CN110575814A - Graphene-coated metal-based environment functional material and preparation method and application thereof - Google Patents
Graphene-coated metal-based environment functional material and preparation method and application thereof Download PDFInfo
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- CN110575814A CN110575814A CN201910799416.7A CN201910799416A CN110575814A CN 110575814 A CN110575814 A CN 110575814A CN 201910799416 A CN201910799416 A CN 201910799416A CN 110575814 A CN110575814 A CN 110575814A
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
the invention discloses an environment functional material based on graphene coated metal, which is provided with core-shell structure powder with metal nanoparticles as cores and graphene as shells, wherein amino groups are modified on the surfaces of graphene shells. The preparation method is carried out in the atmosphere containing ammonia gas or hydrogen/nitrogen mixed gas by adopting an arc discharge method, and the environment function material of the graphene coated metal nano-particles with the surface subjected to amination modification is synthesized in one step by adopting an arc discharge technology.
Description
Technical Field
The invention belongs to the technical field of environment functional materials, and particularly relates to an environment functional material based on graphene coated metal and a preparation method and application thereof.
Background
With the rapid development of economy, various pollutants, such as heavy metal ions (such as chromium, cadmium, copper, mercury, nickel, zinc and the like), radionuclide ions (such as uranium) and the like, can be generated in the industrial production processes of mining and metallurgy, mechanical manufacturing, chemical industry, electronics, instruments, electroplating, pharmacy and the like, and can cause a great amount of pollution when entering the water environment. The water body pollutants have different characteristics and toxicity due to different types, so that the incidence rate of malignant diseases such as cancer and the like can be obviously increased, and the serious threat to the health of people and the environment is caused. Water caused by mercury-containing wastewater and cadmium-containing wastewater polluted water, such as water polluted in Japan, which occurs in 60 s of 20 th century, ensures water caused by diseases and pains; when people drink organic substance polluted water for a long time, dizziness, eruption, itching, anemia and various nervous system diseases can be caused; for heavy metals with chemical toxicity and radioactive toxicity, environmental background radiation can be caused, species genes are distorted, and irreversible damage is caused to plants, farmlands and soil.
Currently, the main physicochemical methods applied to the treatment of water pollutants are: the method comprises an ion exchange method, an adsorption method, a solvent extraction method, a precipitation method, reverse osmosis, electrodialysis, an electrolysis method and the like, wherein among a plurality of treatment methods, the adsorption method is a hotspot technology for the treatment research of water pollutants due to the advantages of simple operation, high efficiency, economy, environmental protection and the like. The adsorbent material applied to the water body can reduce the concentration of various pollutants in the water body through a series of physical, chemical and biological actions such as adsorption, precipitation, complexation, ion exchange, oxidation reduction and the like, so that the concentration of the pollutants reaches the standard of the water body allowed to be discharged. Meanwhile, in order to ensure the safety of the target water body in use, the unknown concentration of the trace pollutants in the water body also needs to be rapidly detected.
In recent years, the plasmon metal nano material has excellent application prospects in the fields of trace detection and concentration control of heavy metal ions, radionuclides and organic pollutants in water due to the specific local plasma resonance characteristic and catalytic activity. Commonly used plasmonic noble metal nanomaterials include nanoscale gold, silver, copper nanoparticles. However, the plasmon precious metal nano-materials are limited in practical application, mainly including the following three points: first, bare metal nanomaterials have low chemical affinity for many analytes and are difficult to selectively interact with the desired analyte in a wide variety of mixtures; secondly, the nano material has high surface activity and is extremely easy to be corroded by substances such as oxygen, moisture and the like to lose activity; thirdly, the nanomaterial itself is prone to agglomeration. In view of the above, it is urgently required to coat the surface of the bare plasmon noble metal nanomaterial with a protective layer to ensure its normal and reliable use. Among the many coating materials, graphite materials are distinguished by their high chemical and thermal stability and good compatibility with a wide variety of substances (e.g., pharmaceutical agents, catalytically active substances). The graphite-based coating shell layer can effectively avoid direct exposure of the metal core, and can also be used as a platform carrier for further functional modification and graft composition.
At present, methods for preparing carbon-coated metal nano materials include laser ablation, arc discharge, chemical vapor deposition, hydrothermal treatment, chemical reduction methods and the like. Some of these methods are limited to harsh reaction conditions and low yields (e.g., chemical vapor deposition), some are limited to expensive equipment (e.g., laser ablation), some are limited to complicated and lengthy reaction procedures, many by-products, and are environmentally unfriendly (e.g., wet chemical synthesis). The arc discharge technology has the advantages of rapidness, convenience, simple equipment, low cost, high product quality, high yield and the like in one-step synthesis, and is widely applied to the method for preparing the carbon-coated metal nano material. In order to prepare a high-efficiency biochar environmental material with high treatment capacity and high treatment rate, the adsorbing material of the carbon-coated metal nano material prepared by arc discharge needs to be further modified and activated. The existing modification method mainly adopts a chemical method to graft polymer functional groups on the surface of the adsorption material, and the method introduces a high-molecular chemical material, so that the price is high and the operation steps are complex.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides an environment functional material based on graphene coated metal and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
The environment functional material based on the graphene coated metal is provided with core-shell structure nano powder with metal nano particles as cores and graphene as shells, and the surface of a graphene shell layer is modified with amino.
Specifically, in the environment functional material, the number of modified amino groups per gram of environment nano is 1.0 multiplied by 1018～9.9×1019。
In particular, the metal nanoparticles are plasmonic gold, silver or copper nanoparticles.
Specifically, the core layer of the environment functional material also comprises magnetic nanoparticles.
More specifically, the magnetic nanoparticles are iron and iron carbide composite particles, nickel and nickel carbide composite particles or cobalt and cobalt carbide composite particles.
The invention also provides a preparation method of the graphene-coated metal-based environment functional material, which comprises the following steps:
S10, preparing a graphite cathode and a graphite anode, wherein one end of the graphite anode is provided with a hole for containing a powder material;
S20, mixing the plasmon metal powder, the graphite powder and the graphite adhesive, or mixing the plasmon metal powder, the graphite powder, the magnetic material powder and the graphite adhesive to prepare a composite powder material;
S30, filling the composite powder material into the holes of the graphite anode to prepare and obtain a composite anode;
S40, assembling the graphite cathode and the composite anode in arc discharge equipment, and introducing mixed gas of ammonia and inert gas or mixed gas of hydrogen, nitrogen and inert gas into the reaction chamber;
And S50, controlling the arc discharge equipment to perform arc discharge between the graphite cathode and the composite anode, and collecting powder materials in the reaction chamber after the discharge is finished to prepare the environment functional material.
Specifically, when arc discharge is performed, the discharge current is 50A to 200A, the discharge voltage is 10V to 30V, the pressure of the discharge atmosphere is 10Torr to 700Torr, and the discharge time is 0.5min to 10 min.
Specifically, when the gas introduced into the reaction chamber is a mixed gas of ammonia gas and inert gas, the volume ratio of the ammonia gas to the inert gas is (0.05% -100.0%) (99.95% -0.0%); when the gas introduced into the reaction chamber is a mixed gas of hydrogen, nitrogen and inert gas, the volume ratio of the hydrogen, the nitrogen and the inert gas is (0.05% -50%) (0.05% -50.0%) (99.0% -0.0%).
Specifically, when the composite powder material is a mixed material of plasmon metal powder, graphite powder and a graphite adhesive, the mass ratio of the plasmon metal powder to the graphite adhesive is (1-10): (10-1): 1; when the composite powder material is a mixed material of plasmon metal powder, graphite powder, magnetic material powder and a graphite adhesive, the mass ratio of the plasmon metal powder, the graphite powder, the magnetic material powder and the graphite adhesive is (1-10): 10-1): 1.
The invention also provides an application of the graphene-coated metal-based environment functional material, which comprises the following steps: the method is used for removing heavy metal ions and nuclide ion pollutants in the water body by adsorption as an adsorbent, carrying out catalytic reduction on aromatic organic pollutants in the water body by using the catalyst, and detecting trace heavy metal ions and nuclide ions in the water body.
The environment functional material based on the graphene coated metal provided by the embodiment of the invention has core-shell structure powder with metal nanoparticles as a core and graphene as a shell, and the surface of the graphene shell is modified with amino. In the preparation method, the metal nano particles coated with the graphene are prepared and obtained by adopting an arc discharge method as the environment functional material, the arc discharge process is carried out in the atmosphere containing ammonia gas or hydrogen/nitrogen mixed gas, the metal environment functional material coated with the graphene is prepared and simultaneously the surface of the material is modified with amino, namely, the metal environment functional material coated with the graphene with the aminated surface is synthesized in one step by adopting the arc discharge technology, the preparation process is simple and easy to realize, and the number of the surface functional groups is increased by modifying the amino groups on the surface of the material, so that the complexing capability of the material on pollutants such as heavy metal ions, radionuclide ions and the like in a water body is improved, and further, the high-sensitivity high-selectivity rapid detection on trace heavy metal ions and radionuclide ions can be realized, and the effective adsorption removal on high-concentration heavy metal ions/radionuclide ions can be realized, Realizing high-efficiency catalytic reduction of aromatic organic pollutants.
drawings
FIG. 1 is a process flow diagram of a method for preparing an environmental functional material according to an embodiment of the present invention;
FIG. 2 is an X-ray photoelectron spectrum of the environmental functional material prepared in example 1 of the present invention.
FIGS. 3 and 4 are TEM images of an environmentally functional material prepared in example 1 of the present invention;
FIGS. 5 and 6 are TEM images of an environmentally functional material prepared in example 2 of the present invention;
FIGS. 7 and 8 are photographic illustrations of reduction tests of organic dyes with the environmental functional materials prepared in example 2 of the present invention;
Fig. 9 and 10 are TEM images of the environment functional material prepared in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment provides an environment functional material based on graphene coated metal, the environment functional material is core-shell structure nano powder with metal nano particles as a core and graphene as a shell, and the surface of the graphene shell is modified with amino. The graphene is adopted to coat the metal nanoparticles to form the environment functional material with a core-shell structure, and the surface of the graphene shell is subjected to high-concentration amino group modification, so that the complexing capability of the environment functional material on pollutants in a water body is improved. Wherein, in the environment functional material, the number of the modified amino groups per gram of the environment functional material can reach 1.0 multiplied by 1018～9.9×1019。
In particular, the metal nanoparticles are plasmonic metal nanomaterials, for example gold, silver or copper nanoparticles. The particle size of the metal nano-particles is 5 nm-5 mu m. It should be noted that the metal nanoparticles described in the present invention may be in the form of nanospheres or nanowires. If the nanosphere is nanosphere, the particle size is 5 nm-500 nm; if the nano-wire is used, the diameter of the nano-wire is 5nm to 100nm, and the length of the nano-wire is 1 μm to 5 μm.
Further, the core layer of the environment functional material also comprises magnetic nanoparticles. After the environmental functional material adsorbs pollutants in a water body, the environmental functional material needs to be separated from a liquid phase, the plasmon metal nano material is difficult to realize effective separation of the environmental functional material and the liquid phase due to the size effect, and the separation cost of the material is undoubtedly further improved by means of centrifugation, filtration and the like. From the practical application perspective, if the magnetic nano material is compositely introduced to the plasmon metal nano material as a composite material, the magnetic nano material is beneficial to economic and effective separation, recovery and reutilization.
In a preferred embodiment, the magnetic nanoparticles are preferably iron/iron carbide nanoparticles. In other embodiments, the magnetic nanoparticles may also be selected to be nickel/nickel carbide nanoparticles or cobalt/cobalt carbide nanoparticles. Further, the particle size of the magnetic nanoparticles is 10nm to 200 nm.
Referring to fig. 1, the method for preparing the graphene-clad metal-based environment functional material includes the steps of:
S10, preparing a graphite cathode and a graphite anode, wherein one end of the graphite anode is provided with a hole for containing the powder material.
Specifically, two graphite electrodes with a diameter of 0.5cm to 2cm and a length of 1cm to 10cm may be selected, one end of one of the two graphite electrodes is sharpened to form the graphite cathode, and the other end of the other graphite electrode is drilled to form the graphite anode, wherein the diameter of the hole may be set within a range of 0.3cm to 1.8cm, and the depth of the hole may be set within a range of 0.9cm to 9 cm.
And S20, mixing the plasmon metal powder, the graphite powder and the graphite adhesive, or mixing the plasmon metal powder, the graphite powder, the magnetic material powder and the graphite adhesive to prepare the composite powder material.
Specifically, when the composite powder material is a mixed material of plasmon metal powder, graphite powder and a graphite adhesive, the mass ratio of the plasmon metal powder to the graphite adhesive is selected to be (1-10): (10-1): 1; when the composite powder material is a mixed material of plasmon metal powder, graphite powder, magnetic material powder and a graphite adhesive, the mass ratio of the plasmon metal powder, the graphite powder, the magnetic material powder and the graphite adhesive is (1-10): 10-1): 1.
Wherein the plasmonic metal powder is, for example, gold powder, silver powder, or copper powder. The magnetic material powder can be selected from iron oxide, nickel oxide or cobalt oxide; when iron oxide is selected and subjected to arc discharge, the finally formed magnetic nanoparticles are composite nanoparticles of iron and iron carbide; when nickel oxide is selected and subjected to arc discharge, the finally formed magnetic nanoparticles are composite nanoparticles of nickel and nickel carbide; when cobalt oxide is selected for use, the finally formed magnetic nanoparticles are composite nanoparticles of cobalt and cobalt carbide after arc discharge.
S30, filling the composite powder material into the holes of the graphite anode to prepare the composite anode.
Specifically, after the composite powder material is filled into the holes of the graphite anode, the graphite anode is heated for 1-24 h at the temperature of 100-300 ℃, and the composite anode is prepared.
S40, assembling the graphite cathode and the composite anode in arc discharge equipment, and introducing mixed gas of ammonia gas and inert gas or mixed gas of hydrogen gas, nitrogen gas and inert gas into the reaction chamber.
Specifically, when the gas introduced into the reaction chamber is a mixed gas of ammonia gas and inert gas, the volume ratio of ammonia gas to inert gas can be selected to be (0.05% -100.0%) (99.95% -0.0%); when the gas introduced into the reaction chamber is a mixed gas of hydrogen, nitrogen and inert gas, the volume ratio of hydrogen, nitrogen and inert gas can be selected to be in the range of (0.05% -50%) (0.05% -50.0%) (99.0% -0.0%). Wherein the inert gas is argon or helium. In the mixed gas, when the volume ratio of the inert gas is 0.0%, that is, the introduced gas is pure ammonia gas or only hydrogen gas and nitrogen gas are introduced.
and S50, controlling the arc discharge equipment to perform arc discharge between the graphite cathode and the composite anode, and collecting the nano powder in the reaction chamber after the discharge is finished to prepare the environment functional material.
specifically, when arc discharge is performed, the discharge current may be set to be in the range of 50A to 200A, the discharge voltage may be set to be in the range of 10V to 30V, the pressure of the discharge atmosphere may be set to be in the range of 10Torr to 700Torr, and the discharge time may be set to be in the range of 0.5min to 10 min.
In the invention, an arc discharge method is adopted, so that the graphene coated plasmon metal nano material can be formed into an environment functional material with a core-shell structure.
On the other hand, the arc discharge process is performed in a discharge atmosphere containing ammonia (or a combination of hydrogen and nitrogen), the surface of the environmental nanomaterial is modified with amino while the environmental functional material with the graphene-coated structure is prepared, and the process principle is as follows: the arc discharge initiates plasma through an electric field, a large amount of high-energy active particles are generated at the center of the plasma, nitrogen particles are effectively bonded with a carbon source to participate in the construction of a graphene shell body, and hydrogen particles are used for regulating and controlling the thickness of the graphene shell through etching the carbon source; and a plurality of metastable active groups such as amino, imino and the like are distributed at a position far away from the center of the electric arc, and the groups form new bonds with carbon atoms on the surface of a graphite shell layer, so that the material surface has new characteristics and the surface amino functionalized modification is realized. Some specific reaction processes include the following reaction formulas:
e+Ar→Ar*+e，
e+C→C*+e，
N2+Ar*→N*+N*+Ar，
H2+Ar*→H*+H*+Ar，
N*+H*→NH，
He*+NH3→NH2+H+He，
He*+NH3→NH+H+H+He，
He*+NH3→N+H+H+H+He，
NH2+C→C-NH2，
NH+C→C-NH，
N+C→C-N。
The environment function material based on the graphene coated metal and the preparation method thereof provided by the embodiment of the invention have the following advantages:
(1) the amino groups are modified on the surface of the core-shell structure material of the graphene coated metal nano particles, so that the number of the amino functional groups on the surface of the environment functional material is increased, and the complexing capability of the environment functional material on pollutants such as heavy metal ions, radionuclide ions and the like in a water body is improved. The environmental nano-material prepared by the embodiment of the invention can rapidly detect heavy metal and nuclide ions with high sensitivity and high selectivity, effectively enrich pollutants such as heavy metal, nuclide ions and the like in water, efficiently reduce and convert aromatic organic pollutants, and realize high value-added utilization of the material.
(2) compared with the prior art that the core-shell structure environment functional material is prepared firstly and then a wet chemical modification mode is adopted, the use of chemical reagents such as a cross-linking agent, a coupling agent and the like can be avoided, a large amount of secondary pollutants are not generated, the working procedures of waste liquid/waste solid treatment and the like which are necessary in the wet chemical treatment process are not needed, and the method has the effects of time saving, high efficiency and environmental friendliness.
In addition, aiming at the environmental functional material prepared under given conditions, the invention can control the parameters such as working voltage, current, time and the like when the arc discharge treatment is carried out, thereby controlling the number of amino groups in the finally obtained amination modified environmental functional material. The method adopts the following method to measure the number of amino groups in the environment functional material:
the Sulfo-LC-SPDP bifunctional cross-linking agent is adopted to react with a certain mass of amination modified environment functional material to generate a Pyridyldithiol activating material; then the material activated by Pyridyldithiol is further reacted with dithiothreitol, and then the Pyridine 2-thione is cut off; quantitatively calculating the concentration of the Pyridine 2-thione by analyzing the absorption peak value of the Pyridine 2-thione at 343 nm; the concentration of the amino group is the same as that of Pyridine 2-thione, so that the specific number of the amino groups contained in the environment functional material per unit mass can be calculated.
example 1
(1) And preparing the arc discharge graphite cathode and the graphite anode, wherein one end of the graphite anode is provided with a hole with the aperture of 0.7cm and the hole depth of 5 cm.
(2) And mixing graphite powder, gold powder, iron oxide powder and a graphite adhesive according to the mass ratio of 2:1:1:1 to prepare the composite powder material.
(3) And filling the composite powder material into holes of the graphite anode, and heating at 120 ℃ for 24h to prepare the composite anode.
(4) And assembling the graphite cathode and the composite anode in arc discharge equipment for arc discharge. The arc discharge atmosphere was ammonia gas and argon gas (volume ratio 1.0%: 99.0%), the operating pressure was 100Torr, the operating current was 200A, the operating voltage was 30V, and the operating time was 2 min. And after the discharge is finished, collecting the powder material after the reaction is finished, and preparing to obtain the environment functional material.
FIG. 2 is an X-ray photoelectron spectrum (curve) of the environmental functional material obtained in the present exampleLine 1.0% NH3). For comparison, in this example, a comparative environment functional material was prepared by changing the discharge atmosphere to pure argon gas only under the same other conditions, and the X-ray photoelectron spectrum thereof is also shown in fig. 2 (curve 0% NH)3)。
1.0% NH from Curve of FIG. 23A clear N1s peak can be seen, indicating that the surface of the prepared ambient functional material contains amino groups when the discharge atmosphere contains ammonia. When the amount of amino groups in the environmental functional material is measured according to the method described above, the amount of amino groups modified by each gram of the environmental functional material in the environmental functional material prepared in this embodiment can reach up to 2.5 × 1019。
Fig. 3 and 4 are TEM images of the environmental functional material prepared in this example at different magnifications, and it can be seen from fig. 3 and 4 that the iron compound and the gold core are both coated with the graphite material, and the gold core is distributed around the iron compound and has a satellite structure.
In this embodiment, the prepared environmental functional material is subjected to experimental verification for controlling water pollutants (mainly heavy metal ions and radionuclide ions), and the experimental verification process is explained below. The experimental process of adsorbing the water pollutants is mainly carried out in a 250mL conical flask by adopting a static adsorption batch experiment, and the specific experimental process is as follows:
(S1), weighing a certain mass of compound containing adsorbate (namely, solution containing pollutant, such as lead chloride, cadmium chloride, copper chloride, uranyl nitrate and the like), and dissolving the compound in deionized water to prepare 1000mg/L stock solution of pollutant adsorbate.
(S2) weighing a certain mass of adsorbent (surface amination modified environment functional material) and placing the adsorbent in a conical flask, and then adding a certain volume of storage solution of pollutant adsorbate and a certain volume of deionized water to enable the concentration of each substance component to reach the set value of the condition experiment.
(S3), standing for a period of time to allow the adsorption reaction to reach equilibrium. In the experiment, 0.1mol/L HCl and 0.01mol/L NaOH solution can be used for adjusting the reaction liquid to a certain pH condition, and the reaction is carried out in a constant-temperature water bath oscillator so as to reach the adsorption equilibrium as soon as possible.
(S4) after the adsorption reaction time is over, separating the adsorbent from the water phase solution by using a high-speed centrifuge, and measuring the concentration of the residual pollutant in the supernatant by using ICP-MS, ultraviolet spectrophotometry or ion chromatography, namely the equilibrium concentration of the pollutant in the water phase. Depending on the initial and equilibrium concentrations of the contaminant and the amount of adsorbent used, the percentage (%) of adsorption of the contaminant and the amount of adsorption (q) can be calculated by the following equations (A) and (B), respectivelye,mg/g)：
In the formulae (A) and (B), C0And CeRespectively is the initial pollutant concentration in the water phase and the residual pollutant concentration in the water phase after adsorption equilibrium, m is the mass of the adsorbent, and V is the total volume of the solution in the adsorption system.
According to the experimental verification method described above, the environmental functional material prepared in this embodiment is used for research on removal of various pollutants in a water body, various experimental conditions are adjusted, and after adsorption equilibrium is completed, the results are shown in table 1 below after analysis and test.
Table 1: performance of environment functional material with amino modified surface for removing pollutants in water body
As can be seen from table 1, the environmental functional material prepared by the present embodiment can effectively adsorb and remove heavy metal ions and radionuclide ion pollutants in a water body, and particularly has a high efficient adsorption capacity for heavy metal ions.
in this embodiment, the performance evaluation of the prepared environmental functional material for efficient catalytic reduction of aromatic organic pollutants is performed, and the evaluation method is as follows: adding a certain mass of sodium borohydride into aqueous solutions of organic pollutants (p-nitrophenol, methyl orange, methylene blue and the like) with specified concentrations respectively, adding a certain mass of environmental functional materials serving as catalysts into the aqueous solutions of the organic pollutants, and recording the change condition of an absorption characteristic peak of the organic pollutants with an ultraviolet-visible spectrophotometer along with reduction time or recording the decoloration condition of the organic pollutants (organic dyes) by using a camera.
According to the above-described evaluation method, the environmental functional material prepared in this example is used for studying the catalytic reduction conversion performance of p-nitrophenol in a water body, and the data in the following table 2 is obtained through an analysis test.
Table 2: catalytic reduction conversion performance of environment functional material with amino modified surface on p-nitrophenol in water body
as can be seen from Table 2, the prepared environment functional material has extremely high activity factor, which is significantly higher than that of many reported catalyst materials for reducing p-nitrophenol.
Example 2
(1) And preparing the arc discharge graphite cathode and the graphite anode, wherein one end of the graphite anode is provided with a hole with the aperture of 1cm and the hole depth of 3 cm.
(2) And mixing graphite powder, copper powder and a graphite adhesive according to the mass ratio of 1:1:2 to prepare the composite powder material.
(3) and filling the composite powder material into holes of the graphite anode, and heating at the temperature of 200 ℃ for 12h to prepare the composite anode.
(4) And assembling the graphite cathode and the composite anode in arc discharge equipment for arc discharge. The arc discharge atmosphere was ammonia gas and argon gas (volume ratio: 75.0%: 25.0%), the operating pressure was 150Torr, the operating current was 150A, the operating voltage was 20V, and the operating time was 1 min. And after the discharge is finished, collecting the powder material after the reaction is finished, and preparing to obtain the environment nano material.
fig. 5 and 6 are TEM images of the environmental functional material prepared in this embodiment at different magnifications, and as can be seen from fig. 5 and 6, the surface of the copper nanowire is coated with 3-5 layers of graphene in the prepared environmental functional material. When the amount of amino groups in the environmental functional material is measured according to the method described above, the amount of amino groups modified per gram of the environmental functional material prepared in this example can reach 5.7 × 1018。
The environmental functional material prepared in this example was used to study the catalytic reduction conversion performance of p-nitrophenol in a water body by referring to the evaluation method described in example 1, and the following data in table 3 were obtained by analytical tests.
Table 3: catalytic reduction conversion performance of environment functional material with amino modified surface on p-nitrophenol in water body
As can be seen from Table 3, the prepared environmental functional material has extremely high activity factor, which is significantly higher than that of many reported catalyst materials for reducing p-nitrophenol.
The environmental functional materials prepared in this example were used to study the catalytic reduction conversion performance of organic dyes (methylene blue, methyl orange) in water, according to the evaluation method described in example 1, and were recorded in the form of photographs in consideration of the excessive reduction efficiency of the organic dyes by the above environmental functional materials. Fig. 7 is a photograph of catalytic reduction decoloring of methylene blue by an environment functional material modified with amino groups on the surface. Fig. 8 is a photograph of methyl orange decolorized by catalytic reduction using an environmental functional material modified with amino groups on the surface.
As can be seen from FIGS. 7 and 8, 10mg/L of methylene blue dye can be completely reduced in only 5 seconds, the reduction efficiency is quite high, and methyl orange which is difficult to reduce or degrade in the prior art is completely reduced in about 60 seconds. The prepared environment functional material shows excellent catalytic activity to dyes methylene blue and methyl orange.
Example 3
(1) And preparing the arc discharge graphite cathode and the graphite anode, wherein one end of the graphite anode is provided with a hole with the aperture of 0.5cm and the hole depth of 1 cm.
(2) And mixing the graphite powder, the silver powder and the graphite adhesive according to the mass ratio of 1:2:1 to prepare the composite powder material.
(3) And filling the composite powder material into holes of the graphite anode, and heating at 260 ℃ for 2h to prepare the composite anode.
(4) And assembling the graphite cathode and the composite anode in arc discharge equipment for arc discharge. The arc discharge atmosphere was ammonia gas and argon gas (volume ratio 20.0%: 80.0%), the operating pressure was 100Torr, the operating current was 100A, the operating voltage was 15V, and the operating time was 3 min. And after the discharge is finished, collecting the powder material after the reaction is finished, and preparing to obtain the environment nano material.
Fig. 9 and 10 are TEM images of the environment functional material prepared in this embodiment at different magnifications, and as can be seen from fig. 9 and 10, the surface of the silver core in the prepared environment functional material is coated with 4-6 layers of graphene. When the amount of the amino group in the environmental functional material is measured according to the method described above, the amount of the amino group modified per gram of the environmental functional material in the environmental functional material prepared in this embodiment can reach 9.3 × 1018。
In this embodiment, the performance evaluation of the prepared environmental functional material for detecting trace heavy metal ions and radionuclides is performed, and the evaluation method is as follows: analyzing the position lambda of the characteristic peak of the local plasma resonance of the environmental functional material in the aqueous solution by adopting an ultraviolet-visible spectrophotometermaxand the absorption peak Abs at that locationmax. Adding a certain mass of environment functional material into heavy metal and nuclide ion aqueous solution with specified concentration respectively, and recording the position lambda of the resonance characteristic peak of the local plasmamaxAnd the absorption peak Abs at that locationmaxand (4) constructing a linear range of detection and calculating a detection limit.
according to the above described evaluation method, the environmental functional material prepared in this embodiment is used for studying the detection performance of trace heavy metal ions and radionuclides in water, and the data in the following table 4 is obtained through analysis and test.
Table 4: detection performance of environment functional material with amino modified surface on trace heavy metal ions and nuclide ions in water body
as can be seen from Table 4, the prepared environment functional material shows excellent linear detection ranges for heavy metal copper, mercury ions and nuclide uranyl ions in water, and the lowest linear detection values are respectively 1.0 multiplied by 10-8mol/L、1.0×10-9mol/L、2.0×10-8mol/L which is far lower than the safe concentration limit of the pollutants in the drinking water, wherein the safe concentration limit of copper, mercury and uranyl in the drinking water is respectively 20 multiplied by 10-6mol/L、5.0×10-9mol/L、1.26×10-7mol/L。
In conclusion, the environment functional material with the surface amino modified graphene coated metal nanoparticles is synthesized in one step by adopting the arc discharge technology, the preparation process is simple and easy to realize, and the prepared environment functional material realizes high-sensitivity and high-selectivity detection on water pollutants and can effectively enrich and efficiently catalyze and reduce the water pollutants.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (10)
1. The environment functional material based on the graphene coated metal is characterized by comprising core-shell structure powder with metal nanoparticles as cores and graphene as shells, wherein amino groups are modified on the surfaces of the graphene shell layers.
2. The graphene-coated metal-based environment functional material according to claim 1, wherein the number of modified amino groups per gram of environment functional material is 1.0 x 1018～9.9×1019。
3. The graphene-coated metal-based environmentally functional material of claim 1, wherein the metal nanoparticles are plasmonic gold, silver or copper nanoparticles.
4. the graphene-coated metal-based environment functional material according to claims 1-3, wherein the core layer of the environment functional material further comprises magnetic nanoparticles.
5. The graphene-coated metal-based environment functional material according to claim 4, wherein the magnetic nanoparticles are iron and iron carbide composite particles, nickel and nickel carbide composite particles or cobalt and cobalt carbide composite particles.
6. the preparation method of the graphene-clad-metal-based environment functional material according to any one of claims 1 to 5, comprising the steps of:
S10, preparing a graphite cathode and a graphite anode, wherein one end of the graphite anode is provided with a hole for containing a powder material;
S20, mixing the plasmon metal powder, the graphite powder and the graphite adhesive, or mixing the plasmon metal powder, the graphite powder, the magnetic material powder and the graphite adhesive to prepare a composite powder material;
S30, filling the composite powder material into the holes of the graphite anode to prepare and obtain a composite anode;
S40, assembling the graphite cathode and the composite anode in arc discharge equipment, and introducing mixed gas of ammonia and inert gas or mixed gas of hydrogen, nitrogen and inert gas into the reaction chamber;
And S50, controlling the arc discharge equipment to perform arc discharge between the graphite cathode and the composite anode, and collecting powder materials in the reaction chamber after the discharge is finished to prepare the environment functional material.
7. The method for preparing the graphene-coated metal-based environment functional material according to claim 6, wherein during arc discharge, the discharge current is 50A to 200A, the discharge voltage is 10V to 30V, the pressure of the discharge atmosphere is 10Torr to 700Torr, and the discharge time is 0.5min to 10 min.
8. The method for preparing the environment functional material based on the graphene coated metal according to claim 6, wherein when the gas introduced into the reaction chamber is a mixed gas of ammonia gas and inert gas, the volume ratio of the ammonia gas to the inert gas is (0.05% -100.0%); when the gas introduced into the reaction chamber is a mixed gas of hydrogen, nitrogen and inert gas, the volume ratio of the hydrogen, the nitrogen and the inert gas is (0.05% -50%) (0.05% -50.0%) (99.0% -0.0%).
9. The method for preparing the graphene-coated metal-based environment functional material according to claim 6, wherein when the composite powder material is a mixed material of plasmon metal powder and graphite powder with a graphite binder, the mass ratio of the plasmon metal powder to the graphite binder is (1-10): (10-1): 1; when the composite powder material is a mixed material of plasmon metal powder, graphite powder, magnetic material powder and a graphite adhesive, the mass ratio of the plasmon metal powder, the graphite powder, the magnetic material powder and the graphite adhesive is (1-10): 10-1): 1.
10. The use of the graphene coated metal based environmentally functional material of any one of claims 1 to 5, comprising: the method is used for removing heavy metal ions and nuclide ion pollutants in the water body by adsorption as an adsorbent, carrying out catalytic reduction on aromatic organic pollutants in the water body by using the catalyst, and detecting trace heavy metal ions and nuclide ions in the water body.
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