CN114226721A - Graphite carbon coated nano zero-valent iron composite material and preparation method and application thereof - Google Patents
Graphite carbon coated nano zero-valent iron composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphite carbon-coated nano zero-valent iron composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: the preparation method comprises the steps of mixing sawdust and iron salt, adding tetrahydrofuran water solution, stirring uniformly, heating for 8-9 hours at 90-100 ℃ to obtain a dry compound, grinding the compound into powder, calcining for 2-3 hours at 550-700 ℃ in a nitrogen or inert gas environment to obtain the graphite carbon coated nano zero-valent iron composite material.
Description
Technical Field
The invention belongs to the technical field of environment functional materials, and particularly relates to a graphite carbon-coated nano zero-valent iron composite material as well as a preparation method and application thereof.
Background
With the rapid development of industry, persistent organic pollutants remaining in groundwater pose a great threat to ecosystem and human health. In recent years, advanced oxidation processes based on sulfate radicals have received much attention as an effective method of degrading persistent organic pollutants. The sulfate radical can be obtained by electron accepting cleavage of an unstable peroxide (-O-O-) bond in persulfate, which has a high redox potential (E)02.5-3.1V) is more effective in oxidative degradation of organic pollutants.
Nano zero-valent iron (nZVI) has been widely used to activate persulfate to degrade persistent organic pollutants due to its large specific surface area and environmental friendliness. However, the high reaction rate and surface energy make conventional nZVI prone to agglomeration and rapid deactivation during storage and use. Currently, various materials can be used as stabilizers to improve the dispersability and stability of nZVI, such as reduced graphene oxide, carbon materials, carboxymethyl cellulose, water-in-oil, and the like. However, for the characteristic that the nano zero-valent iron is easily oxidized, a very effective treatment method is not available at present, and the conventional treatment method usually requires two or more complicated preparation processes, but it is still difficult to obtain the nano zero-valent iron composite material with high oxidation resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a graphitic carbon-coated nano zero-valent iron composite material, the preparation method synthesizes a stabilized graphitic carbon-coated nano zero-valent iron composite material by a tetrahydrofuran-assisted carbothermic method, the preparation method has simple process, and the raw materials are green and pollution-free.
Another aspect of the present inventionAims to provide the graphite carbon-coated nano zero-valent iron composite material (Fe) obtained by the preparation method0@ gBC), the graphite carbon coated nano zero-valent iron composite material not only can maintain the reaction activity of the nano zero-valent iron, has low cost, is environment-friendly and free from secondary pollution, but also can be stably existed in the air environment for a long time without being oxidized, and has good oxidation resistance.
The invention also aims to provide the application of the graphite carbon-coated nano zero-valent iron composite material in degrading 2, 4-dichlorophenol.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a graphite carbon-coated nano zero-valent iron composite material comprises the following steps: mixing sawdust and ferric salt, adding a tetrahydrofuran aqueous solution, stirring uniformly, heating at 90-100 ℃ for 8-9 hours to obtain a dried compound, grinding the compound into powder, calcining at 550-700 ℃ for 2-3 hours in a nitrogen or inert gas environment to obtain the graphite carbon coated nano zero-valent iron composite material, wherein the ratio of the sawdust to the ferric salt is 2: (1-5), wherein the ratio of the mass part of the iron salt to the volume part of the tetrahydrofuran aqueous solution is (1-5): 200, the unit of the mass part is g, and the unit of the volume part is mL.
In the technical scheme, the ratio of the wood chips to the ferric salt is 2: (1-3), wherein the ratio of the mass part of the ferric salt to the volume part of the tetrahydrofuran aqueous solution is (1-3) to 200.
In the above technical scheme, the iron salt is FeCl3·6H2O。
In the technical scheme, the sawdust is sieved by a sieve of 100-150 meshes before use.
In the technical scheme, the concentration of tetrahydrofuran in the tetrahydrofuran aqueous solution is 30-50 wt%.
In the technical scheme, the stirring is performed for at least 1 hour by magnetic stirring.
The graphite carbon-coated nano zero-valent iron composite material obtained by the preparation method.
In the above technical solution, the graphitic carbon-coated nanoscale zero-valent iron composite material comprises: the graphene nano-shell-coated zero-valent iron nanoparticle comprises a carbon-based carrier with a three-dimensional network structure and zero-valent iron nanoparticles coated by graphene nano-shells uniformly loaded on the carbon-based carrier.
In the technical scheme, the particle size of the zero-valent iron nano-particles is 5-70 nm after the zero-valent iron nano-particles are wrapped by the graphene nano-shells.
The application of the graphite carbon-coated nano zero-valent iron composite material in degrading 2, 4-dichlorophenol.
In the technical scheme, the graphite carbon-coated nano zero-valent iron composite material is used as a persulfate activator.
In the technical scheme, the graphite carbon-coated nano zero-valent iron composite material is put into a solution to be degraded containing 2, 4-dichlorophenol, and then persulfate is added to the solution to be degraded, and the solution is vibrated.
In the technical scheme, the removal rate of the 2, 4-dichlorophenol is over 90 percent within 60min after the persulfate is added.
The application of the graphite carbon-coated nano zero-valent iron composite material in improving the stability of the material placed in an air environment.
In the technical scheme, after the material is placed in an air environment for 80 days, the 2, 4-dichlorophenol is degraded to achieve a removal rate of more than 90% within 60 min.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method adopts a one-step carbothermic method, is different from the traditional liquid phase reduction method, selects wood dust as a carbon source in the preparation process, adds a certain amount of ferric salt, blends the mixture into tetrahydrofuran aqueous solution with a certain concentration, fully combines the wood dust and ferric ions through magnetic stirring, then carries out carbothermic reduction at 550-700 ℃, and cools to obtain the graphitic carbon coated nano zero-valent iron composite material.
The carbon source selected by the invention is cheap and easily available forestry waste-wood dust, and the precursor of zero-valent iron is selected from ferric salt FeCl3·6H2O, through a tetrahydrofuran auxiliary anaerobic heating carbonization method and a carbothermic reduction process,the preparation method can avoid the agglomeration of the zero-valent iron and can be carried out in a non-liquid phase environment, thereby avoiding the generation of wastewater in the production process.
The graphite carbon-coated nano zero-valent iron composite material has a core-shell structure, and the shell structure can effectively inhibit the agglomeration of nano zero-valent iron, ensure the activity of the nano zero-valent iron and realize the characteristic of oxidation resistance, and has the effect of efficiently activating persulfate to remove 2, 4-dichlorophenol.
Drawings
FIG. 1 shows the removal rate of 2, 4-dichlorophenol from a graphite carbon-coated nanoscale zero-valent iron composite material;
FIG. 2 is a Fourier infrared scan (FTIR) of a graphitic carbon-coated nano zero-valent iron composite;
FIG. 3 is an X-ray diffraction pattern (XRD) of the graphite carbon-coated nano zero-valent iron composite material;
FIG. 4 shows the removal rate of 2, 4-dichlorophenol from the graphite carbon-coated nanoscale zero-valent iron composite obtained in the third example (under different initial pH values);
FIG. 5 shows the removal rate of 2, 4-dichlorophenol from a graphitic carbon-coated nanoscale zero-valent iron composite;
fig. 6 is a Scanning Electron Microscope (SEM) of the graphitic carbon-coated nano zero-valent iron composite material prepared in example three, wherein (a) is a Scanning Electron Microscope (SEM) obtained by amplifying the graphitic carbon-coated nano zero-valent iron composite material within the square frame in (b) by 30000 times, and (b) is an energy spectrum (Mapping) of the graphitic carbon-coated nano zero-valent iron composite material;
FIG. 7 is a Transmission Electron Micrograph (TEM) of the graphitic carbon-coated nano zero-valent iron composite prepared according to example III, wherein (a) is a transmission electron micrograph (3000 times), (b) is a transmission electron micrograph (10000 times), (c) is a transmission electron micrograph (30000 times), and (d) is a transmission electron micrograph (50000 times);
FIG. 8 is X-ray photoelectron spectroscopy (XPS) analysis of a graphitic carbon-coated nano zero-valent iron composite prepared according to example III before and after persulfate activation, wherein (a) is a C1s energy spectrum of the graphitic carbon-coated nano zero-valent iron composite before persulfate activation; (b) the carbon-coated nano zero-valent iron composite material is a C1s energy spectrum after persulfate is activated; (c) the Fe 2p energy spectrum of the graphite carbon-coated nano zero-valent iron composite material after persulfate is activated; (d) is a Fe 2p energy spectrum of the graphite carbon-coated nano zero-valent iron composite material after persulfate is activated.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
The wood chips used in the following examples were waste wood chips recovered from forest farms, cleaned, air-dried, crushed, and sieved through a 100-mesh sieve before use.
The following examples refer to the following sources of purchase of pharmaceuticals:
the following examples relate to the following types of instruments:
the removal rate in the following examples was obtained by:
parts by mass are in g and parts by volume are in mL.
The filtration adopts: a polytetrafluoroethylene filter membrane with the pore diameter of 0.22 mu m.
The concentration of 2,4-DCP was determined by HPLC using an Agilent C18 column (250 mm. times.4.6 mm, 5 μm).
Removal rate of (1-C)t/C0)*100％
Wherein, CtRepresents the concentration of 2, 4-dichlorophenol at a specific time; c0Represents the concentration of 2, 4-dichlorophenol before degradation.
The high performance liquid chromatography measures the absorbance of 2, 4-dichlorophenol under a certain ultraviolet wavelength, prepares 2, 4-dichlorophenol aqueous solutions with different concentrations to obtain a standard curve of the concentration and the absorbance of the 2, 4-dichlorophenol, and substitutes the absorbance of the solution to be measured into an equation of the standard curve to obtain the concentration of the 2, 4-dichlorophenol in the solution to be measured.
Examples one to five
A preparation method of a graphite carbon-coated nano zero-valent iron composite material comprises the following steps: 2g of wood chips and FeCl as iron salt3·6H2And O, adding 200mL of tetrahydrofuran aqueous solution, magnetically stirring for 1h to be uniform, heating for 9h at 95 ℃ in a water bath to obtain a dry compound, grinding the compound into powder by using a mortar, calcining for 2 h at 700 ℃ in a tubular resistance furnace under a nitrogen environment, and cooling to room temperature of 20-25 ℃ to obtain the graphite carbon-coated nano zero-valent iron composite material, wherein the concentration of tetrahydrofuran in the tetrahydrofuran aqueous solution is 50 wt%.
TABLE 1
| Examples | FeCl3·6H2Mass of O (unit: g) | Numbering of obtained graphite carbon coated nano zero-valent iron composite material |
| Example one | 1 | Fe0@gBC-1 |
| Example two | 2 | Fe0@gBC-2 |
| EXAMPLE III | 3 | Fe0@gBC-3 |
| Example four | 4 | Fe0@gBC-4 |
| EXAMPLE five | 5 | Fe@gBC-5 |
The graphite carbon-coated nano zero-valent iron composite material prepared in the third example was subjected to SEM (fig. 6) test, and it was observed that the carbon-based support exhibited a three-dimensional network structure, and nano zero-valent iron particles (white particles) were uniformly attached to the structure.
TEM (figure 7) tests are carried out on the graphitic carbon-coated nano zero-valent iron composite material prepared in the third embodiment, and the graphitic carbon-coated nano zero-valent iron particles are found to be uniformly dispersed in the amorphous carbon matrix, so that the aggregation phenomenon is avoided and the dispersibility is good. Meanwhile, a core-shell structure is also observed, the graphene nanoshell is formed by wrapping the core of the zero-valent iron nanoparticle with the graphene nanoshell, the graphene nanoshell is formed by multiple layers of graphene carbon layers which are closely and orderly arranged, and the formation of a shell structure is favorable for preventing the zero-valent iron core from contacting with air and enhancing the oxidation resistance of the composite material. The particle size of the zero-valent iron nanoparticles wrapped by the graphene nanosheets is 5-70 nm through particle size statistical analysis of SEM and TEM.
EXAMPLE six
The method for degrading 2, 4-dichlorophenol by using the graphite carbon-coated nano zero-valent iron composite material in the first to fifth embodiments as the persulfate activator comprises the following steps: 10mg of graphite carbon-coated nano zero-valent iron composite material is put into 50mL of solution to be degraded, the solution to be degraded is a mixture of water and 2, 4-dichlorophenol, and the solution to be degraded isThe concentration of the 2, 4-dichlorophenol is 20mg/L to be used as C0Adding sodium persulfate so that the concentration of sodium persulfate is 2mM, shaking at 180r/min for 1h in a constant temperature shaker (room temperature), and determining the concentration of the remaining 2, 4-dichlorophenol as C by high performance liquid chromatographyt。
Comparative example 1
The commercial nano zero-valent iron (Beijing Yinaoka science and technology Co., Ltd.) is used as persulfate activator in degrading 2, 4-dichlorophenol, and the specific method comprises the following steps: 3.25mg of commercial nano zero-valent iron is put into 50mL of solution to be degraded, the solution to be degraded is a mixture of water and 2, 4-dichlorophenol, and the concentration of the 2, 4-dichlorophenol in the solution to be degraded is 20mg/L and is taken as C0Adding sodium persulfate so that the concentration of sodium persulfate is 2mM, shaking at 180r/min for 1 hr in a constant temperature oscillator, and determining the concentration of residual 2, 4-dichlorophenol by high performance liquid chromatography as Ct。
FIG. 1 shows the degradation rate of 2, 4-dichlorophenol in the sixth example and the first comparative example, and it can be seen from FIG. 1 that the degradation efficiency (removal rate) of 2, 4-dichlorophenol in the first comparative example can reach 69.2% at 1h of reaction. The degradation rates of the graphite carbon-coated nano zero-valent iron composite materials prepared in the first to fifth examples to 2, 4-dichlorophenol are respectively 75.5%, 96.8%, 100%, 52.9% and 22.1% in sequence, which shows that the graphite carbon-coated nano zero-valent iron composite materials prepared in the first to third examples have better activation effect on persulfate compared with commercial nano zero-valent iron.
FTIR (figure 2) analysis is carried out on the graphitic carbon-coated nano zero-valent iron composite materials in the first to fifth examples, and the graphitic carbon-coated nano zero-valent iron composite materials synthesized in different examples contain less functional groups and 581cm along with the continuous reduction of the mass ratio of carbon source wood chips-1The strength of Fe-O bond is continuously enhanced, which shows that the content of carbon source is one of the important factors influencing the reduction degree of iron oxide.
The graphite carbon-coated nano zero-valent iron composite material in the first to fifth examples and the graphite carbon-coated nano zero in the third example after being placed in the air for 80 daysXRD (figure 3) analysis is carried out on the valence iron composite material, and as can be seen from figure 3, the reduction degree of the iron oxide is continuously enhanced along with the increase of the content of the carbon source, and the iron oxide is finally reduced into the nano zero-valent iron (Fe)0) And, further, by leaving in air Fe after 80 days0The XRD of @ gBC-3 (FIG. 3) shows that the graphite carbon-coated nano zero-valent iron composite material prepared in example III still maintains the state of zero-valent iron, which indicates that the graphite carbon-coated nano zero-valent iron composite material can realize the oxidation resistance of nano zero-valent iron.
EXAMPLE seven
The graphite carbon-coated nano zero-valent iron composite material obtained in the third embodiment is used as a persulfate activator in the degradation of 2, 4-dichlorophenol, and the specific method comprises the following steps: adding 10mg of graphite carbon-coated nano zero-valent iron composite material into 50mL of solution to be degraded, wherein the solution to be degraded has different initial pH values, the pH values are 3, 5, 7, 9 and 11, the solution to be degraded is a mixture of water and 2, 4-dichlorophenol, and the concentration of the 2, 4-dichlorophenol in the solution to be degraded is 20mg/L and is marked as C0Adding sodium persulfate so that the concentration of sodium persulfate is 2mM, shaking at 180r/min for 1 hr in a constant temperature oscillator, and measuring the concentration of residual 2, 4-dichlorophenol by high performance liquid chromatography as Ct。
Fig. 4 shows the removal rate of 2, 4-dichlorophenol degraded by the method in example seven and example six (without adjusting the initial pH value, pH 6.53, No adjustment of pH in fig. 4) by using the graphitic carbon-coated nano zero-valent iron composite prepared in example three, and as can be seen from fig. 4, the graphitic carbon-coated nano zero-valent iron composite prepared in example three has wide pH adaptability for removing 2, 4-dichlorophenol by activating persulfate. Under acidic and neutral conditions, 2, 4-dichlorophenol can be completely removed within 15 minutes. In addition, although the removal rate of 2, 4-dichlorophenol gradually decreases with increasing pH, the removal rate still reaches 42% when pH is 11.
Example eight
The graphite carbon-coated nano zero-valent iron composite material obtained in the third embodiment after being placed in the air for 80 days is used as a persulfate activator in the degradation of 2, 4-dichlorophenol, and 10mg of the graphite carbon-coated nano zero-valent iron composite material is added into 50mL of solution to be treatedIn the degradation solution, the solution to be degraded is a mixture of water and 2, 4-dichlorophenol, and the concentration of the 2, 4-dichlorophenol in the solution to be degraded is 20mg/L and is marked as C0Adding sodium persulfate so that the concentration of sodium persulfate is 2mM, shaking at 180r/min for 1 hr in a constant temperature oscillator, and measuring the concentration of residual 2, 4-dichlorophenol by high performance liquid chromatography as Ct。
Fig. 5 shows the removal rate of 2, 4-dichlorophenol by using the graphite carbon-coated nano zero-valent iron composite obtained in the third embodiment according to the methods in the eighth and sixth embodiments (fig. 5 shows the removal rate of 2, 4-dichlorophenol by using the method in the sixth embodiment), and it can be seen from fig. 5 that the graphite carbon-coated nano zero-valent iron composite prepared in the third embodiment can still effectively remove 2, 4-dichlorophenol after being placed in the air for 80 days (fig. 5), and the removal efficiency of 2, 4-dichlorophenol is basically the same as that of the newly prepared graphite carbon-coated nano zero-valent iron composite, which indicates that the graphite carbon-coated nano zero-valent iron composite has good oxidation resistance and stability.
XPS test of the graphitic carbon-coated nano zero-valent iron composite prepared in example III showed that fresh Fe was found as shown in FIG. 8(a and c)0Sp in the C1s peak of @ gBC-32And sp3The characteristic peaks of the hybrid carbon correspond to about 284.5eV and 285.1eV, respectively, and are considered to represent the structures of graphitized carbon and amorphous carbon. While observed at 706.86eV, 710.08eV and 711.91eV, respectively, corresponding to Fe0、Fe2+And Fe3+Characteristic peak of (2). Fe3+And Fe2+The appearance of the peaks indicates that the surface of the zero-valent iron may be partially oxidized during the preparation of the material.
The used graphite carbon of the sixth example is coated with the nano zero-valent iron composite (Fe)0@ gBC-3), as shown in fig. 8(b and d), the graphitized carbon (sp) in the used graphitic carbon-coated nano zero-valent iron composite material was compared with the used graphitic carbon before use2) The content of amorphous carbon decreased from 54.71% to 41.66%, while the content of amorphous carbon increased from 38.26% to 42.20%. Indicating that during the reaction, the highly graphitized graphene nanoshell acts as an electron between nZVI and persulfateThe shuttle body is converted into amorphous carbon, so that the electron transfer is accelerated, and the degradation of the 2, 4-dichlorophenol is promoted. Further, Fe0@ gBC-3 after activation of persulfate, Fe0The characteristic peak of (B) disappears, but Fe2+Increased from 23.08% to 49.73%, while Fe3+The proportion of the peak of (a) was reduced from 58.66% to 51.27%, indicating that electrons were supplied by zero-valent iron as the main electron donor during the activation of persulfate, while excess zero-valent iron reduced trivalent iron to divalent iron, resulting in a large increase in the content of divalent iron.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A preparation method of a graphite carbon-coated nano zero-valent iron composite material is characterized by comprising the following steps: mixing sawdust and ferric salt, adding a tetrahydrofuran aqueous solution, stirring uniformly, heating at 90-100 ℃ for 8-9 hours to obtain a dried compound, grinding the compound into powder, calcining at 550-700 ℃ for 2-3 hours in a nitrogen or inert gas environment to obtain the graphite carbon coated nano zero-valent iron composite material, wherein the ratio of the sawdust to the ferric salt is 2: (1-5), wherein the ratio of the mass part of the iron salt to the volume part of the tetrahydrofuran aqueous solution is (1-5): 200, the unit of the mass part is g, and the unit of the volume part is mL.
2. The preparation method according to claim 1, wherein the ratio of the wood chips to the iron salt is 2: (1-3), wherein the ratio of the mass part of the ferric salt to the volume part of the tetrahydrofuran aqueous solution is (1-3) to 200.
3. The method according to claim 2, wherein the iron salt is FeCl3·6H2O; the sawdust is sieved by a sieve of 100-150 meshes before use; the concentration of tetrahydrofuran in the tetrahydrofuran aqueous solution is 30-50 wt%; the stirring is performed for at least 1h by magnetic stirring.
4. The graphite carbon-coated nano zero-valent iron composite material obtained by the preparation method according to any one of claims 1 to 3.
5. The graphitic carbon-coated nano zero valent iron composite according to claim 4, wherein the graphitic carbon-coated nano zero valent iron composite comprises: the graphene nano-shell particle comprises a carbon-based carrier with a three-dimensional network structure and zero-valent iron nano-particles which are uniformly loaded on the carbon-based carrier and wrapped by a graphene nano-shell; the particle size of the zero-valent iron nano-particles after being wrapped by the graphene nano-shell is 5-70 nm.
6. The use of the graphite carbon-coated nano zero-valent iron composite material according to claim 4 for degrading 2, 4-dichlorophenol.
7. The use according to claim 6, wherein the graphitic carbon-coated nano zero-valent iron composite acts as a persulfate activator.
8. The application of claim 7, wherein the graphitic carbon-coated nano zero-valent iron composite is prepared by putting the graphitic carbon-coated nano zero-valent iron composite into a solution to be degraded containing 2, 4-dichlorophenol, adding persulfate, and oscillating.
9. The use according to claim 8, wherein the removal of 2, 4-dichlorophenol is greater than 90% within 60min of persulfate addition.
10. The use of the graphitic carbon-coated nano zero-valent iron composite according to claim 4 for improving the stability of the material placed in an air environment.
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| CN114853144A (en) * | 2022-05-17 | 2022-08-05 | 南昌大学 | Preparation method of iron-nickel alloy @ graphene powder for effectively degrading azo dye wastewater |
| CN115228446A (en) * | 2022-06-30 | 2022-10-25 | 大连工业大学 | Lignin-derived carbon-coated nano zero-valent iron composite material and preparation method and application thereof |
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