CN112108169A - Carbon cloth loaded nitrogen-doped graphene material and preparation method and application thereof - Google Patents
Carbon cloth loaded nitrogen-doped graphene material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 119
- 239000004744 fabric Substances 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 32
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 230000003213 activating effect Effects 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
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- 239000013179 MIL-101(Fe) Substances 0.000 claims description 27
- -1 ZIF-67(Co) Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000197 pyrolysis Methods 0.000 claims description 20
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- 238000002791 soaking Methods 0.000 claims description 10
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- 229910052786 argon Inorganic materials 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000013132 MOF-5 Substances 0.000 claims description 8
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000013215 MIL-88B Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 23
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 13
- 238000011068 loading method Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
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- 230000000694 effects Effects 0.000 description 11
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 11
- 229940012189 methyl orange Drugs 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
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- 239000000975 dye Substances 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 3
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
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- 238000004435 EPR spectroscopy Methods 0.000 description 1
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- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/58—
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention belongs to the technical field of solid catalysts for activating persulfate, and particularly discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps: (1) firstly, dispersing a nitrogen source into an organic solvent, then adding non-noble metal-MOF (metal organic framework) nano particles serving as precursors, and stirring and mixing at 60 ℃ to obtain a compound dispersion liquid; wherein the mass ratio of the nitrogen source to the non-noble metal-MOF is (1-20) to 1; (2) and then dropwise adding the composite dispersion liquid onto the carbon cloth subjected to acidification treatment, and pyrolyzing to obtain the carbon cloth loaded nitrogen-doped graphene material. The carbon cloth is used as a substrate, and the self-assembled compound of the non-noble metal MOF and the nitrogen source is pyrolyzed, so that the active nitrogen component in the catalyst is improved, the catalytic degradation performance is promoted, and the material has good catalytic activity and stability. The invention also discloses application of the material as a catalyst for activating persulfate.
Description
Technical Field
The invention belongs to the technical field of solid catalysts for activating persulfate, and particularly relates to a carbon cloth loaded nitrogen-doped graphene material as well as a preparation method and application thereof.
Background
The advanced oxidation technology is a novel technology which is newly developed in recent years and is used for treating refractory organic pollutants, has the advantages of short period, quick response, low cost, good treatment effect and the like, and becomes a hotspot and frontier of the research in the field of domestic and foreign medical wastewater treatment. Especially, compared with the traditional advanced oxidation technology such as Fenton method, the persulfate-activated advanced oxidation technology has the advantages of strong stability, good solubility, wide applicable pH range, long service life of generated sulfate radical and the like, and is more favorable for degrading high-concentration organic pollutants.
Under the condition of normal temperature, the persulfate is relatively stable, and can generate strong-oxidability sulfate radicals and hydroxyl radicals after being activated by carbon materials such as heating, chelated or non-chelated transition metal ions, light, alkali, activated carbon and the like, so that target pollutants can be efficiently and quickly removed. The thermal activation persulfate technology has high energy consumption, the optical activation persulfate technology is harsh to the operation conditions, the alkali activation persulfate technology can cause the pH value in water to be too high, and the transition metal activation persulfate technology has heavy metal leakage risk. Compared with other activation modes, the carbon material activation has the advantages of high catalytic efficiency, strong oxidation capacity, good reusability, environmental friendliness and the like. As a emerging pollutant oxidation removal technology at present, the method has a huge application prospect in the aspect of treatment of organic polluted water in the fields of underground water, printing and dyeing and the like. However, most carbon catalysts are powder, and have the problems of difficult recovery, insufficient stability, low catalytic efficiency and the like.
Disclosure of Invention
The invention aims to provide a carbon cloth loaded nitrogen-doped graphene material, and a preparation method and application thereof, and solves the problems of difficult recovery, insufficient stability and low catalytic efficiency of the existing catalyst.
The invention is realized by the following technical scheme:
a preparation method of a carbon cloth loaded nitrogen-doped graphene material comprises the following steps:
(1) firstly, dispersing a nitrogen source into an organic solvent, then adding non-noble metal-MOF (metal organic framework) nano particles serving as precursors, and stirring and mixing at 60 ℃ to obtain a compound dispersion liquid; wherein the mass ratio of the nitrogen source to the non-noble metal-MOF is (1-20) to 1;
(2) and then dropwise adding the composite dispersion liquid onto the carbon cloth subjected to acidification treatment, and pyrolyzing to obtain the carbon cloth loaded nitrogen-doped graphene material.
Further, the mass ratio of the nitrogen source to the non-noble metal-MOF is (5-20): 1.
Further, the nitrogen source is one or more of urea, dicyandiamide, melamine, acetonitrile and polyaniline.
Further, the organic solvent is one or more of methanol, ethanol, isopropanol, ethylene glycol, polyethylene glycol, etc.
Further, the non-noble metal-MOF is one or more of MOF-5(Zn), ZIF-8(Zn), ZIF-67(Co), MIL-88B (Fe) and MIL-101 (Fe).
Further, the processing method of the carbon cloth comprises the following steps: in the presence of concentrated mixed acid and KMnO4Soaking in solution, wherein the concentrated mixed acid is one or more of concentrated phosphoric acid and concentrated hydrochloric acid, concentrated sulfuric acid, and concentrated nitric acid.
Further, the pyrolysis temperature is 300-1200 ℃, and the pyrolysis time is 5 minutes-5 hours.
Further, the pyrolysis atmosphere is nitrogen, argon or helium.
The invention also discloses the carbon cloth loaded nitrogen-doped graphene material prepared by the preparation method.
The invention also discloses application of the carbon cloth loaded nitrogen-doped graphene material as a catalyst for activating persulfate, and sulfate radicals are generated when the carbon cloth loaded nitrogen-doped graphene material activates persulfate.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material. The high content proportion of graphite nitrogen and graphitized carbon in the catalyst is beneficial to improving the electron transfer capability of the material, so that the catalyst has good conductivity; at present, the catalyst with less milligram-level addition amount can reach more than 82% of degradation rate in 20 minutes under the condition of 0.3mM persulfate oxidant, which indicates that the catalyst has excellent catalytic activity; in addition, the catalyst prepared by the scheme can still basically keep the original catalytic degradation capability after being circulated for 5 times, and has good stability. The preparation process is environment-friendly and safe, the preparation process is simple, and the preparation cost is low; does not adopt sacrificial elements and noble metals, and belongs to an atom economic preparation method. In addition, in practical application, the problem of recycling and reusing the catalyst must be solved, so that the catalyst takes carbon cloth as a carrier, which is beneficial to recycling of the powder catalyst and realizes sustainable development of resources.
Further, after the carbon cloth is acidified, oxygen-containing functional groups with negative charges can be grafted on the surface of the carbon cloth to form binding sites of metal cations, so that the loading capacity of the MOF/nitrogen source compound on the carbon cloth is increased, and the loading fastness of the MOF/nitrogen source compound on the carbon cloth is improved.
Further, on one hand, the precursor MOF crystal lattice can be reconstructed and carbonized through pyrolysis treatment to form a graphene carbon layer capable of carrying out electron transfer; on the other hand, nitrogen atoms in the nitrogen source can be made to enter into the carbon lattice of the MOF precursor by atomic thermal movement to form active nitrogen components with persulfate catalytic activity, such as pyridine nitrogen, graphite nitrogen, and the like.
The material has good catalytic activity and stability, can be used for degrading persulfate to treat sewage, can be used at normal temperature in a dark place, has the advantages of wide application range, high catalytic efficiency, strong oxidation capacity, convenience in recovery, good reusability and the like, and has a huge application prospect in the treatment of organic polluted water in the fields of underground water, printing and dyeing and the like.
Drawings
Fig. 1 is an SEM image of a carbon cloth-loaded nitrogen-doped graphene material of the present invention;
FIG. 2 is a graph comparing the time-degradation efficiency of activated persulfate for degradation of methyl orange dye liquor of example one and comparative examples one, two and three;
FIG. 3 is a graph showing the relationship between different reaction pH values and corresponding time-degradation efficiencies when activated persulfate of the carbon cloth loaded nitrogen-doped graphene material degrades rhodamine B wastewater;
fig. 4 is an X-ray photoelectron spectrum N1s spectrogram of the carbon cloth-supported nitrogen-doped graphene material of the present invention;
fig. 5 is a raman spectrum of the carbon cloth loaded nitrogen-doped graphene material of the present invention;
fig. 6 is an electron paramagnetic resonance spectrum of the carbon cloth loaded nitrogen-doped graphene material and a 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) system after 10 minutes of adding oxone.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) firstly, dispersing a nitrogen source into an organic solvent, then adding non-noble metal-MOF (metal organic framework) nano particles serving as precursors, and stirring and mixing at 60 ℃ to obtain a compound dispersion liquid; wherein the mass ratio of the nitrogen source to the non-noble metal-MOF is (1-20) to 1;
(2) and then dropwise adding the composite dispersion liquid onto the carbon cloth subjected to acidification treatment, and pyrolyzing to obtain the carbon cloth loaded nitrogen-doped graphene material.
Specifically, the nitrogen source is one or more of urea, dicyandiamide, melamine, acetonitrile and polyaniline.
Specifically, the organic solvent is one or more of methanol, ethanol, isopropanol, ethylene glycol, polyethylene glycol, etc.
Specifically, the non-noble metal-MOF is one or more of MOF-5(Zn), ZIF-8(Zn), ZIF-67(Co), MIL-88B (Fe) and MIL-101 (Fe).
Example one
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) 5.231g of dicyandiamide is dissolved in 167mL of ethanol, after stirring and heating at 60 ℃, 0.5231g of MIL-101(Fe) is added, namely the mass ratio of the nitrogen source to the MOF is 10: 1; after stirring uniformly for 4 hours, a pale orange solution was obtained, i.e., MIL-101 (Fe)/dicyandiamide complex dispersion.
(2) The carbon cloth was mixed with concentrated acid and 2.5g KMnO at 50 deg.C4And soaking in the solution for 5min, and then washing and drying to obtain the treated carbon cloth. Wherein the concentrated mixed acid is 5ml of concentrated phosphoric acid and 45ml of concentrated hydrochloric acid.
(3) And dropwise adding the MIL-101 (Fe)/dicyandiamide compound dispersion liquid onto the treated carbon cloth, loading the MIL-101 (Fe)/dicyandiamide compound on the carbon cloth, putting the carbon cloth into a quartz boat of a tubular furnace for pyrolysis, introducing argon gas with the flow rate of 80mL/min, heating at the rate of 5 ℃ per minute, keeping the temperature at 1000 ℃ for 2 hours, and naturally cooling to obtain the carbon cloth loaded nitrogen-doped graphene material, which is marked as CC-MIL-10 DCD-1000.
Example two
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) 7.068g of dicyandiamide is dissolved in 226mL of ethylene glycol, after stirring and heating at 60 ℃, 0.3534g of MOF-5(Zn) is added, namely the mass ratio of a nitrogen source to the MOF is 20: 1; after being uniformly stirred for 4 hours, a white solution, namely MOF-5 (Zn)/dicyandiamide compound dispersion liquid is obtained.
(2) The carbon cloth was mixed with concentrated acid and 2.5g KMnO at 50 deg.C4And soaking in the solution for 5min, and then washing and drying to obtain the treated carbon cloth. Wherein the concentrated mixed acid is 5ml of concentrated phosphoric acid and 45ml of concentrated nitric acid.
(3) Dropwise adding the MOF-5 (Zn)/dicyandiamide compound dispersion liquid onto the treated carbon cloth, loading the MIL-101 (Fe)/dicyandiamide compound on the carbon cloth, then placing the carbon cloth in a quartz boat of a tube furnace for pyrolysis, introducing nitrogen with the flow rate of 80mL/min, heating at the rate of 5 ℃ per minute, keeping the temperature at 700 ℃ for 1 hour, and then naturally cooling to obtain the carbon cloth loaded nitrogen-doped graphene material, which is marked as CC-MOF-20 DCD-700.
EXAMPLE III
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) dissolving 3.534g of dicyandiamide in 113mL of mixed solvent of ethanol and isopropanol, stirring and heating at 60 ℃, adding 0.6311g of MIL-101(Fe), namely, the mass ratio of nitrogen source to MOF is 5.6: 1; after stirring uniformly for 2 hours, a pale orange solution was obtained, i.e., MIL-101 (Fe)/dicyandiamide complex dispersion.
(2) The carbon cloth was mixed with concentrated acid and 2.5g KMnO at 50 deg.C4And soaking in the solution for 5min, and then washing and drying to obtain the treated carbon cloth. Wherein the concentrated mixed acid is 5ml of concentrated phosphoric acid and 45ml of concentrated sulfuric acid.
(3) And dropwise adding the MIL-101 (Fe)/dicyandiamide compound dispersion liquid onto the treated carbon cloth, loading the MIL-101 (Fe)/dicyandiamide compound on the carbon cloth, then placing the carbon cloth in a quartz boat of a tube furnace for pyrolysis, introducing helium with the flow rate of 80mL/min, raising the temperature at 5 ℃ per minute, keeping the temperature at 800 ℃ for 5 hours, and then naturally cooling to obtain the carbon cloth loaded nitrogen-doped graphene material, which is marked as CC-MIL-5.6 DCD-800.
Example four
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) 0.6311g of melamine is dissolved in 20mL of ethanol, stirred and heated at 60 ℃ to be dissolved, and 0.6311g of ZIF-8(Zn) is added, namely the mass ratio of the nitrogen source to the MOF is 1: 1; and uniformly stirring for 2 hours to obtain a white solution, namely a ZIF-8 (Zn)/dicyandiamide compound dispersion liquid.
(2) The carbon cloth was mixed with concentrated acid and 2.5g KMnO at 50 deg.C4And soaking in the solution for 5min, and then washing and drying to obtain the treated carbon cloth. Wherein the concentrated mixed acid is 5ml of concentrated phosphoric acid, 25ml of concentrated hydrochloric acid and 20ml of concentrated sulfuric acid.
(3) Dropwise adding the ZIF-8 (Zn)/dicyandiamide compound dispersion liquid onto the treated carbon cloth, loading the ZIF-8 (Zn)/dicyandiamide compound on the carbon cloth, then placing the carbon cloth in a quartz boat of a tube furnace for pyrolysis, introducing argon gas with the flow rate of 80mL/min, heating at the rate of 5 ℃ per minute, keeping the temperature at 1100 ℃ for 5 minutes, and then naturally cooling to obtain the carbon cloth loaded nitrogen-doped graphene material, which is marked as CC-ZIF-1 melamine-1100.
EXAMPLE five
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) 5.231g of dicyandiamide and melamine are dissolved in 167mL of ethanol, stirred and heated at 60 ℃ to be dissolved, and 0.5231g of MIL-101(Fe) is added, namely the mass ratio of the nitrogen source to the MOF is 10: 1; after stirring homogeneously for 3 hours, a pale orange dispersion of the complex is obtained.
(2) The carbon cloth was mixed with concentrated acid and 2.5g KMnO at 50 deg.C4And soaking in the solution for 5min, and then washing and drying to obtain the treated carbon cloth. Wherein the concentrated mixed acid is 5ml of concentrated phosphoric acid and 45ml of concentrated nitric acid.
(3) And dropwise adding the compound dispersion liquid onto the treated carbon cloth, loading the MIL-101 (Fe)/dicyandiamide compound on the carbon cloth, then putting the carbon cloth into a quartz boat of a tube furnace for pyrolysis, introducing nitrogen with the flow rate of 80mL/min, keeping the temperature at 300 ℃ for 2 hours at the temperature rising rate of 5 ℃ per minute, and then naturally cooling to obtain the carbon cloth loaded nitrogen-doped graphene material, which is marked as CC-MIL-10 DCD/melamine-300.
EXAMPLE six
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) 2.616g of dicyandiamide is dissolved in 84mL of ethanol, after stirring and heating at 60 ℃, 0.5231g of MIL-101(Fe) is added, namely the mass ratio of the nitrogen source to the MOF is 5: 1; after stirring uniformly for 3 hours, a pale orange solution was obtained, i.e., MIL-101 (Fe)/dicyandiamide complex dispersion.
(2) The carbon cloth was mixed with concentrated acid and 2.5g KMnO at 50 deg.C4And soaking in the solution for 5min, and then washing and drying to obtain the treated carbon cloth. Wherein the concentrated mixed acid is 5ml of concentrated phosphoric acid and 45ml of concentrated sulfuric acid.
(3) And dropwise adding the MIL-101 (Fe)/dicyandiamide compound dispersion liquid onto the treated carbon cloth, loading the MIL-101 (Fe)/dicyandiamide compound on the carbon cloth, then placing the carbon cloth in a quartz boat of a tube furnace for pyrolysis, introducing argon gas with the flow rate of 80mL/min, heating at the rate of 5 ℃ per minute, keeping the temperature at 900 ℃ for 2 hours, and then naturally cooling to obtain the carbon cloth loaded nitrogen-doped graphene material, which is marked as CC-MIL-5 DCD-900.
EXAMPLE seven
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) dissolving 3.534g of dicyandiamide in 113mL of ethanol, stirring and heating at 60 ℃ to dissolve, and adding 0.3534g of a mixture of ZIF-8(Zn) and ZIF-67(Co), wherein the mass ratio of a nitrogen source to MOF is 10: 1; after stirring homogeneously for 2 hours, a pale purple dispersion of the complex is obtained.
(2) The carbon cloth was mixed with concentrated acid and 2.5g KMnO at 50 deg.C4And soaking in the solution for 5min, and then washing and drying to obtain the treated carbon cloth. Wherein the concentrated mixed acid is 5ml of concentrated phosphoric acid, 20ml of concentrated hydrochloric acid and 25ml of concentrated nitric acid.
(3) And dropwise adding the MIL-101 (Fe)/dicyandiamide compound dispersion liquid onto the treated carbon cloth, loading the MIL-101 (Fe)/dicyandiamide compound on the carbon cloth, then placing the carbon cloth in a quartz boat of a tubular furnace for pyrolysis, introducing nitrogen with the flow rate of 80mL/min, heating at the rate of 5 ℃ per minute, keeping the temperature at 1000 ℃ for 3 hours, and then naturally cooling to obtain the carbon cloth loaded nitrogen-doped graphene material, which is marked as CC-MOF-10 DCD-1000.
Example eight
The invention discloses a preparation method of a carbon cloth loaded nitrogen-doped graphene material, which comprises the following steps:
(1) adding 5.301g of dicyandiamide into a single-neck flask, adding 170mL of ethanol, stirring and heating at 60 ℃, dissolving, and adding 0.3534g of MOF-5, wherein the mass ratio of a nitrogen source to MOF is 15: 1; after stirring uniformly for 2 hours, a light orange solution, namely MOF-5/dicyandiamide compound dispersion liquid, is obtained.
(2) The carbon cloth was mixed with concentrated acid and 2.5g KMnO at 50 deg.C4And soaking in the solution for 5min, and then washing and drying to obtain the treated carbon cloth. Wherein the concentrated mixed acid is 5ml of concentrated phosphoric acid and 45ml of concentrated sulfuric acid.
(3) And dropwise adding the MIL-101 (Fe)/dicyandiamide compound dispersion liquid onto the treated carbon cloth, loading the MIL-101 (Fe)/dicyandiamide compound on the carbon cloth, then placing the carbon cloth in a quartz boat of a tube furnace for pyrolysis, introducing argon gas with the flow rate of 80mL/min, heating at the rate of 5 ℃ per minute, keeping the temperature at 900 ℃ for 3 hours, and then naturally cooling to obtain the carbon cloth loaded nitrogen-doped graphene material, which is marked as CC-MIL-15 DCD-900.
As shown in fig. 1, SEM images of the carbon cloth-supported nitrogen-doped graphene material of the present invention clearly show that the wrinkled monolayer graphene is attached to the surface of the carbon fiber, which explains the existence of the nitrogen-doped graphene
As shown in fig. 4, it can be seen from the energy spectrum diagram of N1s of the carbon cloth-supported nitrogen-doped graphene material of the present invention that the main valence states of the nitrogen element in the material are pyridine nitrogen and graphite nitrogen, which indicates that after pyrolysis, the nitrogen source is doped into the carbon lattice to form a higher proportion of pyridine nitrogen and graphite nitrogen, wherein the graphite nitrogen is more favorable for electron transport to improve the conductivity, and the graphite nitrogen is resistant to high temperature to improve the catalyst stability; pyridine nitrogen is beneficial to adsorption of oxygen-oxygen bonds, and persulfate is convenient to pyrolyze to generate active free radicals, so that the catalytic performance of the catalyst is improved.
As shown in fig. 5, in a raman spectrogram of the carbon cloth-loaded nitrogen-doped graphene material, the intensity ratio of a D peak to a G peak of the catalyst material is 0.62, which is lower than 0.8-1 commonly found in reports, which indicates that the graphitization degree of the catalyst carbon material is high, which facilitates electron transmission in catalytic reaction, and further facilitates catalytic degradation of dyes.
As shown in fig. 6, after potassium hydrogen persulfate is added for 10 minutes, the electron paramagnetic resonance spectrogram of the carbon cloth-loaded nitrogen-doped graphene material and the 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) system of the present invention shows that the peak intensity of a classical DMPO-OH is 1: 2: 2: 1 quartet and DMPO-. SO4 -The six-fold characteristic peak indicates that the catalyst material of the invention has obvious effect of activating persulfate to generate OH & and SO & lt- & gt4 -The ability to activate free radicals.
Comparative example one:
dispersing 0.3534g of MIL-101(Fe) light pink powder in an ethanol solution to obtain an MIL-101(Fe) dispersion liquid, namely the mass ratio of a nitrogen source to MOF is 0:1, dripping the dispersion liquid on a pretreated carbon cloth, and drying; placing the carbon cloth loaded MIL-101(Fe) compound in a quartz boat of a tube furnace for pyrolysis; and introducing argon gas with the flow rate of 80mL/min, keeping the temperature at 1000 ℃ for 2 hours at the temperature of 5 ℃ per minute, and naturally cooling to obtain the CC-MIL-0DCD-1000 catalyst.
Comparative example two:
dissolving 3.534g of dicyandiamide in 113mL of ethanol to obtain dicyandiamide dispersion liquid, dripping the dispersion liquid on a pretreated carbon cloth, and drying, wherein the mass ratio of a nitrogen source to MOF is 1: 0; placing the carbon cloth loaded dicyandiamide compound in a quartz boat of a tube furnace for pyrolysis; and introducing argon gas with the flow rate of 80mL/min, keeping the temperature at 1100 ℃ for 2 hours at the temperature rising rate of 5 ℃ per minute, and naturally cooling to obtain the CC-DCD-1100 catalyst.
Comparative example three:
dissolving 3.534g of dicyandiamide in 113mL of ethanol to obtain dicyandiamide dispersion liquid, adding 0.3534g of MIL-101(Fe), dripping the dispersion liquid on untreated carbon cloth, and drying; placing the carbon cloth loaded dicyandiamide compound in a quartz boat of a tube furnace for pyrolysis, wherein the mass ratio of the nitrogen source to the MOF is 5.6: 1; introducing argon gas with the flow rate of 80mL/min, keeping the temperature at 1000 ℃ for 2 hours at the temperature of 5 ℃ per minute, and then naturally cooling to obtain the NCC-10DCD-1000 catalyst.
The application of the materials prepared in the first example, the second comparative example and the third comparative example in the oxidative degradation of methyl orange by activating persulfate is compared and researched, and the application comprises the following steps:
four groups of methyl orange solutions with the concentration of 50mg/L, the volume of 100mL and the pH value of 7 are prepared, 5 pieces of 1cm × 1cm CC-MIL-10DCD-1000 of the first embodiment, 5 pieces of 1cm × 1cm CC-MIL-0DCD-1000 of the first comparative embodiment and 5 pieces of 1cm × 1cm NCC-MIL-10DCD-1000 of the third comparative embodiment are correspondingly added in the three groups, stirring is carried out for one hour under dark conditions until adsorption is balanced, 20mg (0.3mM) of potassium hydrogen persulfate is added in the fourth group of methyl orange solutions respectively, and degradation of methyl orange is finished after the reaction is completed.
Determination of degradation efficiency: and (3) respectively absorbing 2mL of reaction solution from each reaction solution every 5min, adding the reaction solution into a centrifuge tube filled with 2mL of methanol quenching agent with the same volume, and detecting on an ultraviolet-visible spectrophotometer instrument, wherein the actual concentration is twice of the concentration of the dye solution.
FIG. 2 is a graph comparing the time-degradation efficiency of the material prepared in the first example of the present invention and the material prepared in the first and third comparative examples when persulfate is activated to degrade methyl orange dye liquor. The degradation effect after 20 minutes is shown in table 1.
Table 1 results of the effect of example one and comparative examples one to three on the degradation of methyl orange by activated persulfate
The above experiment compares the degradation effect of the nitrogen source addition and the carbon cloth pretreatment on the degradation of methyl orange wastewater by the carbon cloth loaded nitrogen-doped graphene catalyst, and as can be seen from fig. 2, compared with CC-MIL-0DCD-1000, the CC-MIL-10DCD-1000 catalyst can generate active nitrogen components after the pyrolysis of dicyandiamide added with the additional nitrogen source is added, so that the activation effect on persulfate is greatly improved, the persulfate is effectively promoted to generate sulfate radicals and hydroxyl radicals to oxidize and degrade methyl orange, and the degradation effect of methyl orange wastewater is obviously improved. In addition, compared with NCC-MIL-10DCD-1000, the CC-MIL-10DCD-1000 catalyst obtained by the carbon cloth through mixed acid pretreatment has a certain improvement on the performance of catalytic degradation of methyl orange, which indicates that the loading capacity and the loading fastness of the MIL-101 (Fe)/dicyandiamide compound can be effectively improved by performing hydrophilic modification pretreatment on the carbon cloth, so that the catalyst is effectively promoted to generate active free radicals to degrade organic pollutants.
The following are researches on the influence of different pH values on the carbon cloth loaded nitrogen-doped graphene material as a catalyst for activating persulfate so as to degrade rhodamine B wastewater, and specifically include the following steps:
and (2) respectively adding 5 pieces of 1 cm-1 cm CC-MOF-20DCD-700 of the second embodiment into four rhodamine B wastewater with the concentration of 50mg/L, the volume of 50mL and the pH values of 3, 5, 7 and 9, stirring for one hour under dark conditions, adding 10mg (0.3mM) of potassium hydrogen persulfate after adsorption equilibrium, and finishing the degradation of the rhodamine B wastewater after the reaction is completed.
FIG. 3 is a graph showing the relationship between the time and the degradation efficiency of different reaction pH values when the CC-MOF-20DCD-700 catalyst activates persulfate to degrade rhodamine B wastewater. The degradation effect after 20 minutes is shown in table 2.
Table 2 results of the effect of different pH values on the degradation of rhodamine B wastewater by activated persulfate
| pH value | 3 | 5 | 7 | 9 |
| Degradation Rate (%) | 92 | 96 | 98 | 64 |
The results in table 2 show that the carbon cloth-loaded nitrogen-doped graphene material prepared by the invention is more suitable for exerting the activation performance in a neutral or acidic rhodamine B wastewater environment when being used as a catalyst for activating persulfate. The acidic condition has slight inhibition effect on the catalytic activity of the catalyst, and the catalyst is not suitable for strong alkaline conditions at the same time, probably because sulfate radicals can be decomposed under the strong alkaline conditions, so that the degradation performance is reduced.
The catalyst prepared by the invention can still basically maintain the original catalytic degradation capability after being circulated for 5 times, which shows that the catalyst has good stability.
In conclusion, the persulfate activator disclosed by the invention has the advantages of excellent activation catalytic performance, easiness in recovery, better stability, low price and the like, and therefore, the persulfate activator has better application prospect in treatment of waste water such as dye and the like.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A preparation method of a carbon cloth loaded nitrogen-doped graphene material is characterized by comprising the following steps:
(1) firstly, dispersing a nitrogen source into an organic solvent, then adding non-noble metal-MOF (metal organic framework) nano particles serving as precursors, and stirring and mixing at 60 ℃ to obtain a compound dispersion liquid; wherein the mass ratio of the nitrogen source to the non-noble metal-MOF is (1-20) to 1;
(2) and then dropwise adding the composite dispersion liquid onto the carbon cloth subjected to acidification treatment, and pyrolyzing to obtain the carbon cloth loaded nitrogen-doped graphene material.
2. The preparation method of the carbon cloth-loaded nitrogen-doped graphene material according to claim 1, wherein the mass ratio of the nitrogen source to the non-noble metal-MOF is (5-20): 1.
3. The method for preparing the carbon cloth-loaded nitrogen-doped graphene material according to claim 1, wherein the nitrogen source is one or more of urea, dicyandiamide, melamine, acetonitrile and polyaniline.
4. The method for preparing the carbon cloth-loaded nitrogen-doped graphene material according to claim 1, wherein the organic solvent is one or more of methanol, ethanol, isopropanol, ethylene glycol, polyethylene glycol and the like.
5. The method for preparing the carbon cloth supported nitrogen-doped graphene material according to claim 1, wherein the non-noble metal-MOF is one or more of MOF-5(Zn), ZIF-8(Zn), ZIF-67(Co), MIL-88B (Fe) and MIL-101 (Fe).
6. The preparation method of the carbon cloth loaded nitrogen-doped graphene material according to claim 1, wherein the carbon cloth is processed by the following steps: in the presence of concentrated mixed acid and KMnO4Soaking in solution, wherein the concentrated mixed acid is one or more of concentrated phosphoric acid and concentrated hydrochloric acid, concentrated sulfuric acid, and concentrated nitric acid.
7. The method as claimed in claim 1, wherein the pyrolysis temperature is 300-1200 ℃, and the pyrolysis time is 5 minutes-5 hours.
8. The method for preparing the carbon cloth-loaded nitrogen-doped graphene material according to claim 1, wherein the pyrolysis atmosphere is nitrogen, argon or helium.
9. The carbon cloth loaded nitrogen-doped graphene material prepared by the preparation method of any one of claims 1 to 8.
10. The use of the carbon cloth-supported nitrogen-doped graphene material of claim 9 as a catalyst for activating persulfate, wherein the carbon cloth-supported nitrogen-doped graphene material generates sulfate radicals when activating persulfate.
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