CN110560029B - Graphene-based metal-free Fenton catalyst, and preparation method and application thereof - Google Patents
Graphene-based metal-free Fenton catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000002699 waste material Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000010893 paper waste Substances 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- SBNFWQZLDJGRLK-RTWAWAEBSA-N (1R)-trans-phenothrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 SBNFWQZLDJGRLK-RTWAWAEBSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229960003536 phenothrin Drugs 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 210000003608 fece Anatomy 0.000 claims description 3
- 239000010794 food waste Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229940117955 isoamyl acetate Drugs 0.000 claims description 3
- 229940095102 methyl benzoate Drugs 0.000 claims description 3
- 229960001047 methyl salicylate Drugs 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 13
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 238000005067 remediation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000218628 Ginkgo Species 0.000 description 2
- 235000011201 Ginkgo Nutrition 0.000 description 2
- 235000008100 Ginkgo biloba Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- -1 pericarp Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A graphene-based metal-free Fenton catalyst, a preparation method and application thereof are disclosed, wherein the preparation method comprises the steps of carrying out acid washing treatment on waste; soaking the treated waste in a solution containing an auxiliary agent; and then drying and calcining the obtained product to obtain the graphene-based metal-free Fenton catalyst. The invention has wide sources of wastes and low cost, and greatly reduces the preparation cost of the material; the obtained graphene has catalytic sites by using the aid, and has excellent Fenton catalytic performance; the product has a three-dimensional macroscopic structure and is easy for solid-liquid separation; the preparation method is simple and efficient, and has wide application prospect in environmental pollution treatment.
Description
Technical Field
The invention belongs to the field of research of environmental functional materials, and particularly relates to a graphene-based metal-free Fenton catalyst, and a preparation method and application thereof.
Background
The metal-free fenton catalyst has drawn much attention because it avoids metal leakage of the conventional metal catalyst and has excellent catalytic performance and good environmental compatibility. The development of a low-cost high-yield method to obtain a graphene-based metal-free catalyst will further broaden the application of the metal-free catalyst in environmental management.
Disclosure of Invention
In view of the above, one of the main objectives of the present invention is to provide a graphene-based metal-free fenton catalyst, a preparation method thereof and an application thereof, so as to at least partially solve at least one of the above technical problems.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing a graphene-based metal-free fenton catalyst from waste, comprising the steps of:
1) pickling the waste;
2) soaking the waste treated in the step 1) in a solution containing an auxiliary agent;
3) drying and calcining the product obtained in the step 2) to obtain the graphene-based metal-free Fenton catalyst.
As another aspect of the present invention, there is also provided a graphene-based metal-free fenton catalyst obtained by the above-described preparation method.
As another aspect of the present invention, there is also provided an application of the graphene-based metal-free fenton catalyst in the field of environmental improvement.
Based on the above technical solutions, the graphene-based metal-free fenton catalyst, the preparation method and the application thereof of the present invention have at least one of the following advantages over the prior art:
(1) the waste sources are wide, the cost is low, and the preparation cost of the material is greatly reduced;
(2) the obtained graphene has catalytic sites by using the aid, and has excellent Fenton catalytic performance;
(3) the product has a three-dimensional macroscopic structure and is easy for solid-liquid separation;
(4) the preparation method is simple and efficient, and has wide application prospect in environmental pollution treatment.
Drawings
Fig. 1 is a photo-graph of a graphene-based metal-free fenton catalyst in example 1 of the present invention;
fig. 2 is a scanning electron microscope image of the graphene-based metal-free fenton catalyst in example 1 of the present invention;
fig. 3 is a graph showing the degradation effect of the graphene-based metal-free fenton catalyst on perfluorooctanoic acid in example 1 of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The method utilizes the waste to prepare the metal-free Fenton catalyst, has wide raw material sources, low cost and simple preparation process, has high yield, and the obtained material has high-efficiency Fenton catalytic performance, is easy for solid-liquid separation and has good application potential in environmental management.
The invention discloses a method for preparing a graphene-based metal-free Fenton catalyst by using wastes, which is characterized by comprising the following steps of:
1) pickling the waste;
2) soaking the waste treated in the step 1) in a solution containing an auxiliary agent;
3) drying and calcining the product obtained in the step 2) to obtain the graphene-based metal-free Fenton catalyst.
Wherein the waste comprises any one or more of leaves, hair, feces, food residue, waste paper, pericarp and straw.
Wherein, the acid in the step 1) comprises any one or a combination of more of hydrochloric acid, sulfuric acid, nitric acid and acetic acid;
wherein the concentration of the acid is 0.01-200 mM; can be 0.1 to 100mM or 0.5 to 50 mM.
Wherein, the auxiliary agent comprises any one or more of phenothrin, isoamyl acetate, methyl benzoate, methyl salicylate, tetrahydrofuran and diethyl ether.
Wherein the mass ratio of the auxiliary agent to the waste is (0.01-1) to 1, which can be (0.05-0.8) to 1, and can also be (0.1-0.5) to 1; specific examples thereof include 0.02: 1, 0.05: 1, 0.1: 1, 0.15: 1, 0.2: 1, 0.3: 1, 0.4: 1, 0.5: 1, 0.6: 1, 0.8: 1 and 1: 1.
Wherein, the calcining step in the step 3) is carried out under protective gas;
the protective gas comprises inert gas or reducing gas;
wherein the inert gas comprises nitrogen and argon, and the reducing gas comprises hydrogen.
Wherein the calcining temperature in the calcining step in the step 3) is 600-1000 ℃, and the calcining time is 6-24 h;
wherein, the calcining step in the step 3) is catalyzed by a metal substrate;
wherein the metal in the metal substrate comprises any one or more of iron, cobalt, copper, silver, manganese and nickel.
Wherein the drying method in step 3) comprises freeze drying.
Wherein the waste after the pickling is dried before the step 2) is started after the step 1) is finished.
The invention also discloses the graphene-based metal-free Fenton catalyst prepared by the preparation method.
The invention also discloses an application of the graphene-based metal-free Fenton catalyst in the field of environmental management.
In an exemplary embodiment of the present invention, a method for preparing a graphene-based metal-free fenton catalyst using waste is disclosed, comprising the steps of:
1) washing the waste with acid and drying;
2) soaking the waste treated in the step 1 in a solution containing an auxiliary agent;
3) and (3) freeze-drying and calcining the product obtained in the step (2) to obtain the graphene-based metal-free Fenton catalyst.
In the above preparation method, the waste comprises leaves, hair, feces, food residue, waste paper, pericarp, straw, etc.
In the preparation method, the acid is organic or inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the like, and the concentration of the acid is 0.01-200 mM.
In the preparation method, the auxiliary agent is esters such as phenothrin, isoamyl acetate, methyl benzoate and methyl salicylate, or ethers such as tetrahydrofuran and diethyl ether.
In the above preparation method, the protective gas may be inert gas such as nitrogen, argon, etc. or reducing gas such as hydrogen, etc., and the metal substrate is catalyzed into transition metal such as iron, cobalt, copper, silver, manganese, nickel, etc., wherein nickel is preferred, the temperature is 600-.
The technical solution of the present invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
Example 1
The preparation method of the graphene-based metal-free Fenton catalyst in the embodiment specifically comprises the following steps:
soaking folium Ginkgo in 15% diluted hydrochloric acid for 10min, taking out folium Ginkgo, oven drying at 40 deg.C, soaking 0.5g sample in 25mL ethanol solution containing 0.2g phenothrin for 12h, taking out sample from the solution, and freeze drying. And wrapping the dried sample in a nickel substrate, and calcining for 6 hours at 800 ℃ under the protection of nitrogen. Thus obtaining the graphene-based metal-free Fenton catalyst. An optical photograph of the graphene-based metal-free Fenton catalyst is shown in figure 1, and a sample has a three-dimensional macroscopic structure and is easy to separate solid from liquid. The scanning electron micrograph of the graphene-based metal-free fenton catalyst is shown in fig. 2, and it can be seen that the sample has a regular porous structure. The degradation effect of the graphene-based metal-free Fenton catalyst on the perfluorinated octanoic acid of the refractory organic matter is shown in figure 3, the removal rate of 97% and the defluorination rate of 38% can be achieved within 2 hours, and the graphene-based metal-free Fenton catalyst has an excellent removal effect on the refractory organic matter.
Example 2
Soaking feather in 5% dilute sulfuric acid for 10min, taking out feather, oven drying at 40 deg.C, soaking 0.8g sample in 25mL aqueous solution containing 0.8g tetrahydrofuran for 12h, taking out sample from solution, and freeze drying. And wrapping the dried sample in a nickel substrate, and calcining for 6 hours at 500 ℃ under the protection of nitrogen. Thus obtaining the graphene-based metal-free Fenton catalyst. The specific surface area of the sample is up to 320m2The removal rate of perfluorooctanoic acid was 92%.
Example 3
Soaking waste paper in 20% nitric acid for 10min, taking out waste paper, oven drying at 40 deg.C, soaking 0.5g sample in 25mL aqueous solution containing 5mL diethyl ether for 12h, taking out sample from solution, and freeze drying. And wrapping the dried sample in a nickel substrate, and calcining the sample for 12 hours at 800 ℃ under the protection of nitrogen. Thus obtaining the graphene-based metal-free Fenton catalyst. The specific surface area of the sample is up to 240m2The removal rate of perfluorooctanoic acid was 86%.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. A method for preparing a graphene-based metal-free Fenton catalyst by using wastes is characterized by comprising the following steps of:
1) pickling the waste;
2) soaking the waste treated in the step 1) in a solution containing an auxiliary agent, wherein the auxiliary agent comprises any one or a combination of more of phenothrin, isoamyl acetate, methyl benzoate, methyl salicylate, tetrahydrofuran and diethyl ether;
3) drying and calcining the product obtained in the step 2) to obtain the graphene-based metal-free Fenton catalyst.
2. The production method according to claim 1,
the waste comprises any one or more of leaves, hair, feces, food residues, waste paper, fruit peel and straw.
3. The production method according to claim 1,
the acid in the step 1) comprises any one or more of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
4. The production method according to claim 1,
the concentration of the acid is 0.01-200 mM.
5. The production method according to claim 4,
the concentration of the acid is 0.1-100 mM.
6. The production method according to claim 5,
the concentration of the acid is 0.5-50 mM.
7. The production method according to claim 1,
the mass ratio of the auxiliary agent to the waste is (0.01-1): 1.
8. the production method according to claim 7,
the mass ratio of the auxiliary agent to the waste is (0.05-0.8): 1.
9. the method according to claim 8,
the mass ratio of the auxiliary agent to the waste is (0.1-0.5): 1.
10. the production method according to claim 1,
the calcining step in the step 3) is carried out under protective gas;
the protective gas comprises inert atmosphere or reducing gas.
11. The production method according to claim 10,
the inert atmosphere comprises nitrogen and argon, and the reducing gas comprises hydrogen.
12. The production method according to claim 1,
the calcination temperature in the calcination step in the step 3) is 600-1000 ℃, and the calcination time is 6-24 h;
in the step 3), the calcination step is catalyzed by a metal substrate;
the metal in the metal substrate comprises any one or combination of iron, cobalt, copper, silver, manganese and nickel.
13. The production method according to claim 1,
the drying method described in step 3) comprises freeze-drying.
14. The production method according to claim 1,
drying the waste after the pickling before the step 2) is started after the step 1).
15. The graphene-based metal-free fenton catalyst obtained by the production method according to any one of claims 1 to 14.
16. The use of the graphene-based metal-free fenton catalyst according to claim 15 in the field of environmental remediation.
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| CN106807444B (en) * | 2015-11-27 | 2019-11-05 | 中国科学院过程工程研究所 | Heterogeneous no metal fenton catalyst of one kind and its preparation method and application |
| CN109529888B (en) * | 2018-11-26 | 2020-10-20 | 中国科学院生态环境研究中心 | Three-dimensional graphene-based heterogeneous Fenton catalyst, and preparation method and application thereof |
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| CN109772285A (en) * | 2019-03-01 | 2019-05-21 | 北京航空航天大学 | A kind of preparation method and application of heterogeneous light Fenton catalyst |
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