CN111468169A - Carbon-three-nitrogen-four-load FeCo2S4Catalyst of nano particles and application thereof - Google Patents
Carbon-three-nitrogen-four-load FeCo2S4Catalyst of nano particles and application thereof Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 95
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 53
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- 239000011593 sulfur Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 17
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 17
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- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- 238000006479 redox reaction Methods 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- MJIFVKOEJRMYHU-UHFFFAOYSA-N [N].[N].[N].[C] Chemical compound [N].[N].[N].[C] MJIFVKOEJRMYHU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010931 gold Substances 0.000 abstract 1
- 229910052737 gold Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229960000623 carbamazepine Drugs 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
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- 229920006362 Teflon® Polymers 0.000 description 3
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- KRBKACYISIZIBQ-UHFFFAOYSA-N [C].[C].[N] Chemical compound [C].[C].[N] KRBKACYISIZIBQ-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of water treatment, in particular to carbon-three-nitrogen-four-load FeCo2S4A catalyst of nano particles, a preparation method and application thereof. The invention relates to carbon-three-nitrogen-four-load FeCo2S4Nanoparticle catalyst comprising carbon trinitrogen IV and FeCo supported on the carbon trinitrogen IV2S4A nanoparticle; the FeCo2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is (0.05-0.1): 1. the invention is realized by adding FeCo2S4The nano particles are loaded on carbon, nitrogen and nitrogen, and FeCo is improved2S4The dispersibility of the nano particles can be reduced, and the free gold can be reducedThe obtained catalyst has good catalytic performance and can remove organic pollutants in water by high-efficiency catalytic oxidation.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to carbon-three-nitrogen-four-load FeCo2S4A catalyst of nano particles, a preparation method and application thereof.
Background
With the continuous progress of science and technology and the rapid development of industry, a large amount of pollutants enter water bodies through different ways, so that water pollution becomes one of the main environmental problems facing China. In recent years, the removal of organic pollutants in water by using advanced oxidation technology is becoming a research hotspot of scholars at home and abroad.
In the advanced oxidation technology, the reaction rate of oxidizing organic matters by using an independent oxidant is low, a catalyst is generally required to catalyze oxidants such as hydrogen peroxide, persulfate, ozone, permanganate and the like to decompose and generate active oxygen species with higher oxidation potential, the active oxygen species has the characteristic of high reaction rate with the organic matters, and toxic and nondegradable pollutants in the converted wastewater can be effectively decomposed, so that the toxicity of the wastewater is reduced, and the biodegradability is improved. The catalyst generally includes a homogeneous catalyst which is some transition metal ions, and a heterogeneous catalyst which is some transition metal oxides or sulfides, etc. Compared with homogeneous catalysts, heterogeneous catalysts have the characteristics of high catalytic effect, recycling and small secondary pollution. Therefore, heterogeneous catalysts are widely used to study the catalytic oxidative degradation of organic pollutants in water.
The metal sulfide has the excellent properties of wide source, good catalytic performance and good effect, and is often used for pollution remediation and treatment in the environmental field. In the research of metal sulfides, the bimetallic sulfide metal ions are found to possibly generate synergistic effect, and better electrochemical and catalytic performances can be shown. Therefore, the bimetal sulfide is widely applied to environmental remediation and treatment. FeCo2S4Nanoparticles have a low intrinsic resistivity and are widely studied. FeCo2S4Contains abundant metal active sites, can catalyze various advanced oxidation processes, such as Peroxymonosulfate (PMS), ozone and other water treatment processes, and has huge potentialAnd (4) environmental benefits. However, FeCo2S4The nano particles have poor dispersibility and are easy to agglomerate to form particles with large particle size, thereby influencing the catalytic performance of the particles. Furthermore, leaching of metal ions into the environment can be harmful to the environment, so FeCo alone2S4The application of nanoparticles is very limited.
Disclosure of Invention
The invention aims to provide carbon-three-nitrogen-four-load FeCo2S4Catalyst of nanoparticles, preparation method and application thereof, prepared by mixing FeCo2S4The nano particles are loaded on carbon, nitrogen and nitrogen, and FeCo is improved2S4The dispersibility of the nano particles can reduce the leaching of free metal ions, and the obtained catalyst has good catalytic performance and can remove organic pollutants in water by high-efficiency catalytic oxidation.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides carbon-three-nitrogen-four-load FeCo2S4Nanoparticle catalyst comprising carbon trinitrogen IV and FeCo supported on the carbon trinitrogen IV2S4A nanoparticle; the FeCo2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is (0.05-0.1): 1.
the invention provides carbon-three-nitrogen-four-load FeCo in the scheme2S4A method for preparing a nanoparticle catalyst comprising the steps of:
calcining the carbon source in a nitrogen atmosphere to obtain carbon III-N IV;
dispersing the carbon, the nitrogen and the carbon into water to obtain a carbon, the nitrogen and the carbon dispersion liquid;
mixing the carbon three nitrogen four dispersion liquid with FeCl2、Co(NO3)2And NH4F, mixing, and carrying out hydrothermal reaction to obtain carbon III-N IV loaded with the Fe-Co compound;
mixing the Fe-Co compound-loaded carbon-nitrogen-IV with a sulfur source solution, and carrying out a vulcanization reaction to obtain carbon-nitrogen-IV-loaded FeCo2S4Catalysis of nanoparticlesAn oxidizing agent;
the FeCl2、Co(NO3)2、NH4The molar ratio of the F to the sulfur source in the sulfur source solution is 1:2:2: 10;
the carbon, the nitrogen and the carbon are mixed with FeCl2The dosage ratio of the components is 3.02 g: (0.5 to 1) mmol.
Preferably, the carbon source is one or more of urea, melamine, cyanamide and dicyandiamide;
the sulfur source in the sulfur source solution is one or more of thioacetamide, sodium thiosulfate, sodium sulfide and thiourea.
Preferably, the temperature of the hydrothermal reaction is 130-150 ℃ and the time is 8-10 h.
Preferably, the temperature of the vulcanization reaction is 140-170 ℃, and the time is 5-7 h.
The invention provides carbon-three-nitrogen-four-load FeCo in the scheme2S4Catalyst of nano particles or carbon-nitrogen-four-loaded FeCo prepared by the preparation method in the scheme2S4Use of a nanoparticle catalyst for the treatment of organic wastewater.
Preferably, the method of application comprises: loading carbon, three nitrogen and four with FeCo2S4Mixing the catalyst of the nano particles, the oxidant and the organic wastewater to carry out oxidation-reduction reaction.
Preferably, the carbon-three-nitrogen-four-loaded FeCo2S4The concentration of the nano-particle catalyst in the organic wastewater is 5-500 mg/L, the concentration of the oxidant in the organic wastewater is 0.05-5 mmol/L, the concentration of the organic pollutants in the organic wastewater is less than 0.5 mmol/L, and the oxidant is ozone, persulfate, peroxymonosulfate or hydrogen peroxide.
Preferably, the temperature of the oxidation-reduction reaction is 5-35 ℃ and the time is 5-120 min.
Preferably, the pH value of the organic wastewater is 3-10.
The invention provides carbon-three-nitrogen-four-load FeCo2S4The catalyst of nano particles comprises carbon three nitrogen four and catalyst loaded on the carbon three nitrogen fourFeCo of2S4A nanoparticle; the FeCo2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is (0.05-0.1): 1. the invention is realized by adding FeCo2S4Nanoparticles loaded on carbon-three-nitrogen-four and controlling FeCo2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is increased, and the FeCo is improved2S4The obtained catalyst has rich active sites due to the dispersibility of the nano particles, and has excellent electron conduction capability with carbon, nitrogen and carbon, and FeCo2S4The synergistic effect is generated, and the catalytic effect of the catalyst is further improved; the carbon, the nitrogen and the nitrogen contain six nitrogen arc pairs and can be used as an electron donor to be complexed with metal ions, so that the leaching of free metal ions can be reduced, and the harm to the environment can be avoided. The results of the examples show that the catalyst of the invention can remove 100% of carbamazepine in 15 minutes by using the catalyst for catalytic treatment of organic wastewater, and has good catalytic performance.
Drawings
FIG. 1 is an XRD pattern of a sample prepared in example 1;
fig. 2 is an SEM image of the sample prepared in comparative example 1.
Detailed Description
The invention provides carbon-three-nitrogen-four-load FeCo2S4Nanoparticle catalyst comprising carbon trinitrogen IV and FeCo supported on the carbon trinitrogen IV2S4And (3) nanoparticles.
In the present invention, the FeCo2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is (0.05-0.1): 1, preferably (0.05-0.08): 1. in the present invention, the FeCo2S4The particle size of the nano particles is preferably 150-250 nm, more preferably 200nm, and the particle size of the carbon-nitrogen-IV is preferably 8-12 μm, more preferably 10 μm.
The invention is realized by adding FeCo2S4Nanoparticles loaded on carbon-three-nitrogen-four and controlling FeCo2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is increased, and the FeCo is improved2S4The dispersibility of the nano particles, and the obtained catalyst has rich activitySex sites, and excellent electron conductivity due to carbon, three, and four, with FeCo2S4The synergistic effect is generated, and the catalytic effect of the catalyst is further improved; the carbon, the nitrogen and the nitrogen contain six nitrogen arc pairs and can be used as an electron donor to be complexed with metal ions, so that the leaching of free metal ions can be reduced, and the harm to the environment can be avoided.
The invention provides carbon-three-nitrogen-four-load FeCo in the scheme2S4A method for preparing a nanoparticle catalyst comprising the steps of:
calcining the carbon source in a nitrogen atmosphere to obtain carbon III-N IV;
dispersing the carbon, the nitrogen and the carbon into water to obtain a carbon, the nitrogen and the carbon dispersion liquid;
mixing the carbon three nitrogen four dispersion liquid with FeCl2、Co(NO3)2And NH4F, mixing, and carrying out hydrothermal reaction to obtain carbon III-N IV loaded with the Fe-Co compound;
mixing the Fe-Co compound-loaded carbon-nitrogen-IV with a sulfur source solution, and carrying out a vulcanization reaction to obtain carbon-nitrogen-IV-loaded FeCo2S4A catalyst of nanoparticles;
the FeCl2、Co(NO3)2、NH4The molar ratio of the F to the sulfur source in the sulfur source solution is 1:2:2: 10;
the carbon, the nitrogen and the carbon are mixed with FeCl2The dosage ratio of the components is 3.02 g: (0.5 to 1) mmol.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
According to the invention, the carbon source is calcined in a nitrogen atmosphere to obtain carbon III-N. In the present invention, the carbon source is preferably one or more of urea, melamine, dicyandiamide and dicyandiamide. In the invention, the calcining temperature is preferably 500-600 ℃, and more preferably 550 ℃; the time is preferably 3 h. In the calcining process, a carbon source reacts with nitrogen to generate carbon III, nitrogen IV. According to the invention, the obtained carbon, nitrogen and carbon four is preferably ground and then subjected to subsequent steps, the grinding degree is not particularly limited, and no granular sensation can be observed visually.
After the carbon-nitrogen-IV is obtained, the carbon-nitrogen-IV is dispersed into water to obtain a carbon-nitrogen-IV dispersion liquid, the dispersion mode is preferably ultrasonic, the ultrasonic condition is not specially required, and the uniform dispersion of the carbon-nitrogen-IV can be ensured.
After the carbon three nitrogen four dispersion liquid is obtained, the carbon three nitrogen four dispersion liquid and FeCl are mixed2、 Co(NO3)2And NH4And F, mixing, and carrying out hydrothermal reaction to obtain the Fe-Co compound-loaded carbon III-N IV. The present invention does not require any particular mixing means, and mixing means well known in the art may be used. The amounts of each are discussed below. In the embodiment of the invention, stirring and mixing are specifically carried out for 30 min. In the invention, the temperature of the hydrothermal reaction is preferably 130-150 ℃, and more preferably 140 ℃; the time is preferably 8-10 h, and more preferably 9 h. The hydrothermal reaction is preferably carried out in an autoclave lined with teflon. In the hydrothermal reaction process, FeCl is added2、Co(NO3)2And NH4F reacts to generate Fe-Co compound which is loaded on carbon III-N.
After the hydrothermal reaction is finished, the method preferably further comprises the steps of cooling the hydrothermal reaction product to room temperature, washing the hydrothermal reaction product with ethanol and deionized water in sequence, and then drying the hydrothermal reaction product in vacuum to obtain the Fe-Co compound-loaded carbon-nitrogen-III-IV. In the present invention, the number of ethanol washes is preferably 2; the number of deionized water washes is preferably 2. The invention has no special requirements on the vacuum drying condition, and the drying is carried out until the weight is constant.
After the carbon three nitrogen four of the load Fe-Co compound is obtained, the invention mixes the carbon three nitrogen four of the load Fe-Co compound with a sulfur source solution for carrying out a vulcanization reaction to obtain carbon three nitrogen four load FeCo2S4A catalyst of nanoparticles.
In the present invention, the sulfur source solution is preferably one of thioacetamide, sodium thiosulfate, sodium sulfide and thioureaIn the present invention, the concentration of the sulfur source solution is preferably 100 mmol/L. in the present invention, the amount of the sulfur source solution is such that the FeCl is satisfied2、 Co(NO3)2、NH4The molar ratio of the F to the sulfur source in the sulfur source solution is 1:2:2:10, and the carbon, the nitrogen, the carbon, the nitrogen and the FeCl are2The dosage ratio of the components is 3.02 g: (0.5 to 1) mmol. The present invention does not require any particular mixing means, and mixing means well known in the art may be used. In the invention, the temperature of the vulcanization reaction is preferably 140-170 ℃, and more preferably 150-160 ℃; the time is preferably 5-7 h, and more preferably 6 h. In the vulcanization reaction process, the Fe-Co compound is subjected to vulcanization reaction on the surface of the carbon-nitrogen-III-IV to form Fe-Co sulfide, so that carbon-nitrogen-III-IV-loaded FeCo is formed2S4A catalyst of nanoparticles.
After the sulfuration reaction is finished, the invention preferably further comprises the steps of cooling the obtained reaction product to room temperature, and collecting carbon-three-nitrogen-four-loaded FeCo2S4Washing and vacuum drying the catalyst of nano particles to obtain the carbon-three-nitrogen-four-loaded FeCo2S4A catalyst of nanoparticles. The method of collection is not particularly required in the present invention, and a collection method well known in the art may be used. The washing and vacuum drying process of the present invention is not particularly required, and a washing and vacuum drying process well known in the art may be used.
The invention provides carbon-three-nitrogen-four-load FeCo in the scheme2S4Catalyst of nano particles or carbon-nitrogen-four-loaded FeCo prepared by the preparation method in the scheme2S4Use of a nanoparticle catalyst for the treatment of organic wastewater.
In the invention, the pH value of the organic wastewater is preferably 3-10, more preferably 4-9. the invention has no special requirement on the types of organic pollutants in the organic wastewater, and the organic pollutants known in the art can be any, and can be specifically but not limited to antibiotics and pesticides.
In the present invention, the method of application preferably comprises: loading carbon, three nitrogen and four with FeCo2S4Mixing the catalyst of the nano particles, the oxidant and the organic wastewater to carry out oxidation-reduction reaction.
In the invention, the carbon-three-nitrogen-four-load FeCo2S4The concentration of the nanoparticle catalyst in the organic wastewater is preferably 5-500 mg/L, more preferably 50-400 mg/L, and further preferably 100-300 mg/L, the concentration of the oxidant in the organic wastewater is preferably 0.05-5 mmol/L, more preferably 0.1-4.5 mmol/L, and further preferably 1-3.5 mmol/L, the ratio of the molar concentration of the oxidant in the organic wastewater to the molar concentration of the organic pollutant is preferably 0.1-10: 1, and more preferably 1-8: 1.
The invention has no special requirement on the mixing mode, and carbon, three and nitrogen and four-load FeCo are directly added2S4Adding the catalyst and the oxidant of the nano particles into the organic wastewater.
In the invention, the temperature of the oxidation-reduction reaction is preferably 5-35 ℃, and the time is preferably 5-120 min. The redox reaction according to the invention is preferably carried out under stirring. The present invention does not require any particular speed of agitation, and can employ agitation speeds well known in the art.
In the oxidation-reduction reaction process, carbon, three and nitrogen four load FeCo2S4The nano particles are used as a catalyst, and a catalytic oxidant generates active free radicals to oxidize organic pollutants in the organic wastewater into non-toxic small molecular substances.
The following examples are provided to illustrate the carbon-nitrogen-loaded FeCo of the present invention2S4The preparation and use of the nanoparticle catalyst are described in detail, but they should not be construed as limiting the scope of the invention.
Example 1
FeCo2S4The preparation method of the carbon-nitrogen-rich material comprises the following steps:
using urea as raw material, heating at 550 ℃ for 3h under nitrogen atmosphere to prepare carbon-nitrogen-IV, grinding the prepared carbon-nitrogen-IV to obtain carbon-nitrogen-IV powder, adding 3.02g of the carbon-nitrogen-IV powder into 50m L water and carrying out ultrasonic treatment for 30min to obtain a uniform solution, and then adding 0.5mmol of FeCl2、1mmol Co(NO3)2And 1mmol NH4Adding F into the solution mixed with the carbon-nitrogen-tetrapowder, mixing for 30 minutes at 25 ℃, transferring the mixture to a 100m L Teflon-lined autoclave after mixing, heating for 9 hours at 140 ℃, washing for multiple times by deionized water and ethanol after cooling to room temperature, then drying for 6 hours under vacuum at 60 ℃ to obtain the Fe-Co complex-loaded carbon-nitrogen-tetrapowder, uniformly mixing the obtained Fe-Co complex-loaded carbon-nitrogen-tetrapowder with 50m L100 mmo/L thioacetamide solution, then transferring the mixture to a 100m L polytetrafluoroethylene-lined autoclave, heating for 6 hours at 160 ℃, taking back the catalyst after cooling to room temperature, washing and drying at 60 ℃ overnight to obtain FeCo2S4FeCo in carbon-three-nitrogen-four material2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is 0.05: 1.
for carbon three nitrogen four-loaded FeCo prepared in example 12S4The nano-particle catalytic material is detected by X-ray diffraction (XRD), the result is shown in figure 1, and carbon, three and nitrogen and four-loaded FeCo2S4The peaks of the nanoparticle material matched the peaks corresponding to JCPDS cards 47-1738. However, the peak position was slightly shifted in the direction of 2. theta. height, indicating that Co was partially substituted with Fe3S4Co element in (1) to generate FeCo2S4And maintain Co3S4The crystal structure of (1). Prove FeCo2S4Formed on carbon three nitrogen four.
FeCo loaded with carbon, three nitrogen and four by SEM2S4The catalytic material of the nanoparticles was detected, and the result is shown in FIG. 2, in which the spherical FeCo2S4The particles are generated on the carbon-nitrogen-carbon four material to form a nano flower-shaped structure, which shows that the material has rich active sites and can be fully contacted with an oxidant. Furthermore, from FIG. 1, it can also be seen that FeCo2S4The particle size of the particles was about 200nm and the particle size of C, N, C, D was about 10 μm.
Example 2
The difference from example 1 is that FeCl2、Co(NO3)2、NH4The amounts of F and the solution of the thioacetamide used were 0.75mmol, 1.5mmol and 75m L (100 mmol/L), the remainder being FeCo obtained in example 12S4FeCo in carbon-three-nitrogen-four material2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is 0.075: 1.
XRD and SEM characterization of the catalytic material prepared in example 2 was performed, and the results were similar to those of example 1. XRD results showed FeCo2S4Formed on C, N, and SEM results show that spherical FeCo2S4The particles are generated on the carbon-nitrogen-carbon four material to form a nano flower-shaped structure, which shows that the material has rich active sites and can be fully contacted with an oxidant.
Comparative example 1
The preparation of the carbon, three and four nitrogen material comprises the following steps:
heating urea as raw material at 550 deg.C for 3 hr in nitrogen atmosphere to prepare carbon-nitrogen-IV, and grinding the prepared carbon-nitrogen-IV.
Comparative example 2
FeCo2S4The preparation of the material comprises the following steps:
adding 0.5mmol FeCl2、1mmol Co(NO3)2And 1mmol NH4F was added to a 50m L solution, mixed for 30 minutes at 25 ℃, transferred after mixing to a 100m L teflon lined autoclave, heated at 140 ℃ for 9 hours, after cooling to room temperature, washed several times with deionized water and ethanol, and then dried under vacuum at 60 ℃ for 6 hours, the Fe-Co complex obtained was mixed well with a 50m L100 mmol/L thioacetamide solution, then transferred to a 100m L teflon lined autoclave, heated at 160 ℃ for 6 hours, after cooling to room temperature, the catalyst was withdrawn, washed and dried at 60 ℃ overnight.
Application example
Carbon, three nitrogen and fourMaterial loaded FeCo2S4The application of the nano-particle catalyst in the aspect of water treatment is verified by the following tests:
adding six groups of different substances into the water to be treated, reacting for a period of time, precipitating and filtering, separating out the catalyst to obtain effluent, and finishing the water treatment process.
In which PMS (peroxymonosulfate) was selected as the oxidant to verify the performance of the catalyst of the present invention. Six groups of tests are respectively carried out, wherein the first group is a single PMS, and the second group is a single FeCo2S4C-three N four (prepared in example 1), third group being FeCo2S4C-Trinitrotetra (prepared in example 1) + PMS, fourth group of FeCo2S4+ PMS, a fifth group of C, N, and IV + PMS, and a sixth group of FeCo2S4Trinitrotetra carbon (prepared in example 2) + PMS. All conditions were the same except for the reagents and catalysts added as described above.
Taking a carbamazepine solution as a simulated pollutant, taking 150m L15 mu mol/L carbamazepine solution, placing the solution in a beaker, adding the six groups of different substances, taking the reaction solution at a specified reaction time, filtering the reaction solution by a filter membrane, adding Na which is placed with a terminator in advance and has a concentration of 0.3 mmol/L, wherein the reaction conditions are that the initial pH is 6.5, the concentration of a catalyst is 30 mg/L, and the concentration of PMS is 0.3 mmol/L2S2O3The degradation rate of CBZ can be obtained by measuring the concentration of CBZ (personal care drug carbamazepine) in the sample using high performance liquid chromatography.
The results show that when the reaction time is 15 minutes, the CBZ is degraded by 9.1% in the presence of PMS alone in the first group, and FeCo in the second group2S4C-III-N-IV adsorbed only 4.2% of CBZ, and a third group of FeCo2S4the/C, N, C and N activated PMS can remove 84.5 percent of CBZ and the sixth group of FeCo2S4the/C-N-activated PMS can remove 100% of CBZ, and the fourth group of FeCo2S4Activated PMS removed only 40.5% of CBZ, and group five carbon, three nitrogen, four activated PMS removed only 12.5% of CBZ. The results show FeCo2S4the/C-N-C material has the property of stronger catalytic performance and can degrade in the process of activating PMSHas better application potential in organic pollutants.
As can be seen from the above embodiments, the present invention provides a carbon-three-nitrogen-four-loaded FeCo2S4Catalyst of nanoparticles, preparation method and application thereof, prepared by mixing FeCo2S4The nano particles are loaded on carbon, nitrogen and nitrogen, and FeCo is improved2S4The dispersibility of the nano particles can reduce the leaching of free metal ions, and the obtained catalyst has good catalytic performance and can remove organic pollutants in water by high-efficiency catalytic oxidation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Carbon-three-nitrogen-four-load FeCo2S4A nanoparticle catalyst, comprising carbon-three-nitrogen-four and FeCo supported on the carbon-three-nitrogen-four2S4A nanoparticle; the FeCo2S4The mass ratio of the nano particles to the carbon, the nitrogen and the carbon is (0.05-0.1): 1.
2. the carbon-nitrogen-triple-supported FeCo of claim 12S4A method for preparing a nanoparticle catalyst comprising the steps of:
calcining the carbon source in a nitrogen atmosphere to obtain carbon III-N IV;
dispersing the carbon, the nitrogen and the carbon into water to obtain a carbon, the nitrogen and the carbon dispersion liquid;
mixing the carbon three nitrogen four dispersion liquid with FeCl2、Co(NO3)2And NH4F, mixing, and carrying out hydrothermal reaction to obtain carbon III-N IV loaded with the Fe-Co compound;
mixing the Fe-Co compound-loaded carbon-nitrogen-IV with a sulfur source solution, and carrying out a vulcanization reaction to obtain carbon-nitrogen-IV-loaded FeCo2S4A catalyst of nanoparticles;
the FeCl2、Co(NO3)2、NH4The molar ratio of the F to the sulfur source in the sulfur source solution is 1:2:2: 10;
the carbon, the nitrogen and the carbon are mixed with FeCl2The dosage ratio of the components is 3.02 g: (0.5 to 1) mmol.
3. The method according to claim 2, wherein the carbon source is one or more of urea, melamine, cyanamide and dicyandiamide;
the sulfur source in the sulfur source solution is one or more of thioacetamide, sodium thiosulfate, sodium sulfide and thiourea.
4. The preparation method according to claim 2, wherein the hydrothermal reaction is carried out at a temperature of 130 to 150 ℃ for 8 to 10 hours.
5. The preparation method according to claim 2, wherein the temperature of the vulcanization reaction is 140-170 ℃ and the time is 5-7 h.
6. The carbon-nitrogen-triple-supported FeCo of claim 12S4Catalyst of nano particles or carbon-nitrogen-four-loaded FeCo prepared by the preparation method of any one of claims 2 to 52S4Use of a nanoparticle catalyst for the treatment of organic wastewater.
7. The application according to claim 6, wherein the method of applying comprises: loading carbon, three nitrogen and four with FeCo2S4Mixing the catalyst of the nano particles, the oxidant and the organic wastewater to carry out oxidation-reduction reaction.
8. Use according to claim 7, wherein said carbon-nitrogen-triple-supported FeCo2S4The concentration of the nano-particle catalyst in the organic wastewater is 5-500 mg/L, the concentration of the oxidant in the organic wastewater is 0.05-5 mmol/L, and the catalyst isThe concentration of organic pollutants in the organic wastewater is less than 0.5 mmol/L, and the oxidant is ozone, persulfate, peroxymonosulfate or hydrogen peroxide.
9. The use according to claim 7, wherein the temperature of the redox reaction is 5-35 ℃ and the time is 5-120 min.
10. The use according to claim 6 or 7, wherein the organic wastewater has a pH of 3 to 10.
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