CN110420655B - Preparation method and application of graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst - Google Patents
Preparation method and application of graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst Download PDFInfo
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- CN110420655B CN110420655B CN201910690815.XA CN201910690815A CN110420655B CN 110420655 B CN110420655 B CN 110420655B CN 201910690815 A CN201910690815 A CN 201910690815A CN 110420655 B CN110420655 B CN 110420655B
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Abstract
The invention relates to the technical field of preparation of solid-phase Fenton catalysts, and particularly discloses a preparation method of a graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst and application of the graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst in treatment of organic wastewater. The preparation method of the catalyst comprises the following steps: mixing and melting a carbon source and a nitrogen source according to a certain proportion, then adding an iron source according to a certain proportion, fully stirring and dissolving, transferring the mixture to a drying oven at 150-180 ℃ for drying for 12-24 h, and then calcining under the protection of nitrogen atmosphere to obtain the iron-based catalyst. The catalyst prepared by the invention is FeN and Fe coated by graphite carbon3C coexisting iron-nitrogen-carbon catalyst, the size of the nano particles is 5-30 nm, and the specific surface area of the catalyst is 80-300 m2(ii)/g, wherein FeN is the main active site for decomposing hydrogen peroxide. The catalyst can be applied to electro-Fenton and Fenton systems to treat organic wastewater with the pH value ranging from 3 to 9. The preparation method has the advantages of simple steps, easily obtained raw materials, excellent performance, high stability and recycling.
Description
Technical Field
The invention relates to the technical field of preparation of solid-phase Fenton catalysts, in particular to a preparation method of a graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst and application of the graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst in treatment of organic wastewater.
Background
Fenton reaction (Fenton reaction) is used as an advanced oxidation technology and mainly refers to the utilization of Fe2+Catalytic decomposition of H2O2The process of generating a product OH (2.8eV) having a highly oxidative radical is shown in the formula (1). Fe2+And H2O2Referred to as Fenton reagent.
Fe2++H2O2+H+→Fe3++H2O+·OH (1)
The Fenton method is widely researched because a large amount of high-activity OH can be generated, and organic wastewater can be efficiently degraded and treated, and at present, common Fenton methods comprise electro-Fenton, photo-Fenton, homogeneous Fenton, solid-phase Fenton and the like. In general, these methods can be categorized into two major directions: (1) h2O2The generation and utilization efficiency is improved, such as electro-Fenton; (2) fe catalytic decomposition and cycle performance improvement, such as solid-phase Fenton. Solid-phase Fenton is the decomposition of H by using solid2O2The general name of the reaction for generating free radicals aims at solving the problem of Fe in the homogeneous Fenton technology2+The method has the problems of no circulation, easy sludge generation, pH limitation on application and the like. Researches report that the main component of the solid-phase Fenton catalyst is Fe2O3、Fe3O4、CuFeO2Similar to hematite and the like, the main action mechanism of the catalyst is that Fe in a solid catalyst is dissolved out in a solution phase to form Fe2+To H2O2Catalytic decomposition of Fe produced after reaction3+Adsorbed on the solid phase surface and reduced to form Fe2+And realizing iron circulation. The mechanism can improve the Fe circulation or the problem of limited pH application to a certain extent, but still has the problems of easy flocculation to form sludge after Fe is dissolved out, narrow pH application range, poor stability and catalyst circulation performance and the like, thereby limiting the application of the technology. From the viewpoint of the technical development of solid-phase Fenton catalyst, how to promote H simultaneously2O2The main challenges of generating and decomposing catalytic activity, promoting Fe circulation, improving the problem of pH limitation and improving the stability of the catalyst are faced.
The literature reports that after being modified by PTFE, an iron-carbon catalyst (FeC) can improve the Fe dissolution problem, broaden the pH application window of the solid-phase Fenton catalyst, better degrade and mineralize organic pollutants, greatly improve the stability and the recycling performance (15-time recycling effect) of the catalyst, but have low catalytic activity, so that a large amount of catalyst (6g/L) needs to be added to improve the treatment effect.
Graphite carbon coated iron carbide catalyst (Fe)3C/Fe5C2The @ Graphite C) is proved to show better catalytic activity and stability in other catalytic technology (C1 chemical or electrochemical reduction) fields, such as Fischer-Tropsch synthesis, zinc-air batteries and catalytic Persulfate (PMS) systems, and the Graphite carbon coated with the outer layer can play double roles of transferring electrons and protecting active sites, and shows higher activity and stability. In addition, nitrogen-doped iron-carbon (Fe-N-C) catalysts in O2Reduction of four electrons to OH-The research shows that the existence of Fe-N site has obvious effect on improving the catalytic efficiency because of the Fe-N sitexThe sites can improve the electron cloud density on the surface of the material on the interface where the catalytic reaction occurs, improve the adsorption rate of reactants and play a role in improving the catalytic activity. But whether it is Fe3Decomposition of H with C @ C or Fe-N-C as solid phase Fenton catalyst2O2The research of the method has not been reported clearly, and the performance and the mechanism of the method are not clear. At present, graphite carbon coated Fe has been reported3The synthesis method of the C catalyst is mostly obtained by compounding graphene, carbon nanotubes and iron phthalocyanine and then carrying out a series of complex steps, and the cost is high.
The catalyst synthesis method with coexisting iron-nitrogen active sites or iron-nitrogen species and carbon-iron species needs to be further developed, and H is treated2O2The role of decomposition remains to be investigated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst, wherein the catalyst simultaneously contains Fe3The sizes of the C and FeN nanoparticles are 5-30 nm (particle size), and the specific surface area of the catalyst is 80-300 cm2(preferably 200 to 300 cm)/g2/g) mesoporous structures being present in the catalyst. The prepared catalyst is used as a solid-phase Fenton catalyst for H in Fenton reaction2O2The organic wastewater is treated by catalytic decomposition and degradation. The method has the advantages of cheap and easily obtained required reagents, simple synthesis method and steps and high stability of the prepared catalyst.
The catalyst prepared by the method is used asSolid phase Fenton's catalyst, catalytic decomposition of H2O2The efficiency is high, the graphite carbon coating effectively prevents Fe from dissolving out, the catalyst shows better stability and cyclability, and the pH application range is wide.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst is prepared by the following steps:
mixing a carbon source and a nitrogen source according to a certain proportion, heating and melting (preferably 100-150 ℃), adding an iron source, fully stirring and dissolving, transferring to a 150-180 ℃ oven for drying for 12-24 h, and calcining under the protection of nitrogen atmosphere to obtain the iron-nitrogen-carbon solid-phase Fenton catalyst.
Further, the carbon source is selected from any one of saccharides such as glucose, fructose, sucrose and chitosan;
the nitrogen source refers to urea, and the molar ratio of the carbon source to the nitrogen source is 1: (5-11), preferably 1: (8-11).
Further, the iron source is selected from any one of ferric nitrate, ferric chloride, ferric acetylacetonate and iron phthalocyanine, and in the prepared catalyst, the weight of the iron element accounts for 20-60% of the mass of the catalyst, and preferably 20-50%.
Further, the calcination temperature under the protection of nitrogen atmosphere is 700-900 ℃, and the calcination time is 2-4 h.
An application of graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst in treating organic wastewater.
Adding the graphite carbon-coated iron-nitrogen-carbon catalyst into organic wastewater under different pH environments, wherein the application range comprises Fenton reactions such as a common Fenton method and an electro-Fenton method, and the pH range is 3-9;
the concentration of the catalyst used in the organic wastewater is more than 0.3g/L, preferably 0.4g-1.0 g/L.
The organic wastewater comprises chlorophenol compounds, dye compounds and/or endocrine disruptor compounds;
the chlorophenols comprise 2-cp, 3-cp, 4-cp, 2,4-dcp and/or 2,4, 6-tcp;
the dye compound comprises X3B and/or acid orange;
the endocrine disruptor compound refers to methyl phthalate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the raw materials related by the invention are easy to obtain, the cost is low, and the synthesis steps are simple.
2. In the process of preparing the catalyst, the invention synthesizes Fe coated by graphite carbon by controlling the proportion of the carbon source and the nitrogen source3C and FeN coexisting nano-particle catalyst.
3. Graphite carbon coated Fe synthesized by the invention3The C and FeN coexisting nano-particle catalyst has excellent performance in a Fenton system, wherein FeN is a main active site for decomposing hydrogen peroxide, graphite carbon protects the stability of particles, and Fe3C synergizes with the active site to promote the decomposition.
4. The catalyst prepared by the invention is used for decomposing H in a Fenton system2O2The method generates free radicals, degrades organic pollutants within the range of pH 3-9, has excellent performance and high stability, and can be recycled.
Drawings
FIG. 1(A), FIG. 1(B), FIG. 1(C), FIG. 1(D) are respectively TEM images of the catalyst C prepared in example 4 and FeNC @ C-20 prepared in example 2, FeNC @ C-35 prepared in example 1, and FeNC @ C-50 prepared in example 3.
FIG. 2 is a particle size distribution diagram of the catalyst prepared in example 1.
FIG. 3 is a high resolution transmission electron microscope image of the FeNC @ C-35 catalyst prepared in example 1.
FIG. 4 is a scanning electron micrograph and elemental distribution of the FeNC @ C-35 catalyst prepared in example 1.
Fig. 5 is a high-resolution transmission electron microscope image of the catalysts prepared in example 5 (fig. 5A), example 6 (fig. 5B), and example 7 (fig. 5C).
FIG. 6 is an X-ray diffraction pattern (XRD pattern) of FeNC @ C catalysts of varying iron content prepared in examples 1-3 versus catalyst C prepared in example 4.
FIG. 7 is a graph of the desorption by physical adsorption of FeNC @ C catalysts of varying iron content prepared in examples 1-3 versus catalyst C prepared in example 4.
FIG. 8 is a high resolution X-ray photoelectron spectroscopy (XPS) of the N element in the FeNC @ C-35 catalyst prepared in example 1.
Figure 9 is a graph of the kinetics of 2-cp degradation in the electro-Fenton system (pH 3) for FeNC @ C catalysts of different iron contents prepared in examples 1-3 and catalyst C prepared in example 4.
FIG. 10 is a graph of the kinetics of 2-cp degradation in the electro-Fenton system at various pH conditions for the FeNC @ C-35 catalyst prepared in example 1.
Fig. 11 is a fluorescence spectrum of hydroxyl radical generation in the electro-Fenton system at pH3 for the FeNC @ C-35 catalyst prepared in example 1.
FIG. 12 shows the generation of H by the FeNC @ C-35 catalyst prepared in example 1 before and after poisoning by KSCN in an electro-Fenton system (pH 3)2O2A comparative graph of (a).
FIG. 13 is a graph of the 2-cp degradation for recycle of the FeNC @ C-35 catalyst prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to the following specific examples:
example 1
A graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst is prepared by the following steps:
1) 3g of glucose was mixed with 8g of urea (molar ratio of carbon source to nitrogen source 1: 8) heating and melting to be clear at 150 ℃, adding 3.03g of ferric nitrate nonahydrate, stirring until the ferric nitrate nonahydrate is completely dissolved, transferring the mixture into an oven at 180 ℃ for drying for 12 hours, and then calcining for 2 hours at 750 ℃ under the protection of nitrogen atmosphere to obtain the graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst, wherein the mass fraction of Fe element in the synthesized catalyst is 35%, and the synthesized catalyst is marked as FeNC @ C-35.
Example 2
A graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst is prepared by the following steps:
mixing 3g of glucose and 5g of urea (the molar ratio of a carbon source to a nitrogen source is 1: 5), heating and melting at 150 ℃ until the mixture is clear, adding 1.73g of ferric nitrate nonahydrate, stirring until the ferric nitrate nonahydrate is completely dissolved, transferring the mixture into an oven at 180 ℃ for drying for 12 hours, and then calcining the dried mixture for 2 hours at 750 ℃ under the protection of nitrogen atmosphere to obtain the graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst, wherein the mass fraction of Fe element in the synthesized catalyst is 20%, and the synthesized catalyst is marked as FeNC @ C-20.
Example 3
A graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst is prepared by the following steps:
mixing 3g of glucose and 11g of urea (the molar ratio of a carbon source to a nitrogen source is 1: 11), heating and melting at 150 ℃ until the mixture is clear, adding 4.32g of ferric nitrate nonahydrate, stirring until the ferric nitrate nonahydrate is completely dissolved, transferring the mixture into an oven at 180 ℃ for drying for 24 hours, and then calcining the dried mixture for 2 hours at 750 ℃ under the protection of nitrogen atmosphere to obtain the graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst, wherein the mass fraction of Fe element in the synthesized catalyst is 50%, and the synthesized catalyst is marked as FeNC @ C-50.
Example 4
A graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst is prepared by the following steps:
mixing 3g of glucose and 11g of urea (the molar ratio of a carbon source to a nitrogen source is 1: 11), heating and melting at 150 ℃ until the mixture is clear, transferring the mixture into an oven at 180 ℃ for drying for 12h, and then calcining at 750 ℃ for 2h under the protection of nitrogen atmosphere, wherein the synthesized catalyst is named as C.
Example 5
A graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst is prepared by the following steps:
mixing fructose 3g and urea 11g (molar ratio of carbon source to nitrogen source is 1: 11), heating and melting at 150 deg.C to clarify, adding ferric chloride hexahydrate 2.1g, stirring to dissolve completely, drying in oven at 150 deg.C for 24 hr, calcining at 750 deg.C under protection of nitrogen atmosphereObtaining a graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst after 2h, wherein the mass fraction of Fe element in the synthesized catalyst is 35%, and the specific surface area is 250m2The grain diameter is 5-30 nm.
Example 6
A graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst is prepared by the following steps:
mixing 2.85g of sucrose and 5g of urea (the molar ratio of a carbon source to a nitrogen source is 1: 10), heating and melting at 150 ℃ until the mixture is clear, adding 2.5g of ferric acetylacetonate, stirring until the mixture is completely dispersed, transferring the mixture into an oven at 180 ℃ for drying for 12 hours, and calcining the dried mixture at 750 ℃ for 2 hours under the protection of nitrogen atmosphere to obtain a graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst, wherein the mass fraction of Fe element in the synthesized catalyst is 35%, and the specific surface area is 262m2(ii)/g, the particle size range is 5-30 nm.
Example 7
A graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst is prepared by the following steps:
mixing 3g of chitosan and 9g of urea (the molar ratio of a carbon source to a nitrogen source is 1: 8), heating and melting at 150 ℃ until the mixture is clear, adding 4.3g of iron phthalocyanine, stirring until the mixture is completely dispersed, transferring the mixture into an oven at 180 ℃ for drying for 12h, and calcining the dried mixture at 750 ℃ for 2h under the protection of nitrogen atmosphere to obtain the graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst, wherein the mass fraction of Fe element in the synthesized catalyst is 35%, and the specific surface area is 281m2(ii)/g, the particle size range is 5-30 nm.
From the TEM morphology results (fig. 1), the catalyst C (fig. 1(a)) does not contain nanoparticles and has a distinct pore structure, compared with the FeNC @ C catalysts with different iron contents (fig. 1(B) (C) (D)), the particle size distribution is between 5nm and 30nm, the dispersion is uniform, the mean particle size of the FeNC @ C-35 catalyst is about 15.1nm (see fig. 2), and the particle size distribution and the size of the catalysts prepared in other examples of the present invention have no significant difference. In addition, the results of the high resolution TEM (FIG. 3) of the FeNC @ C-35 catalyst show that the catalyst has graphite carbon coating on the outer layer and Fe in the inner part3C. FeN two different nanoparticles.
From the results of the morphology and the element distribution of the FeNC @ C-35 catalyst prepared in example 1 (FIG. 4), the catalyst contains three elements of Fe, N and C, and the distribution is relatively uniform.
HRTEM (FIG. 5) results of the catalysts prepared in examples 5-7 show that by adjusting the type of carbon source and the ratio of the carbon source to the nitrogen source, FeNC @ C catalysts with similar morphology and similar particle size can still be prepared.
XRD results of the catalysts shown in FIG. 6 indicate that the FeNC @ C-20, FeNC @ C-35 and FeNC @ C-50 catalysts mainly contain graphite carbon, FeN (JSPDS NO.88-2153), Fe3C (JSPDS NO.35-0772) and a small amount of Fe0(JSPDS NO.06-0696) and the like.
The nitrogen adsorption and desorption curve of the catalyst is shown in figure 7, and the physical structure parameters are shown in table 1. Due to the introduction of Fe, an obvious hysteresis loop appears on a physical adsorption and desorption curve of the catalyst, and the existence of a mesoporous structure is prompted. With the increase of Fe content, the specific surface area of the catalyst tends to increase and then decrease, and the pore diameter slightly increases with the increase of the loading amount. The change of Fe content directly causes the phase, morphology and structure of the catalyst to change, and influences the adsorption and desorption behaviors and mass transfer efficiency of substances on the surface of the catalyst, thereby influencing the catalytic performance.
TABLE 1 physical Structure parameters of FeNC @ C catalysts of different Fe contents
The high-resolution electron spectrum XPS analysis of the N element in the catalyst shows that Fe-N (399.57eV) exists on the surface of the catalyst, and further confirms that FeN exists in the catalyst, as shown in FIG. 8.
From the above characterization results, it can be confirmed that FeN and Fe coated with graphite carbon can be prepared by the method of the present invention3C iron nitrogen carbon catalyst coexisting with nano particles.
Test example 1
The FenC @ C catalysts with different iron contents prepared in examples 1-3 and the catalyst C prepared in example 4 are applied to an electro-Fenton system, and 2-chlorophenol (2-cp) is used as a simulated pollutant for degradation, and the specific method is as follows:
the degradation method of the pollutants comprises the following steps: the electrochemical conditions used were: the graphite plate of 4cm by 4cm is used as a cathode and an anode, a saturated calomel electrode is used as a reference electrode, the working voltage is-0.6V, and the oxygen flow rate is 0.3L/min. In a solution system with 50ml of pH of 3.0/7.0/9.0, the concentration of the contained simulated pollutants is 0.2mmol/L, and Na2SO4The concentration of the electrolyte is 0.1mol/L, the concentration of the catalyst is 0.5g/L, and the calculation formula of the pollutant degradation rate is as follows: (c) degradation rate0-ct)/c0Wherein c is0Refers to the initial concentration of the contaminant, ctRefers to the concentration of the contaminant after it has been degraded at time t.
Detection method of hydroxyl free radical: the catalyst used was the FeNC @ C-35 catalyst prepared in example 1.
1) And (3) testing a system: 50mL of 0.1mol/L sodium sulfate (Na)2SO4) The solution used as electrolyte contains 0.5mmol/L coumarin, pH 3.0, oxygen flow rate of 0.3L/min, and catalyst amount of 0.5 g/L.
2) And (3) testing conditions are as follows: the CHI-660E electrochemical workstation provided-0.6V using a three-electrode system (4 cm by 4cm graphite plates as cathode and anode, saturated calomel electrode as reference electrode). Coumarin with the concentration of 0.5mol/L is used as a molecular fluorescent probe, and the relative yield of hydroxyl radicals is detected by adopting an analytical fluorescence method.
The detection method of hydrogen peroxide produced by electro-Fenton comprises the following steps: 1) and (3) testing a system: 50mL of sodium sulfate (Na) with a concentration of 0.1mol/L2SO4) The solution was used as an electrolyte, pH 3.0, and oxygen flow rate was 0.3L/min. 2) And (3) testing conditions are as follows: the CHI-660E electrochemical workstation provided-0.6V using a three-electrode system (4 cm by 4cm graphite plates as cathode and anode, saturated calomel electrode as reference electrode). Hydrogen peroxide was detected using the titanium potassium oxalate method: mixing water and titanium reagent (0.05mol/L titanium potassium oxalate and 3mol/L sulfuric acid are mixed according to the volume ratio of 1: 1) according to the volume ratio of 1:3, and taking 2mL of the mixed solution to the ratioIn the cuvette, 0.5mL of the sample taken out of the test system was further added to the cuvette, shaken up, and measured at a maximum absorption wavelength of 400 nm. Stability test: the specific method is referred to the method for degrading contaminants described in the experimental example, wherein the pH is 3.0. After the catalyst is used, the catalyst is washed for 3 times by distilled water and is used for the next time after being naturally dried.
From the experimental results (see fig. 9), the catalysts prepared according to examples 1-3 were added in place of Fe in an electro-Fenton system at pH32+The catalyst has the catalytic action that the FeNC @ C-x (x is 20, 35 and 50) catalyst can efficiently degrade 2-cp, wherein the performance of the FeNC @ C-35 system is optimal, and the degradation rate of the 2-cp reaches more than 99 percent after the reaction is carried out for 30 min.
As shown in FIG. 10, the FenC @ C-35 is applied to an electric Fenton system under different pH environments to degrade 2-cp, and the experimental result shows that: the FeNC @ C-35 can effectively degrade 2-cp within the pH range of 3-9, and the catalyst has a wider pH application window.
As shown in figure 11, 7-hydroxycoumarin is generated by coumarin in solution under the action of OH, a fluorescence signal appears at 450nm, and the signal is remarkably enhanced along with the change of time, which indicates that OH is H in an electro-Fenton system by a FeNC @ C-35 catalyst2O2The main product of the decomposition.
The catalyst used was FeNC @ C-35 prepared in example 1, C prepared in example 4, in an amount of 0.5g/L, and a catalyst blank was used as a control. Further, active sites of the catalyst are explored, and SCN is considered in combination with literature reports-Has toxic action on FeN sites. On the basis of the method for detecting hydrogen peroxide in the test example, H accumulated and generated in an electric Fenton system is detected by comparing whether the system contains 0.05mol/L of KSCN or not2O2The effect of (b) indirectly verifies the effect of the active site. From the experimental results (FIG. 12), SCN was observed in the presence of 0.05mol/LKSCN in the system-After FeN is poisoned, FeN loses the effect, and after the reaction is carried out for 120min, the concentration of hydrogen peroxide (FeNC @ C-35+ KSCN) in the system is 4 times of that of the hydrogen peroxide which is not poisoned (FeNC @ C-35), further explaining that FeN is decomposed by a FeNC @ C-35 catalystHydrogen peroxide generates the primary active site of hydroxyl radicals.
The stability test method provided by the test example is used for carrying out a circulation test, the result is shown in FIG. 13, and it can be seen that the FeNC @ C-35 catalyst has good circulation performance, and still shows good 2-cp degradation performance after 5 times of circulation.
Test example 2
The FenC @ C catalysts with different iron contents prepared in examples 1-3 and the catalyst C prepared in example 4 are applied to a Fenton system, and methyl phthalate (DMP) is used as a simulated pollutant for degradation, and the specific method is as follows:
the degradation method of the simulated pollutants in the test example comprises the following steps: in a solution system with 50ml of pH of 3.0, the concentration of the simulated pollutant is 0.2mmol/L, and H2O2The concentration of (2) is 2mmol/L, the concentration of the added catalyst is 0.5g/L, and the calculation formula of the pollutant degradation rate is as follows: (c) degradation rate0-ct)/c0Wherein c is0Refers to the initial concentration of the contaminant, ctRefers to the concentration of the contaminant after it has been degraded at time t.
FeNC @ C catalysts with different iron contents can be used as solid-phase Fenton catalysts to catalytically decompose hydrogen peroxide and DMP. After the reaction is carried out for 12min, the degradation rates of FeNC @ C-20, FeNC @ C-35 and FeNC @ C-50 systems are respectively 70.5%, 97.2% and 99.5%. The efficiency of DMP degradation increases with increasing iron content in the catalyst.
In addition, there is literature indicating that the FeN site in the catalyst can be SCN-On the basis of the method system for degrading pollutants described in the test example, DMP can not be degraded basically under the condition that the concentration in the system is 0.05mol/LKSCN, and the reduction rate of the concentration of DMP is less than 20 percent after 120min of reaction. Thereby indirectly proving that the FeN species has decomposition H in a Fenton system2O2Free radicals are generated, and organic pollutants are degraded.
Test example 3
The graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalysts prepared in examples 1 and 5 to 7 were used for degrading 2-cp in an electro-Fenton system, and the degradation rate obtained in 120min was used as an index in the same manner as in test example 1 under the condition that the pH was 3.0/7.0, and the results are shown in table 2. The catalyst of the invention can better degrade organic matters in both acidic environment and neutral environment.
TABLE 2 degradation Rate results for different catalysts degrading 2-cp at different pH
Claims (4)
1. The application of a graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst in treating organic wastewater;
the pH range of the organic wastewater is 3-9;
the application range is an electro-Fenton method;
the preparation method of the graphite carbon-coated iron-nitrogen-carbon solid-phase Fenton catalyst comprises the following steps: mixing a carbon source and a nitrogen source according to a certain proportion, heating to 150 ℃ for melting, adding an iron source according to a certain proportion, fully stirring and dissolving, transferring the mixture to a 150-180 ℃ oven for drying for 12-24 h, and calcining under the protection of nitrogen atmosphere to obtain an iron-nitrogen-carbon solid-phase Fenton catalyst;
the catalyst contains Fe3C and FeN nanoparticles;
the molar ratio of the carbon source to the nitrogen source is 1: (5-11);
in the prepared catalyst, the weight of the iron element accounts for 20-60% of the mass of the catalyst;
the carbon source refers to glucose; the nitrogen source refers to urea; the iron source is selected from any one of ferric nitrate, ferric chloride, ferric acetylacetonate and iron phthalocyanine;
the calcination conditions are as follows: the calcination temperature is 700-900 ℃, and the calcination time is 2-4 h;
the specific surface area of the catalyst is 80-300 cm2(ii) g of said Fe3The particle sizes of C and FeN are both 5-30 nm.
2. Use according to claim 1, wherein the organic waste water comprises chlorophenols, dyes and/or endocrine disruptors.
3. The use according to claim 2, wherein the chlorophenolic compound refers to one or more of 2-cp, 3-cp, 4-cp, 2,4-dcp and 2,4, 6-tcp; the dye compound refers to X3B and/or acid orange; the endocrine disruptor compound refers to methyl phthalate.
4. The use according to any one of claims 1 to 3, wherein the concentration of the catalyst in the treatment of organic waste water is from 0.3g/L to 1.0 g/L.
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| CN112295573B (en) * | 2020-11-24 | 2021-12-10 | 中国科学院南京土壤研究所 | electro-Fenton catalyst and preparation method and application thereof |
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| CN114146723B (en) * | 2021-12-20 | 2023-02-28 | 山东大学 | Iron-nitrogen co-doped nano carbon composite catalyst, preparation method and application |
| CN114368807B (en) * | 2022-01-14 | 2023-03-10 | 中国科学技术大学 | Preparation method and application of chitosan-coated electro-Fenton cathode |
| CN114349296A (en) * | 2022-01-17 | 2022-04-15 | 江西颖南原环能有限公司 | Comprehensive recycling treatment method for Fenton iron mud |
| CN114618554B (en) * | 2022-03-24 | 2023-11-07 | 湖南大学 | Iron porphyrin derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material, and preparation method and application thereof |
| CN114849760B (en) * | 2022-06-08 | 2023-10-17 | 四川轻化工大学 | Catalyst and preparation method and application thereof |
| CN116371446A (en) * | 2023-04-19 | 2023-07-04 | 中国科学院生态环境研究中心 | Iron-nitrogen compound-carbon nano tube composite material, preparation method and application |
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