CN111875025A - Graphene type nitrogen carbide loaded nano zero-valent iron composite material and preparation method and application thereof - Google Patents
Graphene type nitrogen carbide loaded nano zero-valent iron composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a graphene type nitrogen carbide loaded nano zero-valent iron composite material as well as a preparation method and application thereof, wherein the composite material is prepared by the following steps: (1) synthesizing graphene type nitrogen carbide; (2) g to C3N4Dispersed in FeCl3In solution; (3) preparing a sodium borohydride solution; (4) dropwise adding the sodium borohydride solution into the suspension while stirring to generate the graphene type nitrogen carbide loaded nanoscale zero-valent iron composite material; (5) and (3) storing the graphene type nitrogen carbide loaded nano zero-valent iron composite material. Compared with the prior art, the method has the advantages of improving the stability of the nano zero-valent iron particles, prolonging the reaction activity of the nano zero-valent iron particles, being used for removing heavy metal lead ions in water bodies and the like.
Description
Technical Field
The invention relates to the field of nano iron materials, in particular to a graphene type nitrogen carbide loaded nano zero-valent iron composite material and a preparation method and application thereof.
Background
The problem of lead contamination is a significant concern today. Prolonged exposure to lead-containing water causes notorious neurotoxicity which can affect multiple body systems. In order to maintain the environment and human health, an urgent challenge is presented, namely, the adoption of efficient, green and economic lead removal technology is required.
Conventional removal methods, packagesIncluding adsorption, precipitation, solvent extraction, ion exchange, coagulation, etc., however, these methods have the disadvantages of high operation cost, low efficiency, incomplete removal, secondary pollution, etc. Among these methods, the adsorption method is the most widely used lead purification technique because ions are easy to operate in water and relatively inexpensive. From another perspective, the synthesis has the ability to stabilize Pb (II) in the free state to Pb0The ability to treat agents and effect separation may be a promising direction. At present, a great deal of research work aiming at removing lead ions in water bodies is carried out at home and abroad, and nanometer zero-valent iron (nZVI), namely, a material which is in a nanometer scale range in at least one dimension in three-dimensional scale and takes the zero-valent iron as a main component, has attracted wide attention by the characteristics of high specific surface area, strong reducibility and the like, and becomes one of the most widely applied underground water and hazardous waste treatment nanometer materials at present.
However, due to chemical and magnetic interactions, pure iron nanoparticles tend to be connected into linear or fractal aggregates, and thus their undesirable colloidal stability and transportability are receiving increasing attention. Meanwhile, considering the service life of nZVI and the long-term effectiveness of nZVI in pollutant remediation, improving the electron selectivity to target pollutants or controlling electron transfer is also a prominent problem that needs to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a graphene type nitrogen carbide loaded nano zero-valent iron composite material which can improve the stability of nano zero-valent iron particles and prolong the reaction activity of the nano zero-valent iron particles and can be used for removing heavy metal lead ions in a water body, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the composite material is made of Fe3+The graphene-based carbon nitride nanoparticle has a complexing effect with functional groups on graphene-type carbon nitride, changes the microstructure of nano zero-valent iron and enables nano zero-valent iron particles to be uniformly dispersed on the carbon nitride, and the specific preparation method comprises the following steps:
a preparation method of a graphene type nitrogen carbide loaded nano zero-valent iron composite material comprises the following steps:
(1) synthesis of graphene type nitrogen carbide: heating urea powder, keeping the temperature, and naturally cooling to obtain g-C3N4(ii) a The resulting yellow powder was collected for use without further treatment.
(2) G to C3N4Dispersed in FeCl3Carrying out ultrasonic dispersion in the solution to obtain a suspension, and continuously introducing high-purity nitrogen in the whole process; (>99.9%) to remove dissolved oxygen to ensure an anaerobic environment.
(3) Preparation of sodium borohydride solution: dissolving sodium borohydride, a strong reducing agent, in deionized water for later use;
(4) dropwise adding a sodium borohydride solution into the suspension while stirring, continuously introducing high-purity nitrogen, stopping dropwise adding when the color of the mixed solution is changed from dark orange to dark gray, and generating the graphene type nitrogen carbide loaded nano zero-valent iron composite material; the solution was initially dark orange in color due to the presence of Fe in the solution3+(ii) a And then turned into light green color because the trivalent iron is reduced into Fe2+(ii) a Finally, the carbon nano-grade composite material is changed into dark gray, namely the graphene type nitrogen carbide loaded nano zero-valent iron composite material.
(5) Preservation of the graphene type nitrogen carbide loaded nano zero-valent iron composite material: the mixed solution was centrifuged to collect the resulting dark gray nanoparticles, washed with deionized water and absolute ethanol, and then stored in ethanol.
Further, the heating temperature is 520-600 ℃, and the heating speed is 4-5 ℃/min; the heat preservation time is 2-4 h.
Further, the g-C3N4With FeCl3The mass ratio of Fe element in the solution is 0.5-2.5.
Further, the time of ultrasonic dispersion is 8-12 min.
Further, the concentration of the sodium borohydride solution is 5-6 g/L.
Further, the dropping speed of the sodium borohydride solution is 10-15 ml/min.
Further, the stirring speed is 200-300 r/min.
Further, the graphene type nitrogen carbide loaded nano zero-valent iron composite material is stored in liquid ethanol at the temperature of below 4 ℃.
The graphene type nitrogen carbide loaded nano zero-valent iron composite material prepared by the method.
In the invention, the N-containing functional group on the iron/graphene type nitrogen carbide interface plays a vital role, on one hand, the interaction of the lone pair electrons of N and the surface iron ion vacancy tracks can prevent the excessive corrosion of iron, and can improve the stability of the nano zero-valent iron particles and prolong the reaction activity of the nano zero-valent iron particles. On the other hand, the N atom of the graphene-type nitrogen carbide monolayer may serve as a binding site for pb (ii) capture. When the coordinated Pb (II) ions receive electrons from the core and are reduced to elemental metal, the actively occupied binding sites are liberated again, and the process continues. In addition, because the nano zero-valent iron loaded by the graphene type nitrogen carbide has good dispersibility and corrosion resistance, the pH value near the nano iron-water interface is relatively slowly increased, which provides favorable conditions for Pb (II) reduction.
The application of the graphene type nitrogen carbide loaded nano zero-valent iron composite material is applied to removal of heavy metal lead ions in water.
Compared with the prior art, the invention has the following advantages:
(1) the load material graphene type nitrogen carbide can prevent the agglomeration of nano zero-valent iron particles, change the microstructure of the nano zero-valent iron so as to improve the stability of the nano zero-valent iron, and inhibit the corrosion of water on the nano zero-valent iron to a certain extent so as to prolong the reaction activity of the nano zero-valent iron;
(2) the graphene type nitrogen carbide loaded nano zero-valent iron composite material can effectively remove lead ions in water and reduce and fix the lead ions into zero-valent lead; this is because the N-containing functional group at the iron/graphene type nitrogen carbide interface also plays a crucial role, and on the one hand, the interaction of the lone pair of N electrons with the surface iron ion vacancy tracks prevents excessive corrosion of iron. On the other hand, the N atom of the graphene-type nitrogen carbide monolayer may serve as a binding site for pb (ii) capture. When the coordinated Pb (II) ions receive electrons from the core and are reduced to elemental metal, the actively occupied binding sites are liberated again, and the process continues. In addition, because the nano zero-valent iron loaded by the graphene type nitrogen carbide has good dispersibility and corrosion resistance, the pH value near the nano iron-water interface is relatively slowly increased, which provides favorable conditions for Pb (II) reduction;
(3) the load material graphene type nitrogen carbide raw material has low source price, high chemical stability, no toxicity and reusability; in addition, the synthetic method of the composite material is simple and easy to implement and is easy for batch production.
Drawings
Fig. 1 is an SEM image of the graphene-type nitrogen carbide-supported nano zero-valent iron composite prepared in example 2 and pure nZVI in a comparative example;
FIG. 2 is a TAFEL curve measured for the nZVI electrode in comparative example and the g-nZVI electrode in example 2 in a 10mmol/L sodium chloride solution;
FIG. 3 is a schematic view of a reactor for evaluating the removal effect of lead ions in water according to the present invention;
FIG. 4 is a comparison of the Pb (II) removal effect of different materials in water according to the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A preparation method of a graphene type nitrogen carbide loaded nano zero-valent iron composite material.
(1) Synthesis of graphene type nitrogen carbide: putting 10g of urea powder into an alumina crucible with a cover, heating the mixture to 550 ℃ in a tube furnace at the speed of 4.6 ℃/min, keeping the temperature in the air atmosphere for 2h, and naturally cooling the mixture to room temperature, wherein the obtained yellow powder can be collected for use without further treatment;
(2) 1.25g of g-C3N4Dispersed in 250mL of 8.8mmol FeCl3·6H2O, g-C of sample3N4The mass ratio of Fe/Fe is 2.5 (i.e. 2.5@ g-nZVI), the suspension is dispersed for 10 minutes by ultrasound and high-purity nitrogen gas is continuously introduced throughout (b)>99.9%) to discharge dissolved oxygen to ensure anaerobic environment;
(3) preparation of sodium borohydride solution: dissolving 1.33g of strong reducing agent sodium borohydride in 250ml of deionized water for later use;
(4) pouring the suspension treated in the step (2) into a 500ml three-neck flask, and adding the sodium borohydride solution prepared in the step (3) into the three-neck flask at the dropping speed of 12.5ml/min, wherein the solution is dark orange (Fe)3+) Changed to light green (Fe)2+) Finally, the mixture is changed into dark gray (namely the graphene type nitrogen carbide loaded nano zero-valent iron composite material), and in the whole synthesis process, a mechanical stirrer is used for stirring the mixed solution at the speed of 250r/min, and high-purity nitrogen gas is continuously introduced (>99.9%) to discharge dissolved oxygen to ensure anaerobic environment;
(5) preservation of the graphene type nitrogen carbide loaded nano zero-valent iron composite material: and (3) collecting the suspension obtained after the step (4) by centrifugation to obtain dark gray nano particles, washing the dark gray nano particles for 4 times by using deionized water and absolute ethyl alcohol (> 99.8%), and then storing the dark gray nano particles in the ethyl alcohol at 4 ℃.
Test for lead ion removal Effect
The effect of the graphene type nitrogen carbide loaded nano zero-valent iron composite material on removing lead ions in water is evaluated by adopting a 'reaction-separation-recycling' type nano zero-valent iron reactor. The experimental setup is shown in fig. 3. The reactor experimental device consists of a reaction tank, a gravity settling separator and a plurality of peristaltic pumps.
Raw water (influent [ Pb)2+]10mg/L) was first continuously flowed by a peristaltic pump into a reaction zone equipped with a stirrer to ensure sufficient and uniform mixing and reaction of the reactant (graphene type nitrogen carbide supported nano zero valent iron composite) with the raw water, and further equipped with online ORP and pH electrodes to monitor the operating conditions of the reaction system.
Next, the reactant is separated from the wastewater by gravity settling in the separator, and the reactant settled at the bottom of the separator is refluxed to the reaction zone using a recirculation pump to increase the utilization rate of the reactant, and the removal effect is shown in fig. 4.
Example 2
The difference from example 1 is that, in step (2):
0.50g of g-C3N4Dispersed in 250mL of 8.8mmol FeCl3·6H2O, g-C of sample3N4The mass ratio of/Fe is 1.0[ i.e. 1.0@ g-nZVI as shown in (b) of FIG. 1]The suspension is ultrasonically dispersed for 10 minutes and high-purity nitrogen is continuously introduced throughout (A)>99.9%) to remove dissolved oxygen to ensure an anaerobic environment.
Test for lead ion removal Effect
The method for evaluating the lead ion removal effect in this example is the same as that in example 1, that is, a reaction-separation-reuse type nano zero-valent iron reactor is used. The removal effect is shown in fig. 4.
The TAFEL curve of the g-nZVI electrode in 10mmol/L sodium chloride solution is determined by Tafel extrapolation method as shown in FIG. 2, and the Ecorr value of the loaded nano zero-valent iron is slightly shifted forward compared with the Ecorr of pure nano zero-valent iron, which shows that the g-nZVI has better corrosion resistance and stability than nZVI (comparative example).
Example 3
The difference from example 1 is that, in step (2):
0.25g of g-C3N4Dispersed in 250mL of 8.8mmol FeCl3·6H2O, g-C of sample3N4The mass ratio of Fe/Fe is 0.5 (i.e. 0.5@ g-nZVI), the suspension is dispersed for 10 minutes by ultrasound and high-purity nitrogen gas is continuously introduced throughout (b)>99.9%) to remove dissolved oxygen to ensure an anaerobic environment.
Test for lead ion removal Effect
The method for evaluating the lead ion removal effect in this example is the same as that in example 1, that is, a reaction-separation-reuse type nano zero-valent iron reactor is used. The removal effect is shown in fig. 4.
Comparative example
The comparative example uses pure nanoscale zero-valent iron without modification as a control.
Preparation method of nano zero-valent iron
Preparation of a volume of 0.05M FeCl3Solution and 0.2M NaBH in the same volume4A solution; under the protection of nitrogen, NaBH is added4FeCl is added dropwise into the solution at the dropping speed of 12.5ml/min3In the solution, the synthesized nano zero-valent iron, as shown in figure 1 (a), is subjected to vacuum filtration, repeated washing by deionized water and absolute ethyl alcohol, and then is stored in absolute ethyl alcohol for later use, in the whole synthesis process, a mechanical stirrer is used for stirring the mixed solution at the speed of 250r/min, and high-purity nitrogen gas is continuously introduced (a) ((A))>99.9%) to remove dissolved oxygen to ensure an anaerobic environment.
Test for lead ion removal Effect
The method for evaluating the lead ion removal effect in the comparative example is the same as that in example 1, namely, a reaction-separation-reuse type nano zero-valent iron reactor is adopted. The removal effect is shown in fig. 4.
As can be seen from fig. 4, the graphene type nitrogen carbide nano zero-valent iron composite materials of examples 1 to 3, which have different loading ratios, all exhibited a greater removal amount of lead ions, as compared to the comparative example, with example 2 being the most preferable.
Claims (10)
1. A preparation method of a graphene type nitrogen carbide loaded nano zero-valent iron composite material is characterized by comprising the following steps:
(1) synthesis of graphene type nitrogen carbide: heating urea powder, keeping the temperature, and naturally cooling to obtain g-C3N4；
(2) G to C3N4Dispersed in FeCl3Carrying out ultrasonic dispersion in the solution to obtain a suspension, and continuously introducing high-purity nitrogen in the whole process;
(3) preparation of sodium borohydride solution: dissolving sodium borohydride, a strong reducing agent, in deionized water for later use;
(4) dropwise adding a sodium borohydride solution into the suspension while stirring, continuously introducing high-purity nitrogen, stopping dropwise adding when the color of the mixed solution is changed from dark orange to dark gray, and generating the graphene type nitrogen carbide loaded nano zero-valent iron composite material;
(5) preservation of the graphene type nitrogen carbide loaded nano zero-valent iron composite material: the mixed solution was centrifuged to collect the resulting dark gray nanoparticles, washed with deionized water and absolute ethanol, and then stored in ethanol.
2. The method for preparing the graphene type nitrogen carbide-loaded nanoscale zero-valent iron composite material as claimed in claim 1, wherein the heating temperature is 520-; the heat preservation time is 2-4 h.
3. The preparation method of the graphene type nitrogen carbide-loaded nano zero-valent iron composite material according to claim 1, wherein g-C is3N4With FeCl3The mass ratio of Fe element in the solution is 0.5-2.5.
4. The preparation method of the graphene type nitrogen carbide-supported nano zero-valent iron composite material according to claim 1, wherein the ultrasonic dispersion time is 8-12 min.
5. The preparation method of the graphene type nitrogen carbide-supported nano zero-valent iron composite material according to claim 1, wherein the concentration of the sodium borohydride solution is 5-6 g/L.
6. The preparation method of the graphene type nitrogen carbide-supported nano zero-valent iron composite material according to claim 1, wherein the dropping speed of the sodium borohydride solution is 10-15 ml/min.
7. The method for preparing the graphene type nitrogen carbide-supported nano zero-valent iron composite material as claimed in claim 1, wherein the stirring rate is 200-300 r/min.
8. The method for preparing the graphene type nitrogen carbide loaded nano zero-valent iron composite material according to claim 1, wherein the graphene type nitrogen carbide loaded nano zero-valent iron composite material is stored in liquid ethanol at a temperature of 4 ℃ or lower.
9. A graphene-type nitrogen carbide-supported nano zero-valent iron composite prepared according to the method of any one of claims 1 to 8.
10. The application of the graphene type nitrogen carbide loaded nano zero-valent iron composite material as claimed in claim 9, wherein the composite material is applied to removal of heavy metal lead ions in water.
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| CN114702211A (en) * | 2022-04-07 | 2022-07-05 | 扬州大学 | Preparation method and application of supported nano zero-valent iron |
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