30 | 北京工业大学 | Preparation of activated carbon supported catalyst applied to heterogeneous electro-Fenton degradation of organic wastewater |
| CN113209968A (en) * | 2021-04-27 | 2021-08-06 | 北京工业大学 | Preparation method and application of magnetic copper-iron bimetallic biomass carbon microspheres |
| CN113209968B (en) * | 2021-04-27 | 2023-06-02 | 北京工业大学 | Preparation method and application of magnetic copper-iron bimetallic biomass charcoal microsphere |
| CN114620826A (en) * | 2022-03-28 | 2022-06-14 | 中化学朗正环保科技有限公司 | Iron-carbon coupled biological particle carrier material for wastewater denitrification and preparation method thereof |
| CN114620826B (en) * | 2022-03-28 | 2024-04-02 | 中化学朗正环保科技有限公司 | Iron-carbon coupled biological particle carrier material for wastewater denitrification and preparation method thereof |
| CN115518614A (en) * | 2022-07-12 | 2022-12-27 | 山东大学 | Iron-copper bimetal modified biochar material and preparation method and application thereof |
| CN115155671A (en) * | 2022-08-02 | 2022-10-11 | 江苏省环境工程技术有限公司 | Functional multiphase Fenton catalytic material and preparation method thereof |
| CN115155671B (en) * | 2022-08-02 | 2023-09-26 | 江苏省环境工程技术有限公司 | Functional multiphase Fenton catalytic material and preparation method thereof |
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