CN110252305B - Preparation and application of iron-carbon micro-electrolysis material capable of maintaining long-acting catalytic activity of Fenton system - Google Patents
Preparation and application of iron-carbon micro-electrolysis material capable of maintaining long-acting catalytic activity of Fenton system Download PDFInfo
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Abstract
The invention provides a preparation method and application of an iron-carbon micro-electrolysis material capable of keeping long-acting catalytic activity of a Fenton system. The catalyst is derived from iron metal organic frameworks (Fe-MOFs) and montmorillonite. Fe-MOFs prepared by a mechanochemical method is mixed with montmorillonite and then carbonized at high temperature to form a core-shell type iron-carbon filler micro-electrolysis material (Fe @ C-MMT) dispersed among montmorillonite lamellar structures. The high-dispersion Fe @ C-MMT material in a water sample can delay the ineffective decomposition of hydrogen peroxide and selectively generate hydroxyl free radicals, so that the hydrogen peroxide in the system has long-acting oxidation capacity. The catalyst has certain pH regulating capacity, and organic pollutants can be degraded efficiently when the initial pH is 3-6.5. The catalyst has good stability, can be repeatedly utilized for many times, and is very suitable for removing the nondegradable organic pollutants such as phenol, methyl orange and the like in an environmental water sample by using the Fenton reaction of an advanced oxidation technology.
Description
Technical Field
The invention belongs to the technical field of high-toxicity pollutant treatment, and relates to preparation of a high-dispersity core-shell type iron-carbon micro-electrolysis nano material for maintaining long-acting catalytic activity of a Fenton system and application of the nano material as a heterogeneous Fenton catalyst to pollutant degradation.
Background
China is in the fast growth period of economy, and the rapid development of industry is the guarantee of the fast growth of economy, but simultaneously, a large amount of waste water is discharged in industrial production. The industrial wastewater has the characteristics of multiple pollutant types, complex components, high COD concentration, poor biodegradability, high toxicity and the like. If the method is not effectively and comprehensively treated, serious environmental pollution and ecological damage are caused, the health of people is harmed, and the further sustainable development of economy is hindered. The iron-carbon micro-electrolysis method, also called as internal electrolysis method, is a new electrochemical method which is widely applied to treatment of dye, printing and dyeing, electroplating wastewater, oily wastewater, pesticide wastewater, papermaking wastewater, pharmaceutical wastewater, chemical wastewater, garbage leachate and the like for nearly 30 years, has the characteristics of wide application range, simple process, good treatment effect and the like, and particularly has more obvious advantages in treatment of industrial wastewater with high salinity, high COD and higher chromaticity compared with other processes. The BOD/COD ratio of the waste water difficult to biodegrade is greatly improved after the treatment of the iron-carbon micro-electrolysis process, which is beneficial to improving the subsequent biological treatment effect.
The micro-electrolysis technology is to utilize the micro-electrolysis material filled in the wastewater to generate 1.2V potential difference to carry out electrolysis treatment on the wastewater under the condition of no power supply so as to achieve the purpose of degrading organic pollutants. In the reaction, Fe is thereby released at the anode2+The cathode generates activity [ H ]]And O.O.etc. which have high chemical activity and can change the structure and characteristics of a plurality of organic matters in the wastewater to cause the actions of chain scission, ring opening, etc. of the organic matters. In order to improve the treatment capacity of the iron-carbon micro-electrolysis material on high-concentration macromolecular degradation-resistant pollutants in the wastewater, a proper amount of H is added into the wastewater2O2Solution with Fe in wastewater2+Form a Fenton reagent, Fe2+Can catalyze H2O2Decomposition produces hydroxyl radicals. The hydroxyl free radical has strong oxidizing ability, and is especially suitable for treating organic waste water difficult to degrade. Fe released continuously in micro-electrolysis system2+Can promote H2O2The rapid decomposition of (2) and the generation of a large amount of hydroxyl radicals in a short time. These radicals may be trapped by Fe in addition to organic contaminants2+、H2O2And superoxide radical and the like are consumed, so that the utilization rate of hydrogen peroxide and hydroxyl radical is low, and the cost of water treatment is increased.
The preparation of the current commercial iron-carbon micro-electrolysis material is divided into three forms, including physical mixing of scrap iron or iron shaving materials and active carbon, high-temperature sintering of iron powder, carbon powder and adhesive (such as clay) and oxygen-free sintering of the iron powder and the carbon powder which are extremely fine and have large specific gravity. The first filler has the problems of iron scrap caking, blockage, difficult filler replacement, low degradation and conversion efficiency of pollutants in wastewater and the like. The combination of iron and carbon in the high-temperature sintered filler is tight, the blockage phenomenon of filler hardening is also inhibited to a certain degree, and the capacity of adsorbing and degrading pollutants is improved. However, since the optimum pH for microelectrolytic operation is less than 4, in a more acidic solution, the iron exposed at the edges of the filler is easily oxidized by dissolved oxygen in the water, aggravating the corrosion and loss of iron, and increasing the iron ion content in the water sample. Although the iron ions can be used as a coagulant to remove organic pollutants through flocculation precipitation, the precipitates and particles in the wastewater can be attached to the surface of the filler (especially zero-valent iron) to form a passive film, so that the effective contact of the filler and the wastewater is blocked, the activity of the filler is reduced, and the service life of the iron-carbon filler is greatly shortened. Therefore, most of the commercial iron-carbon fillers are replaced or regenerated after being used for half a year to one year, and the operation cost of enterprises is increased.
Therefore, the ideal micro-electrolysis material not only has the characteristics of large specific surface area, strong activity, large current density and the like, but also can avoid the agglomeration of zero-valent iron in the operation process, prevent the corrosion of dissolved oxygen and the pollution of particulate matters in hydroxide and water samples and the like, and can improve the utilization rate of hydrogen peroxide. The novel efficient iron-carbon micro-electrolysis material has great significance for efficiently treating industrial wastewater, and has wide application prospect when being used for removing phenol and methyl orange which are toxic pollutants difficult to degrade in a water environment sample. The relevant documents can be referred to:
[1]X.Yang,Interior microelectrolysis oxidation of polyesterwastewater and its treatment technology.J.Hazard.Mater.2009,169,480-485.
[2]F.Ju,Y.Y.Hu,Removal of EDTA-chelated copper from aqueous solutionby interior microelectrolysis.Sep.Purif.Technol.2011,78,33-41.
[3]L.M.Wu,L.B.Liao,G.C.Lv,F.X.Qin,Y.J.He,X.Y.Wang,Micro-electrolysisof Cr(VI)in the nanoscale zero-valent iron loaded activatedcarbon.J.Hazard.Mater.2013,254-255,277-283.
[4]B.Lai,Y.X.Zhou,P.Yang,J.H.Yang,J.L.Wang,Degradation of 3,3’-iminobis-propanenitrile in aqueous solution by Fe0/GAC micro-electrolysissystem.Chemosphere 2013,90,1470-1477.
[5]Y.H.Han,H.Li,M.L.Liu,Y.M.Sang,C.Z.Liang,J.Q.Chen,Purificationtreatment of dyes wastewater with a novel micro-electrolysisreactor.Sep.Purif.Technol.2016,170,241-247.
[6]Z.M.Yang,Y.P.Ma,Y.Liu,Q.S.Li,Z.Y.Zhou,Z.Q.Ren,Degradation oforganic pollutants in near-neutral pH solution by Fe-C micro-electrolysissystem.Chem.Eng.J.2017,315,403-414.
[7]Y.Z.Liu,C.Wang,Z.Y.Sui,D.L.Zou,Degradation of chlortetracyclineusing nano micro-electrolysis materials with loadingcopper.Sep.Purif.Technol.2018,203,29-35.
[8]X.Y.Zhu,X.J.Chen,Z.M.Yang,Y.Liu,Z.Y.Zhou,Z.Q.Ren,Investigating theinfluences of electrode material property on degradation behavior of organicwastewaters by iron-carbon micro-electrolysis.Chem.Eng.J.2018,338,46-54.
[9]L.M.Ren,J.Dong,Z.F.Chi,H.Z.Huang,Reduced graphene oxide-nano zerovalue iron(rGO-nZVI)micro-elecytrolysis accelerating Cr(VI)removal inaquifer.J.Environ.Sci.2018,73,96-06.
[10]C.Huang,F.Peng,H.J.Guo,C.Wang,M.T.Luo,C.Zhao,L.Xiong,X.F.Chen,X.D.Chen,Efficient COD degradation of turpentine processing wastewater bycombination of Fe-C micro-electrolysis and Fenton treatment:Long-term studyand scale up.Chem.Eng.J.2018,351,697-707.
[11]W.X.Zhang,X.M.Li,Q.Yang,D.B.Wang,Y.Wu,X.F.Zhu,J.Wei,Y.Liu,L.H.Hou,C.Y.Chen,Pretreatment of landfill leachate in near-neutral pHcondition by persulfate activated Fe-C micro-electrolysis system.Chemosphere2019,216,749-756.
[12]X.Y.Xu,Y.Cheng,T.T.Zhang,F.Y.Ji,X.Xu,Treatment of pharmaceuticalwastewater using interior micro-electorlysis/Fenton oxidation-coagulation andbiological degradation.Chemosphere 2016,152,23-30.
[13]L.Q.Wang,Q.Yang,D.B.Wang,X.M.Li,G.M.Zeng,Z.J.Li,Y.C.Deng,J.Liu,K.X.Yi,Advanced landfill leachate treatment using iron-carbonmicroelectrolysis-Fenton process:Process optimization and columnexperiments.J.Hazard.Mater.2016,318,460-467.
disclosure of Invention
The invention aims to provide a high-dispersion core-shell type Fe-C micro-electrolysis material catalyst which is used for efficiently removing phenol and dye type non-degradable organic pollutants in an environmental water sample and can maintain the long-acting catalytic activity of a Fenton system.
The invention also aims to provide a preparation method of the high-dispersion core-shell type Fe-C micro-electrolysis material catalyst for maintaining the long-acting catalytic activity of the Fenton system.
The purpose of the invention is realized by adopting the following technical scheme.
In one aspect, the invention provides a high-dispersion core-shell composite Fe-C micro-electrolysis material (Fe @ C-MMT) which is prepared from a graphitized carbon shell (C) and zero-valent iron (Fe)0) And iron carbide (Fe)3C) Inner core and carrier montmorillonite mineral. The diameter of the core of the zero-valent iron is 10-50nm, the diameter of the carbon shell is 3-5nm, and the core-shell Fe-C is uniformly dispersed among the layered structures of the montmorillonite and on the outer surface.
On the other hand, the invention provides a preparation method of the high-dispersion core-shell type composite Fe-C micro-electrolysis material for maintaining the long-acting catalytic activity of the Fenton system, which comprises the following steps: (1) weighing a certain proportion of inorganic ferric salt and benzene carboxylic acid ligand, and adding into a zirconium oxide grinding tank; (2) adding a certain amount of tetramethylammonium hydroxide solution (1-6mL) into the mixed solid obtained in the step (1), and grinding for 0.5-2h at the speed of 300 r/min to obtain the Fe-MOFs material; (3) and (3) heating the material prepared in the step (2) and a certain proportion of clay mineral at the high temperature of 700-1000 ℃ for 1-4 hours under the protection of nitrogen to obtain the high-dispersion core-shell type Fe-C micro-electrolysis composite catalyst.
In a preferred embodiment of the present invention, the inorganic iron salt is selected from the group consisting of ferric chloride, ferric nitrate, ferric sulfate, and the like.
In a preferred embodiment of the present invention, the benzene carboxylic acid ligand is selected from m-benzene dicarboxylic acid, p-benzene dicarboxylic acid, 2-hydroxy-p-benzene dicarboxylic acid, 2-amino-p-benzene dicarboxylic acid, pyromellitic tricarboxylic acid, and the like.
In a preferred embodiment of the present invention, the clay mineral is selected from montmorillonite, metakaolin, attapulgite, illite, and the like.
In a preferred embodiment of the present invention, the ratio of the tetramethylammonium hydroxide solution used for the synthesis of Fe-MOFs to the iron salt and the organic ligand is 5:1 to 0.5:1(g: mL).
In a preferred embodiment of the invention, the mass ratio of the Fe-MOFs for the synthesis of the high-dispersion core-shell Fe-C micro-electrolysis to the clay mineral montmorillonite is 5:1 to 1: 3.
In a preferred embodiment of the present invention, the high temperature carbonization heating temperature is 700-1000 ℃, and the reaction time is 1-4 hours.
In another aspect, the high-dispersion core-shell Fe-C micro-electrolysis material capable of maintaining the long-acting catalytic activity of the Fenton system is preferably selected from difficultly degradable high-toxicity phenol and methyl orange organic pollutants in the application of removing the pollutants in an environmental water sample.
Therefore, the preparation method of the high-dispersion core-shell Fe-C micro-electrolysis material is simple, short in time consumption and only needs a small amount of organic solvent; the dispersibility is good, and the iron-carbon filler is not easy to agglomerate in the using process. The Fe-C micro-electrolysis technology is combined with Fenton oxidation, so that the capability of decomposing pollutants which are difficult to degrade can be enhanced. Fe continuously generated by zero-valent iron anode2+Can catalyze hydrogen peroxide to decompose and produce hydroxyl free radicals; in addition, electrons generated by the anode can directly reduce hydrogen peroxide to generate hydroxyl radicals, so that the hydrogen peroxide in the micro-electrolysis system is consumed quickly. The rapidly generated hydroxyl radicals, in addition to the oxidative degradation of pollutants, may also be degraded by Fe2+Hydrogen peroxide, superoxide radical and hydroxyl radical are basically consumed, so that the utilization rate of the hydroxyl radical and the hydrogen peroxide is reduced. After the Fe-C filler is loaded in the clay mineral with a layered structure, the probability of capturing electrons by hydrogen peroxide is reduced because the clay mineral is not conductive, and the generation amount of hydroxyl radicals is further reduced. Meanwhile, the surface of the clay mineral is inert, so that hydrogen peroxide can be usedStably exist in the solution. Thus, the low concentration of Fe released continuously in the micro-electrolysis reaction2+And electrons can promote hydrogen peroxide to be slowly and selectively decomposed into hydroxyl radicals. In other words, the hydrogen peroxide added in the system can slowly generate hydroxyl radicals for a long time, which is equivalent to increase the timeliness of the hydrogen peroxide, so that the Fe-C and Fenton combined system can degrade pollutants for a long time. When the dosage of the high-dispersion core-shell type iron-carbon filler is 0.5g/L, the pH value of the solution is adjusted to 4.0, the concentration of methyl orange is 50mg/L, 10mM hydrogen peroxide is added into the solution at one time, and the degradation rate and the mineralization rate of the methyl orange are 100 percent and 80 percent respectively after 7 hours. And then, continuously adding methyl orange into the solution to enable the concentration of the methyl orange to be 50mg/L, and needing no hydrogen peroxide. As a result, the degradation rate of methyl orange after the 5 th addition still reached 80%. It is shown that 10mM hydrogen peroxide can maintain high activity for 40h in the system. When the concentration of methyl orange in the solution is 1000mg/L, the dosage of the catalyst is 0.5g/L, and the concentration of hydrogen peroxide is 40mM (the molar concentration ratio of pollutant to hydrogen peroxide is 13.3), the degradation rate of the methyl orange within 24 hours reaches 86%. The core-shell structure ensures that the zero-valent iron core has strong stability and is not easily oxidized by dissolved oxygen in air and water. Therefore, the material has good stability and reusability. When the pH value is 4 and the solution is repeatedly used for 10 times, the pollutant degradation efficiency still reaches 100 percent, and Fe released in the solution2+Less than 3 ppm. The montmorillonite in the catalyst also has a certain function of adjusting pH, and pollutants can be effectively degraded when the initial pH of the solution is between 3 and 6.5. When the catalyst is soaked in a solution with the pH value of 4 for 3 months, the solution is colorless and transparent, and the catalyst still keeps black, which indicates that zero-valent iron in the catalyst has very excellent capability of resisting the oxidation of dissolved oxygen under the protection of a carbon shell and clay minerals. In a word, the prepared high-dispersion core-shell type Fe-C micro-electrolysis material has the advantages of good stability, high efficiency, low cost, simple preparation method and the like, and the established micro-electrolysis + Fenton treatment method has high utilization rate of hydrogen peroxide and can be applied to removal of various toxic and harmful organic pollutants in polluted water.
Compared with the conventional Fenton-like catalyst and commercial Fe-C micro-electrolysis filler, the high-dispersion core-shell type Fe-C micro-electrolysis material provided by the invention has the following advantages:
(1) the preparation method is simple, easy to operate and needs less organic solvent. The preparation of the precursor by adopting a mechanochemical method has short time consumption, high utilization rate of raw materials and no need of a large amount of toxic solvent; the method for loading the Fe-C filler to the montmorillonite is very simple, and the loading amount of the Fe-C filler is high.
(2) The high-dispersion core-shell type Fe-C micro-electrolysis material has good stability. Because of the protection of the carbon shell, the zero-valent iron core has strong stability and is not easily oxidized by oxygen in air and water, and hydroxide precipitate generated in the reaction process is prevented from depositing on the surface of the zero-valent iron; after the catalyst is loaded on a montmorillonite carrier, the nano-scale iron-carbon filler cannot be agglomerated in the operation process, so that the catalyst keeps high activity and excellent reusability.
(3) In the established Fe-C micro-electrolysis + Fenton system, the utilization rate of hydrogen peroxide is high, and hydroxyl radicals can be selectively generated. The hydrogen peroxide added in the system can slowly generate hydroxyl radicals for a long time, which is equivalent to increase the timeliness of the hydrogen peroxide, so that the Fe-C and Fenton combined system can degrade pollutants for a long time, thereby reducing the cost of sewage treatment.
(4) The clay mineral carrier has good viscosity and is a common auxiliary material for granulating nanometer materials. Therefore, the developed iron-carbon material can be directly granulated, and the granulated iron-carbon filler still maintains high catalytic activity.
Phenol and methyl orange are selected as representatives of common high-toxicity organic pollutants, and the catalytic performance of the high-dispersion core-shell type Fe-C micro-electrolysis material is tested. The results demonstrate that the catalyst can slow down H2O2So that H is decomposed inefficiently2O2Hydroxyl free radicals are selectively generated, so that the degradation and high-efficiency mineralization of high-concentration organic pollutants are promoted. The catalyst has certain pH adjusting capacity, when the initial pH of a reaction solution is 3-6.5, the concentration of the catalyst is 0.5g/L, the concentration of hydrogen peroxide is 5mM, the removal rate of 100ppm phenol and 50ppm methyl orange is 100%, and the mineralization rate is 70-85%. When the concentration of methyl orange in the solution is 1000mg/L, the catalyst dose is 0.5 g-L, the hydrogen peroxide concentration is 40mM (the molar concentration ratio of the pollutants to the hydrogen peroxide is 13.3), and the degradation rate of the methyl orange within 24 hours reaches 86%. When the dosage of the high-dispersion core-shell type iron-carbon filler is 0.5g/L, the pH value of the solution is adjusted to 4.0, the concentration of methyl orange is 50mg/L, 10mM hydrogen peroxide is added into the solution at one time, and the degradation rate and the mineralization rate of the methyl orange are 100 percent and 80 percent respectively after 7 hours. And then, continuously adding methyl orange into the solution to enable the concentration of the methyl orange to be 50mg/L, and needing no hydrogen peroxide. As a result, the degradation rate of methyl orange after the 5 th addition still reached 80%. The high-dispersion core-shell type Fe-C micro-electrolysis material has good stability, can be repeatedly used for 10 times, can completely degrade methyl orange when the pH is 4, and releases Fe2+The concentration of the water sample is kept about 3.0ppm, no red mud is generated, and the water sample after the pollutants are removed can be directly discharged.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a schematic diagram of the synthesis of a high-dispersion core-shell type Fe-C micro-electrolysis material of the invention;
FIG. 2 is TEM and SEM photographs of the high-dispersion core-shell type Fe-C micro-electrolysis material of the invention;
FIG. 3 is an XRD spectrum of the highly dispersed core-shell Fe-C micro-electrolysis material of the present invention;
FIG. 4 is an XPS spectrum of a highly dispersed core-shell Fe-C microelectrolytic material of the present invention;
FIG. 5 is an FTIR profile of a highly dispersed core-shell Fe-C microelectrolytic material of the present invention.
Detailed Description
The present invention is further illustrated below with reference to preferred examples, which are only illustrative and not intended to limit the scope of the present invention.
Example 1: the invention relates to a preparation method of a high-dispersion core-shell type Fe-C micro-electrolysis material
The synthetic schematic diagram of the high-dispersion core-shell type Fe-C micro-electrolysis material provided by the invention is shown in figure 1, and the specific preparation method comprises the following steps:
firstly, a certain amount of FeCl is weighed3And p-benzenedicarboxylic acid is added into a zirconium oxide grinding tank, and then addedAdding a certain volume of tetramethylammonium hydroxide solution and 3-4 zirconium oxide grinding balls, and grinding for 0.5-2h at the speed of 300 r/min to obtain the Fe-MOFs material; and fully mixing the prepared Fe-MOFs with montmorillonite, and heating at the high temperature of 800 ℃ for 2 hours under the protection of nitrogen to obtain the high-dispersion core-shell Fe-C micro-electrolysis material.
Example 2: structural characterization of high-dispersion core-shell type Fe-C micro-electrolysis material
The present embodiment is a structural characterization of a high-dispersion core-shell type Fe-C micro-electrolysis material, and specifically includes the following steps:
1.TEM
and analyzing the grain diameter and the morphology structure of the high-dispersion core-shell type Fe-C micro-electrolysis material by adopting a transmission electron microscope H7500 (Hitachi, Japan).
As can be seen from FIG. 2, the particle size of the core of the zerovalent iron in the Fe-C nanoparticles is 15-30nm, and the thickness of the carbon shell is about 5 nm. The core-shell Fe-C is embedded in a large amount of graphitized carbon, so that the stability of the core zero-valent iron is improved. The core-shell type Fe-C nano particles are uniformly dispersed among the lamellar structures and on the inner and outer surfaces of the montmorillonite with a lamellar structure.
XRD spectrum
The X-ray diffraction (XRD) pattern of the high dispersion core-shell type Fe-C micro-electrolysis material prepared by grinding method and high temperature carbonization method is obtained on b/max-RB diffraction meter (Rigaku, Japan), Cu Ka ray is filtered by nickel, the scanning range is from 10 degrees to 80 degrees, and the scanning speed is 4 degrees/min.
As shown in FIG. 3, on the XRD spectrum of the high-dispersion core-shell type Fe-C micro-electrolysis material, the diffraction peaks with diffraction angles of 44.6 and 65.0 degrees respectively represent the (110) crystal face and the (200) crystal face of α -Fe with a body center structure (JCPDS 06-0696), and the diffraction peaks with diffraction angles of 37.6, 42.8, 43.6, 45.9 and 50.9 degrees respectively contain a certain amount of Fe in the surface material3/C，Fe3the/C has better stability than zero-valent iron; and diffraction peaks at 7.89, 17.9, 20.5, 25.6 and 27.5 degrees are from montmorillonite in the filler; in addition, the diffraction peak of about 25 degrees on the spectrogram comes from the (002) crystal face of the graphitized carbon. The results show that the material consists mainly of zero-valent iron, graphitized carbon and montmorillonite.
XPS spectra
Scanning the high-dispersion Fe-C micro-electrolysis material by using an X-ray spectrometer, and analyzing surface elements of the material.
As shown in FIG. 4, the high resolution spectra of O1s and C1s show that the oxygen content of the high-dispersion Fe-C micro-electrolysis material is greatly reduced compared with that of montmorillonite, and the C element content is obviously increased. The main functional groups on the surface of the montmorillonite comprise hydroxyl, adsorbed water, carbonate and the like, and the surface of the high-dispersion Fe-C micro-electrolysis material mainly contains structures such as hydroxyl, carbonyl, C-C and the like. The high resolution spectrum of Fe2p shows that Fe exists mainly as zero-valent iron after carbonization.
4. Infrared FTIR spectrum
The high dispersion Fe-C micro-electrolysis material was subjected to infrared analysis using a NEXUS 670 fourier transform infrared spectrometer (Nicolet Thermo, Waltham, MA) to examine the functional groups contained on the surface of the material.
As shown in FIG. 5, the surface of the highly dispersed Fe-C microelectrolytes had only a small amount of functional groups such as hydroxyl groups, and methyl and methylene groups were also observed. When the ratio of Fe-MOF to MMT is 2: 1-1: 2, only Si-O-Si at 1100cm was observed-1And peaks associated with coupling vibrations of Si-O-M and M-O in a low frequency region. With small amounts of hydroxyl and methyl, methylene groups present.
Example 3: test of catalytic performance of high-dispersion core-shell type Fe-C micro-electrolysis material
In the embodiment, phenol and methyl orange are selected as representatives, and the catalytic performance of the high-dispersion core-shell type Fe-C micro-electrolysis material is tested.
The operation steps of the test are as follows: preparing 100mg/L phenol and 50mL methyl orange standard substance, placing in 100mL polyethylene plastic vial, adding 25mg high-dispersion core-shell type Fe-C microelectrolysis material to make catalyst concentration be 0.5g/L, adding H with a certain concentration2O2. Shaking in shaking table, taking 0.5mL sample at intervals, adding 0.5mL ethanol, centrifuging, taking supernatant, and performing phenol, methyl orange, TOC and Fe respectively2+And H2O2The measurement of (1). Phenol by HPLCUV measurement, TOC detection with a TOC/TN analyzer, methyl orange, Fe2+And H2O2The measurement was carried out with an ultraviolet-visible spectrophotometer.
The conditions for HPLC-UV determination were as follows:
dikma Diamond C18Chromatography column (4.6mm × 250mm,5 μm);
the column temperature is 30 ℃; the sample size was 20. mu.L, and the flow rate of the mobile phase was 1 mL/min.
An ultraviolet detector with a wavelength of 290 nm; the mobile phase was 49% acetonitrile.
The methyl orange determination conditions are as follows:
and (3) centrifuging the water sample, taking supernatant, measuring the absorbance of a group of standard solutions by using a 2cm cuvette at the wavelength of 460nm, drawing a standard curve, simultaneously measuring the absorbance of methyl orange in the sample, and obtaining the content of the methyl orange in the sample by using the standard curve.
The TOC measurement conditions were as follows:
centrifuging the water sample, taking supernatant, taking deionized water and 0.8% HCl as mobile phases, and detecting by using a TOC/TN analyzer.
Fe2+And H2O2The measurement conditions of (2) were as follows:
determination of hydrogen peroxide by titanophotometry: h2O2Form a stable orange complex-peroxotitanic acid with titanium ions in an acidic solution, the shade of the color of the complex and H in the sample2O2Is in direct proportion. Taking titanium potassium oxalate as a color developing agent, measuring the absorbance of a group of standard color developing solutions in a 2cm cuvette at the wavelength of 400nm, drawing a standard curve, and simultaneously measuring H in a sample2O2The absorbance of (2) was determined by using a standard curve to determine H in the sample2O2The content of (a).
Method for measuring Fe by phenanthroline method2+: measuring the absorbance of a group of standard color development solutions by using phenanthroline as a color development agent and using a 2cm cuvette at the wavelength of 510nm, drawing a standard curve, and simultaneously measuring Fe in a sample2+The absorbance of (2) was measured by using a standard curve to determine Fe in the sample2+The content of (a).
The results show that the score is highThe dispersed Fe-C micro-electrolysis material can continuously generate Fe in aqueous solution2+And electrons, promoting H2O2The hydroxyl free radical is generated by the selective decomposition of the organic pollutants, and the high-efficiency degradation of the organic pollutants is further caused. Within pH 3-6.5, H2O2At concentrations of 10mM and 5mM, 100ppm phenol and 50ppm methyl orange were completely degraded, and TOC removal rate reached 70-85%. The material also has excellent reusability, can completely remove 50ppm of methyl orange within 10 hours after being reused for 10 times, and keeps the concentration of Fe ions at about 3ppm, thereby meeting the water body discharge standard. The clay mineral montmorillonite in the iron-carbon filler has good viscosity, so that the iron-carbon filler can be directly granulated. The produced particles (diameter is 1-3mm) have good catalytic activity, and the pollutant removal capacity of the particles is greatly better than that of commercial iron-carbon fillers.
Claims (9)
1. The preparation method of the high-dispersion core-shell type composite Fe-C micro-electrolysis material is characterized in that the material is prepared from a graphitized carbon shell (C) and zero-valent iron (Fe)0) And iron carbide inner core and carrier montmorillonite mineral, the diameter of the zero-valent iron/iron carbide inner core is 10-50nm, the diameter of the carbon shell is 3-5nm, and the core shell type Fe-C is uniformly dispersed among the layered structures of the montmorillonite and on the outer surface, the preparation method of the micro-electrolysis material comprises the following steps: (1) weighing a certain proportion of inorganic ferric salt and benzene carboxylic acid ligand, and adding into a zirconium oxide grinding tank; (2) adding a certain amount of tetramethylammonium hydroxide solution into the mixed solid obtained in the step (1), and grinding at the speed of 300 revolutions per minute to obtain Fe-MOFs materials; (3) and (3) heating the material prepared in the step (2) and a certain proportion of clay mineral at the high temperature of 700-1000 ℃ under the protection of nitrogen to obtain the high-dispersion core-shell type Fe-C micro-electrolysis composite catalyst.
2. The method of claim 1, wherein in step (1) the inorganic ferric salt is selected from the group consisting of ferric chloride, ferric nitrate, and ferric sulfate.
3. The process of claim 1, wherein in step (1) the benzene carboxylic acid ligand is selected from the group consisting of m-benzene dicarboxylic acid, p-benzene dicarboxylic acid, 2-hydroxy-p-benzene dicarboxylic acid, 2-amino-p-benzene dicarboxylic acid, and trimesic acid.
4. The method according to claim 1, wherein the ratio of the tetramethylammonium hydroxide solution used for synthesizing Fe-MOFs to the iron salt and the organic ligand in step (2) is 5:1 to 0.5:1(g: mL).
5. The method according to claim 1, wherein the clay mineral used for synthesis in step (3) is selected from the group consisting of montmorillonite, metakaolin, attapulgite, and illite.
6. The method according to claim 1, wherein the mass ratio of the Fe-MOFs for synthesizing the high-dispersion core-shell Fe-C micro-electrolysis and the clay mineral montmorillonite in the step (3) is 5:1-1: 3.
7. The method as claimed in claim 1, wherein the high temperature carbonization heating temperature in step (3) is 700 ℃ to 900 ℃ and the reaction time is 1 to 4 hours.
8. A high-dispersion core-shell composite Fe-C microelectrolytic material characterized by being prepared by the method of claim 1.
9. The high-dispersion core-shell type composite Fe-C micro-electrolysis material as claimed in claim 8 is used for degrading high-toxicity organic pollutants in polluted water.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101664668A (en) * | 2009-09-29 | 2010-03-10 | 中国科学院生态环境研究中心 | Preparation method and application of core-shell type Fe3O4/C magnetic nano solid extracting agent |
| CN103041815A (en) * | 2013-01-04 | 2013-04-17 | 南京林业大学 | Preparation method of iron-supported attapulgite heterogeneous fenton catalyst |
| CN105771880A (en) * | 2015-12-25 | 2016-07-20 | 武汉理工大学 | Iron oxyhydroxide supported montmorillonite adsorption and catalysis double-function material and preparation method thereof |
| CN106111156A (en) * | 2016-06-23 | 2016-11-16 | 上海交通大学 | Efficient class Fenton magnetic catalyst based on clay mineral and preparation method and application |
| CN108084449A (en) * | 2017-12-14 | 2018-05-29 | 中国科学院合肥物质科学研究院 | One kind is using Fe-MOFs as presoma controllable preparation is monatomic and cluster iron catalyst |
-
2019
- 2019-03-05 CN CN201910162389.2A patent/CN110252305B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101664668A (en) * | 2009-09-29 | 2010-03-10 | 中国科学院生态环境研究中心 | Preparation method and application of core-shell type Fe3O4/C magnetic nano solid extracting agent |
| CN103041815A (en) * | 2013-01-04 | 2013-04-17 | 南京林业大学 | Preparation method of iron-supported attapulgite heterogeneous fenton catalyst |
| CN105771880A (en) * | 2015-12-25 | 2016-07-20 | 武汉理工大学 | Iron oxyhydroxide supported montmorillonite adsorption and catalysis double-function material and preparation method thereof |
| CN106111156A (en) * | 2016-06-23 | 2016-11-16 | 上海交通大学 | Efficient class Fenton magnetic catalyst based on clay mineral and preparation method and application |
| CN108084449A (en) * | 2017-12-14 | 2018-05-29 | 中国科学院合肥物质科学研究院 | One kind is using Fe-MOFs as presoma controllable preparation is monatomic and cluster iron catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Heterogeneous Fenton-like catalysis of Fe-MOF derived magnetic carbon nanocomposites for degradation of 4-nitrophenol;Dezhi Chen等;《RSC Adv.》;20171018;第7卷;第49024–49030页 * |
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