CN110015746A - A kind of preparation method and application of graphene multi-element metal composite material - Google Patents
A kind of preparation method and application of graphene multi-element metal composite material Download PDFInfo
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- CN110015746A CN110015746A CN201910391675.6A CN201910391675A CN110015746A CN 110015746 A CN110015746 A CN 110015746A CN 201910391675 A CN201910391675 A CN 201910391675A CN 110015746 A CN110015746 A CN 110015746A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a kind of preparation method and applications of graphene multi-element metal composite material, belong to graphene multi-element metal technical field of composite materials.The present invention, which adds graphene oxide into solvent and carries out 1~2h of ultrasonic disperse processing, obtains graphene oxide dispersion；Reducing agent, alkali, dissolving metal salts are obtained into mixed solution in graphene oxide dispersion；Mixed solution is subjected to high temperature hydro-thermal reaction 12-24h, rear centrifugal treating is cooled to room temperature, removes supernatant liquor, adopt and solid is washed with deionized, graphene multi-element metal composite material obtained by drying.The present invention loads nano-scale catalytic site on the surface of graphene, makes more metallic compound high degree of dispersion of material load using the loading concentrations of nanomorphic multi-element metal compound and the regulation of granular size, and pattern is uniform, not easy to reunite, catalytic performance enhancing；Peroxide activator can be synchronized and disinfection by-products is inhibited to generate, disinfectant is substantially improved to the degradation capability of organic matter.
Description
Technical field
The present invention relates to a kind of preparation method and applications of graphene multi-element metal composite material, belong to the polynary gold of graphene
Belong to technical field of composite materials.
Background technique
In our daily life, water be it is essential, the technology of water process is also being continuously improved, wherein organic matter
Removal have been a hot spot of research, peroxide has and stablizes under high water solubility, easily storage, room temperature etc. as oxidating chemicals
Characteristic, in high-level oxidation technology field using more and more extensive.
Specific to the removal process of practical organic matter, by taking persulfate as an example, persulfate ionizes in water generates S2O8 2-
Ion, S2O8 2-Oxidation-reduction potential (relative to standard hydrogen electrode) be about EΘ=2.01V, between common oxidant H2O2(EΘ
=1.77V) and O3(EΘ=2.07V) between；Due to lower reaction rate under normal temperature conditions, persulfate is to organic matter
Oxidation effectiveness is not significant, therefore, in persulfate advanced oxidation processes, needs to activate persulfate to improve it
Oxidability.
Common activation method has thermal activation, ultrasonic wave, ozone, transition metal activation etc., but in practical applications by
Different degrees of limitation: although for example, thermal activation mode can effective activation persulfate, reaction activity is higher, energy consumption
Excessive, economy is not strong, and in research of many about persulfate thermal activation, activation temperature, which is usually more than 60 DEG C, just to be had
Good result causes the practical application of this kind of mode centainly to be restricted；Transition metal ions has persulfate preferable
Activation characteristic, but China's standards for drinking water quality (GB5749-2006) has relatively stringent regulation to transition metal,
Such as Ni 0.02mg/L, Fe 0.3mg/L, Mn 0.1mg/L, Cu 1.0mg/L, therefore how to reduce the exudation of transition metal in water
It is still a difficult point；Although ultrasonic technique has when activating degradation of contaminant, easy to operate, equipment is simple, applied widely
The advantages of, but the problems such as there is also costly, energy consumption is high, contaminant degradation is not thorough；Ozone activation has organic pollutant
Have universal oxidative degradation effect, and easy to operate, processing water outlet be conducive to reuse, it is without secondary pollution the advantages that, but ozone send out
Raw at high cost and utilization rate is low.
And in recent years " solid base " activation persulfate paid close attention to, i.e., by layered double hydroxide (LDH:
Layered double hydroxides) realize that solid base activates persulfate, realize organic pollutant oxidation, and lock
Sulfate ion, and oxidation susceptibility is further promoted using thermal activation degradation of organic substances.But the method has some limitations,
It needs to heat larger waters in practical application, energy consumption is high, and reaction rate is lower, COD and TOC removal rate is low, and living with heat
Changing the process combined has free radical generation, and there are the generation risks of disinfection by-products.
Therefore, it is urgent to provide the new materials and method of a kind of organic pollutants of degrading, to solve to deposit in the prior art
Drawbacks described above.
Summary of the invention
For organic matter degradation in the prior art, the present invention provides a kind of graphene multi-element metals
The preparation method and application of composite material mixes graphene dispersing solution, reducing agent, alkali, metal salt, and hydro-thermal reaction 12~for 24 hours,
It is centrifuged, washes, dried to get nanomorphic graphene multi-element metal composite material after cooling；Synthesis process of the invention is by changing
Become the control graphene reducing degree such as type, concentration, temperature of reducing agent, is nano shape multi-element metal compound in graphene
The load on surface provides the site of different number, to regulate and control the loading concentrations and granular size of nanomorphic multi-element metal compound,
And metallic compound high degree of dispersion, not easy to reunite, particulate load concentration reduces but characteristic enhances.
A kind of preparation method of graphene multi-element metal composite material, the specific steps are as follows:
(1) it adds graphene oxide into solvent and carries out 1~2h of ultrasonic disperse processing and obtain graphene oxide dispersion
Liquid；
(2) reducing agent, alkali, dissolving metal salts are obtained into mixed solution in step (1) graphene oxide dispersion；
(3) step (2) mixed solution is subjected to high temperature hydro-thermal reaction 12-24h, is cooled to room temperature rear centrifugal treating, removes
Supernatant liquor is adopted and solid is washed with deionized, graphene multi-element metal composite material obtained by drying.
Solvent is water and/or alcohol in the step (1), and wherein alcohol is methanol and/or ethyl alcohol, and the volume ratio of water and alcohol is
1:(4~10).
The concentration of graphene oxide is 1~5g/L in graphene oxide dispersion in the step (1).
Step (2) reducing agent be one of hydrazine hydrate, urea, sodium borohydride or a variety of, reducing agent and oxidation stone
The mass ratio of black alkene is (0.1~10): 1.
Step (2) alkali is sodium hydroxide and/or potassium hydroxide, and the molar concentration of alkali is 1~4mol/ in mixed solution
L。
Step (2) metal salt is the mixture of divalent metal salt and trivalent metal salt.
Further, the divalent metal salt is magnesium nitrate, nickel nitrate, copper nitrate, magnesium chloride, nickel chloride, copper chloride
It is one or more；Trivalent metal salt is aluminum nitrate and/or aluminium chloride.
Further, the molar concentration of divalent metal salt is 30~60mmol/L, trivalent metal in the mixed solution
The molar concentration of salt is 10~20mmol/L.
The temperature of step (3) the high temperature hydro-thermal reaction is 50~200 DEG C.
Preferably, the temperature of step (3) the high temperature hydro-thermal reaction is 80~120 DEG C.
Application of the graphene multi-element metal composite material in degradation of organic substances prepared by the present invention.
Application method of the graphene multi-element metal composite material in degradation of organic substances: to containing the liquid for needing degradation of organic substances
Peroxide and graphene metallic composite are added in body, is uniformly mixed, and degradation reaction removes organic matter.
The peroxide be persulfate, hydrogen peroxide, Peracetic acid, percarbonate it is one or more.
The molar ratio of the graphene metallic composite and peroxide is for (1~50): 1.
To concentration≤100mg/L of degradation of organic substances, peroxide and organic matter in the liquid to degradation of organic substances
Molar ratio be (0.5~100): 1.
It preferably, is 3~30mg/L to the concentration of degradation of organic substances in the liquid to degradation of organic substances；Peroxide
Molar ratio with organic matter is (5~20): 1；
Graphene multi-element metal composite material of the present invention can be used for any organic matter handled using peroxide oxidation；
Preferably, the organic matter of the degradation is phenol and/or 4- bromine phenol；
Preferably, the temperature of the degradation reaction is 25 DEG C~70 DEG C；
Graphene metallic composite and peroxide are combined, peroxide activator can be synchronized and inhibit disinfection by-product
Object generates, and has preferably organic matter degradation ability, and processing speed is fast, and high-efficient and solid material easily passes through precipitating removal, after
Adverse effect will not be generated in continuous processing.
The present invention is by graphene and the mutually compound obtained graphene multi-element metal composite material of multi-element metal compound and mistake
Oxide synergy effect, the two combination after can synchronize effective peroxide activator and inhibit disinfection by-products generate, have compared with
Excellent organic matter degradation ability, solves that reaction rate is slow, COD, TOC removal rate while promoting oxidation susceptibility, reducing energy consumption
Low problem, processing speed is fast, and high-efficient and solid material easily passes through precipitating removal, will not generate bad shadow in subsequent processing
It rings；
Principle: graphene has big high-specific surface area, high conductivity, corrosion-resistant, absorption organic matter etc., as multi-element metal
The carrier of composite material is conducive to electron-transport, the reunion accumulation of loaded article in the solution is effectively avoided, so that loaded article uniformly divides
It dissipates；Compared to graphene oxide, redox graphene defective bit is more, and electric conductivity is better, and electron transport ability is stronger, therefore
The reducing degree of graphene is controlled by type, concentration, the temperature etc. that change reducing agent, and then controls the site of graphene surface
Number is to realize the controllable of nano shape metallic compound loading concentrations, metallic compound high degree of dispersion, and concentration reduces but characteristic increases
By force, and electron transport ability enhances, therefore the graphene in graphene multi-element metal composite material is redox graphene,
Redox graphene and multi-element metal compound are mutually compound, give full play to its advantage, act synergistically, reach more with peroxide
Excellent degradation of organic substances effect.
Beneficial effects of the present invention:
(1) preparation method of graphene multi-element metal composite material of the present invention is one pot of change hydro-thermal method green syt, is not necessarily to
Template medicament, process are simple；
(2) the method for the present invention synthesis process controls graphene by type, concentration, the temperature etc. that change reducing agent and restores journey
Degree, provides the site of different number for the load of multi-element metal compound on the surface of graphene, to regulate and control nanomorphic multi-element metal
The loading concentrations and granular size of compound, and metallic compound high degree of dispersion, pattern is uniform, and not easy to reunite, particulate load is dense
Degree reduces but characteristic enhances；The nano shape multi-element metal compound high degree of dispersion grown on the surface of graphene, pattern is uniform, bears
It carries concentration and granular size is controllable；
(3) graphene multi-element metal composite material is used in combination the present invention with persulfate, improves persulfate and utilizes
Rate, organic removal rate may be up to 87.6% at 25 DEG C, hence it is evident that be higher than multi-element metal compound composite material comparative example
(57.9%)；Mineralization of organic material degree is high, COD at 25 DEG CMnRemoval rate, up to 30.5%, is shown up to 55.7%, TOC removal rate
It writes and is higher than comparative example (1.4%, 0%)；In addition, can inhibit the conversion of bromide ion, the generation of bromo disinfection by-products in water is reduced；
(4) the graphene multi-element metal composite material that uses of the present invention, incorporate graphene to the absorption of pollutant, to electricity
The quick transmission of son, the activation to persulfate, nano shape multi-element metal compound high degree of dispersion, multi-element metal compound are living
Change the multifrequency natures such as persulfate, graphene and multi-element metal compound synergistic effect；It can be synchronous after being combined with peroxide
Effective peroxide activator and inhibition disinfection by-products generate, and have preferably organic matter degradation ability, can aoxidize being promoted
It is low with the reaction efficiency that persulfate is used in combination that multi-element metal compound is further solved while performance, reduction energy consumption,
COD, TOC removal rate are low, bromo organic by-products problem caused by underwater trace bromide ion；
(5) graphene multi-element metal composite material of the invention exists in solution in solid form, is easily gone by precipitating
It removes, adverse effect will not be generated in subsequent processing；
(6) operation of the present invention is simple, practical.
Detailed description of the invention
Fig. 1 is the removal rate comparison diagram of phenol in Examples 1 to 3 and comparative example 1~5；
Fig. 2 is COD in Examples 1 to 3 and comparative example 1~5MnRemoval rate comparison diagram；
Fig. 3 is the removal rate comparison diagram of TOC in Examples 1 to 3 and comparative example 1~5；
Fig. 4 is bromide ion concentration comparison diagram in Examples 1 to 3 and comparative example 1~5；
Fig. 5 is Dichloro-monobromo methane concentration comparison diagram in Examples 1 to 3 and comparative example 1~5；
Fig. 6 is the reaction rate K value comparison diagram of Examples 1 to 3 and comparative example 1~5；
In figure, a is the corresponding data of embodiment 1, and b is the corresponding data of embodiment 2, and c is the corresponding data of embodiment 3, d
For the corresponding data of comparative example 1, e is the corresponding data of comparative example 2, and f is the corresponding data of comparative example 3, and g is the phase of comparative example 4
Data are answered, h is the corresponding data of comparative example 5.
Specific embodiment
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
A kind of embodiment 1: preparation method of graphene multi-element metal composite material, the specific steps are as follows:
(1) it adds graphene oxide into 200mL solvent (water) and carries out ultrasonic disperse processing 60min and obtain oxidation stone
Black alkene dispersion liquid；Wherein the concentration of graphene oxide is 5g/L in graphene oxide dispersion；
(2) by reducing agent (hydrazine hydrate), alkali (sodium hydroxide), metal salt (divalent metal salt (magnesium nitrate) and trivalent metal
The mixture of salt (aluminum nitrate)) it is dissolved in step (1) graphene oxide dispersion and obtains mixed solution；Wherein reducing agent (water
Close hydrazine) it with the mass ratio of graphene oxide is 10:1；The molar concentration of alkali (sodium hydroxide) is 4mol/L in mixed solution；Mixing
The molar concentration of divalent metal salt (magnesium nitrate) is 60mmol/L in solution, and the molar concentration of trivalent metal salt (aluminum nitrate) is
20mmol/L；
(3) step (2) mixed solution is placed under the conditions of temperature is 80 DEG C and carries out high temperature hydro-thermal reaction 20h, be cooled to room
Centrifugal treating after temperature, removes supernatant liquor, adopts and solid is washed with deionized, graphene multi-element metal composite wood obtained by drying
Material；
Phenol is the common indication compound of common chemical products and Recalcitrant chemicals matter." Drinking Water is defended
Raw standard " it is 0.002mg/L, China's " groundwater quality mark to volatile phenol limit value regulation (in terms of phenol) in (GB5749-2006)
It is quasi- " (GB/T14848-93) also have similar regulation；
The present embodiment is to add 0.4mmol/L potassium peroxydisulfate in 3mg/L phenol solution to the concentration of 100mL, is mixed
Solution；100mg is prepared gained graphene multi-element metal composite material to add into mixed solution, being placed in temperature is to stir at 25 DEG C
Reaction 60min is mixed, reaction rate is 0.0454 ± 0.0104min-1；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 87.6%, CODMn(permanganate index) removal
Rate is that 55.7%, TOC (total organic carbon) removal rate is 30.5%.
Embodiment 2: the preparation method of the present embodiment graphene multi-element metal composite material, the specific steps are as follows:
(1) it adds graphene oxide into 200mL solvent (water: methanol (v/v)=1:4) and carries out ultrasonic disperse processing
60min obtains graphene oxide dispersion；Wherein the concentration of graphene oxide is 1g/L in graphene oxide dispersion；
(2) by reducing agent (sodium borohydride), alkali (sodium hydroxide), metal salt (divalent metal salt (magnesium nitrate) and trivalent gold
Belong to the mixture of salt (aluminum nitrate)) it is dissolved in step (1) graphene oxide dispersion and obtains mixed solution；Wherein sodium borohydride
Mass ratio with graphene oxide is 0.1:1；The molar concentration of alkali (sodium hydroxide) is 1mol/L in mixed solution；Mixed solution
The molar concentration of middle divalent metal salt (magnesium nitrate) is 30mmol/L, and the molar concentration of trivalent metal salt (aluminum nitrate) is
20mmol/L；
(3) step (2) mixed solution is placed under the conditions of temperature is 100 DEG C and carries out high temperature hydro-thermal reaction 20h, be cooled to room
Centrifugal treating after temperature, removes supernatant liquor, adopts and solid is washed with deionized, graphene multi-element metal composite wood obtained by drying
Material；
The present embodiment is to add 0.4mmol/L potassium peroxydisulfate in 3mg/L phenol solution to the concentration of 100mL, is mixed
Solution；100mg graphene multi-element metal composite material is added into mixed solution, being placed in temperature is to be stirred to react at 50 DEG C
60min, reaction rate are 0.1371 ± 0.0107min-1, water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is
98.4%, CODMn(permanganate index) removal rate is that 74.4%, TOC (total organic carbon) removal rate is 48.2%.
Embodiment 3: the preparation method of the present embodiment graphene multi-element metal composite material, the specific steps are as follows:
(1) it adds graphene oxide into 200mL solvent (water: ethyl alcohol (v/v)=1:10) and carries out at ultrasonic disperse
Reason 60min obtains graphene oxide dispersion；Wherein the concentration of graphene oxide is 4g/L in graphene oxide dispersion；
(2) by reducing agent (urea), alkali (sodium hydroxide), metal salt (divalent metal salt (magnesium nitrate) and trivalent metal salt
The mixture of (aluminum nitrate)) it is dissolved in step (1) graphene oxide dispersion and obtains mixed solution；Wherein urea and oxidation stone
The mass ratio of black alkene is 8:1；The molar concentration of alkali (sodium hydroxide) is 1mol/L in mixed solution；Divalent metal in mixed solution
The molar concentration of salt (magnesium nitrate) is 30mmol/L, and the molar concentration of trivalent metal salt (aluminum nitrate) is 20mmol/L；
(3) step (2) mixed solution is placed under the conditions of temperature is 200 DEG C and carries out high temperature hydro-thermal reaction 12h, be cooled to room
Centrifugal treating after temperature, removes supernatant liquor, adopts and solid is washed with deionized, graphene multi-element metal composite wood obtained by drying
Material；
The present embodiment is to add 0.4mmol/L potassium peroxydisulfate and 1.0mg/L bromine in 3mg/L phenol solution to 100mL concentration
Solion obtains mixed solution；100mg graphene multi-element metal composite material is added into mixed solution, temperature is placed in
It is that 60min is stirred to react at 70 DEG C, reaction rate is 0.3166 ± 0.0256min-1, water sampling measures after reaction, test result
Pyrogentisinic Acid's removal rate is that 100%, CODMn (permanganate index) removal rate is that 74.7%, TOC (total organic carbon) removal rate is
55.3%, Br in solution-Concentration is 0.988mg/L, and Dichloro-monobromo methane concentration is 0.005 μ g/L；
It is stirred to react 120min, water sampling measures after reaction, and Dichloro-monobromo methane concentration is 0.649 μ g/L in solution.
A kind of embodiment 4: preparation method of graphene multi-element metal composite material, the specific steps are as follows:
(1) it adds graphene oxide into 200mL solvent (water: methanol: ethyl alcohol (v/v)=1:5:5) and carries out ultrasound
Decentralized processing 60min obtains graphene oxide dispersion；Wherein the concentration of graphene oxide is 5g/ in graphene oxide dispersion
L；
(2) by reducing agent (hydrazine hydrate), alkali (sodium hydroxide), metal salt (divalent metal salt (magnesium nitrate) and trivalent metal
The mixture of salt (aluminum nitrate) is dissolved in step (1) graphene oxide dispersion and obtains mixed solution；Wherein hydrazine hydrate and oxygen
The mass ratio of graphite alkene is 1:1；The molar concentration of alkali (sodium hydroxide) is 3mol/L in mixed solution；Divalent in mixed solution
The molar concentration of metal salt (magnesium nitrate) is 30mmol/L, and the molar concentration of trivalent metal salt (aluminum nitrate) is 10mmol/L；
(3) step (2) mixed solution is placed under the conditions of temperature is 120 DEG C and carries out high temperature hydro-thermal reaction 12h, be cooled to room
Centrifugal treating after temperature, removes supernatant liquor, adopts and solid is washed with deionized, graphene multi-element metal composite wood obtained by drying
Material；
The present embodiment is to add 0.6mmol/L potassium peroxydisulfate and 2.0mg/L bromine in 5mg/L phenol solution to 200mL concentration
Solion obtains mixed solution；150mg graphene multi-element metal composite material is added into mixed solution, temperature is placed in
It is to be stirred to react 60min at 25 DEG C；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 92.0%, CODMn(permanganate index) removal
Rate is that 45.2%, TOC (total organic carbon) removal rate is 37.5%.
Embodiment 5: the preparation method of the present embodiment graphene multi-element metal composite material is same as Example 4；
The present embodiment to 300mL concentration be 6mg/L phenol solution in add 1mmol/L potassium peroxydisulfate and 2.0mg/L bromine from
Sub- solution obtains mixed solution；100mg graphene multi-element metal composite material is added into mixed solution, being placed in temperature is 25
DEG C it is stirred to react 60min；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 95.2%, CODMn(permanganate index) removal
Rate is that 53.0%, TOC (total organic carbon) removal rate is 39.5%.
Embodiment 6: the preparation method of the present embodiment graphene multi-element metal composite material is same as Example 1；
The present embodiment is to add 0.4mmol/L potassium peroxydisulfate and 1.0mg/L in 3mg/L 4- bromine phenol solution to 100mL concentration
Bromide ion solution, obtains mixed solution；100mg graphene multi-element metal composite material is added into mixed solution, temperature is placed in
Degree is stirred to react 60min for 25 DEG C；
Water sampling measures after reaction, and test result is 100%%, COD to 4- bromine phenol removal rateMn(permanganate index) is gone
It is 50.5% except rate is 32.0%, TOC (total organic carbon) removal rate.
Comparative example 1:
It is 3mg/L phenol solution that the graphene multi-element metal composite material of 100mg embodiment 1, which is added to 100mL concentration,
In, 25 DEG C are stirred to react 60min；Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 16.3%.
Comparative example 2: the preparation method of multi-element metal compound composite material, the specific steps are as follows:
(1) by 8g sodium hydroxide, 75mmol magnesium nitrate, 25mmol aluminum nitrate, 200mL water be uniformly mixed obtain mixing it is molten
Liquid；
(2) mixed solution is placed in temperature is hydro-thermal reaction 20h at 80 DEG C, is centrifugated, washes, dries after being cooled to room temperature
Multi-element metal composite material is obtained after dry；
This comparative example is to add 0.4mmol/L potassium peroxydisulfate and 1.0mg/L bromine in 3mg/L phenol solution to 100mL concentration
Solion obtains mixed solution；100mg multi-element metal compound composite material is added into mixed solution, being placed in temperature is
25 DEG C are stirred to react 60min, and reaction rate is 0.0123 ± 0.0008min-1；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 57.9%, CODMn(permanganate index) removal
Rate is that 1.4%, TOC (total organic carbon) removal rate is 0.
Comparative example 3
This comparative example is to add 0.4mmol/L potassium peroxydisulfate and 1.0mg/L bromine in 3mg/L phenol solution to 100mL concentration
Solion obtains mixed solution；The multi-element metal compound composite material of 100mg comparative example 2 is added into mixed solution,
It is placed in temperature and is stirred to react 60min for 50 DEG C, reaction rate is 0.0458 ± 0.0019min-1；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 100%, CODMn(permanganate index) removal rate
It is 4.8% for 75.8%, TOC (total organic carbon) removal rate.
Comparative example 4
This comparative example is to add 0.4mmol/L potassium peroxydisulfate and 1.0mg/L bromine in 3mg/L phenol solution to 100mL concentration
Solion obtains mixed solution；The multi-element metal compound composite material of 100mg comparative example 2 is added into mixed solution,
70 DEG C are stirred to react 60min, and reaction rate is 0.1280 ± 0.0123min-1；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 100%, CODMn(permanganate index) removal rate
It is 18.0% for 75.0%, TOC (total organic carbon) removal rate, Br in solution-Concentration is 0.661mg/L, and Dichloro-monobromo methane is dense
Degree is 1.625 μ g/L；
It is stirred to react 120min, water sampling measures after reaction, and Dichloro-monobromo methane concentration is 2.068 μ g/L in solution.
Comparative example 5
It is 3mg/L that this comparative example, which adds the multi-element metal compound composite material of 100mg comparative example 2 to 100mL concentration,
In phenol solution, temperature is placed in as 25 DEG C and is stirred to react 60min；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 14.1%.
Comparative example 6
This comparative example is to add 0.4mmol/L potassium peroxydisulfate in 3mg/L phenol solution to 100mL concentration, and being placed in temperature is
60min is stirred to react at 25 DEG C；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 0%, CODMn(permanganate index) removal rate is
0%, TOC (total organic carbon) removal rate are 0%.
Comparative example 7
Redox graphene is prepared, the specific steps of which are as follows:
(1) by 200mg graphene oxide ultrasonic disperse in 200mL water, ultrasonic treatment 60min obtains graphene oxide point
Dispersion liquid；
(2) 600mg hydrazine hydrate is added in step (1) graphene oxide dispersion, being subsequently placed in temperature is 80 DEG C of water
Thermal response 20h obtains redox graphene after being cooled to room temperature rear centrifugal treating, washing, drying；
It is to be placed in temperature in 3mg/L phenol solution that this comparative example, which adds 100mg redox graphene to 100mL concentration,
Degree is stirred to react 60min for 25 DEG C；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 16.3%, CODMn(permanganate index) removal
Rate is that 0%, TOC (total organic carbon) removal rate is 0%.
Comparative example 8
This comparative example is to add 0.4mmol/L potassium peroxydisulfate in 3mg/L phenol solution to 100mL concentration, obtains mixing molten
Material made from comparative example 2 and comparative example 7 is mixed, 100mg is taken to add into mixed solution by liquid, and being placed in temperature is at 25 DEG C
It is stirred to react 60min；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 56.5%, CODMn(permanganate index) removal
Rate is that 3.0%, TOC (total organic carbon) removal rate is 0%；
The result (see Fig. 1~6) in embodiment and comparative example is analyzed it is found that graphene multi-element metal composite material, with mistake
Oxide combination, can efficiently activate peroxide, improve peroxide utilization rate, and organic removal rate may be up at 25 DEG C
87.6%, hence it is evident that be higher than multi-element metal compound comparative example 2 (57.9%)；Mineralization of organic material degree is high, and CODMn is removed at 25 DEG C
Rate, up to 30.5%, is all remarkably higher than corresponding comparative example (1.4%, 0%) up to 55.7%, TOC removal rate；To a certain extent
Inhibit the conversion of bromide ion, reduces the generation of bromo disinfection by-products in water, wherein graphene multi-element metal composite material, it should
Material incorporate graphene to the absorption of pollutant, to the quick transmission of electronics, polynary to the activation of peroxide, nano shape
Metallic compound high degree of dispersion, multi-element metal compound activating peroxide, graphene and multi-element metal compound act synergistically
Etc. multifrequency natures；With peroxide combination after can synchronous effective peroxide activator and inhibit disinfection by-products generation, have
Preferably organic matter degradation ability can further solve multi-element metal chemical combination while promoting oxidation susceptibility, reducing energy consumption
The reaction rate that object and peroxide are used in combination it is slow (be computed, at a temperature of three kinds, compared with multi-element metal compound, graphite
Alkene composite material promotes 3.69,2.99 and 2.47 times of reaction rate respectively), COD, TOC removal rate is low, underwater trace bromide ion is led
The bromo organic by-products problem of cause；Material exists in solution in solid form, is easily removed by precipitating, in subsequent processing not
Adverse effect can be generated.
A kind of embodiment 7: preparation method of graphene multi-element metal composite material, the specific steps are as follows:
(1) it adds graphene oxide into solvent (water: methanol: ethyl alcohol (v/v)=1:4:4) and carries out at ultrasonic disperse
Reason 120min obtains graphene oxide dispersion；Wherein the concentration of graphene oxide is 3g/L in graphene oxide dispersion；
(2) by reducing agent (hydrazine hydrate and sodium borohydride), alkali (sodium hydroxide), metal salt (divalent metal salt (magnesium nitrate)
With the mixture of trivalent metal salt (aluminium chloride)) it is dissolved in step (1) graphene oxide dispersion and obtains mixed solution；Wherein
The mass ratio of reducing agent (hydrazine hydrate and sodium borohydride) and graphene oxide is hydrazine hydrate: sodium borohydride: graphene oxide (m/m)
=5:5:1；The molar concentration of alkali (potassium hydroxide) is 1mol/L in mixed solution；Divalent metal salt (magnesium nitrate) in mixed solution
Molar concentration be 30mmol/L, the molar concentration of trivalent metal salt (aluminium chloride) is 15mmol/L；
(3) step (2) mixed solution is placed under the conditions of temperature is 50 DEG C and carries out high temperature hydro-thermal reaction 18h, be cooled to room
Centrifugal treating after temperature, removes supernatant liquor, adopts and solid is washed with deionized, graphene multi-element metal composite wood obtained by drying
Material；
The present embodiment is to add 2.5mmol/L potassium peroxydisulfate in 5mg/L phenol solution to 300mL concentration, by 100mg graphite
Alkene multi-element metal composite material is added into mixed solution, is placed in temperature as 25 DEG C and is stirred to react 60min；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 90.2%, CODMn(permanganate index) removal
Rate is that 62.0%, TOC (total organic carbon) removal rate is 37.3%.
A kind of embodiment 8: preparation method of graphene multi-element metal composite material, the specific steps are as follows:
(1) it adds graphene oxide into solvent (water: methanol (v/v)=1:6) and carries out ultrasonic disperse processing 90min
Obtain graphene oxide dispersion；Wherein the concentration of graphene oxide is 2g/L in graphene oxide dispersion；
(2) by reducing agent (hydrazine hydrate and urea), alkali (potassium hydroxide), metal salt (divalent metal salt (nickel nitrate and nitric acid
Copper) and trivalent metal salt (aluminium chloride) mixture) be dissolved in step (1) graphene oxide dispersion and obtain mixed solution；
Wherein the mass ratio of reducing agent (hydrazine hydrate and urea) and graphene oxide is hydrazine hydrate: sodium borohydride: graphene oxide (m/m)
=0.1:0.1:1；The molar concentration of alkali (potassium hydroxide) is 2mol/L in mixed solution；Divalent metal salt (nitre in mixed solution
Sour nickel and copper nitrate) mole total concentration be 45mmol/L, the molar concentration of trivalent metal salt (aluminium chloride) is 15mmol/L；
(3) step (2) mixed solution is placed under the conditions of temperature is 120 DEG C and carries out high temperature hydro-thermal reaction 15h, be cooled to room
Centrifugal treating after temperature, removes supernatant liquor, adopts and solid is washed with deionized, graphene multi-element metal composite wood obtained by drying
Material；
The present embodiment is to add 0.4mmol/L potassium peroxydisulfate in 6mg/L phenol solution to 300mL concentration, by 100mg graphite
Alkene multi-element metal composite material is added into mixed solution, is placed in temperature as 50 DEG C and is stirred to react 60min；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 97.1%, CODMn(permanganate index) removal
Rate is that 74.6%, TOC (total organic carbon) removal rate is 52.5%.
A kind of embodiment 9: preparation method of graphene multi-element metal composite material, the specific steps are as follows:
(1) it adds graphene oxide into solvent (water: ethyl alcohol (v/v)=1:8) and carries out ultrasonic disperse processing
120min obtains graphene oxide dispersion；Wherein the concentration of graphene oxide is 3g/L in graphene oxide dispersion；
(2) by reducing agent (sodium borohydride and urea), alkali (sodium hydroxide) metal salt (divalent metal salt (magnesium chloride and chlorine
Change nickel) and trivalent metal salt (aluminum nitrate) mixture) be dissolved in step (1) graphene oxide dispersion obtain mixing it is molten
Liquid；Wherein the mass ratio of reducing agent (sodium borohydride and urea) and graphene oxide is hydrazine hydrate: sodium borohydride: graphene oxide
(m/m)=10:6:1；The molar concentration of alkali (sodium hydroxide) is 1.5mol/L in mixed solution；Divalent metal salt in mixed solution
Mole total concentration of (magnesium chloride and nickel chloride) is 60mmol/L, and the molar concentration of trivalent metal salt (aluminum nitrate) is 15mmol/
L；
(3) step (2) mixed solution is placed under the conditions of temperature is 100 DEG C and carries out high temperature hydro-thermal reaction for 24 hours, be cooled to room
Centrifugal treating after temperature, removes supernatant liquor, adopts and solid is washed with deionized, graphene multi-element metal composite wood obtained by drying
Material；
The present embodiment is to add 1.5mmol/L potassium peroxydisulfate in 4mg/L phenol solution to 300mL concentration, by 100mg graphite
Alkene multi-element metal composite material is added into mixed solution, is placed in temperature as 70 DEG C and is stirred to react 60min；
Water sampling measures after reaction, and test result Pyrogentisinic Acid's removal rate is 100%, CODMn(permanganate index) removal rate
It is 50.5% for 73.0%, TOC (total organic carbon) removal rate.
Claims (10)
1. a kind of preparation method of graphene multi-element metal composite material, which is characterized in that specific step is as follows:
(1) it adds graphene oxide into solvent and carries out 1~2h of ultrasonic disperse processing and obtain graphene oxide dispersion；
(2) reducing agent, alkali, dissolving metal salts are obtained into mixed solution in step (1) graphene oxide dispersion；
(3) step (2) mixed solution is subjected to high temperature hydro-thermal reaction 12~for 24 hours, is cooled to room temperature rear centrifugal treating, removes upper layer
Clear liquid is adopted and solid is washed with deionized, graphene multi-element metal composite material obtained by drying.
2. the preparation method of graphene multi-element metal composite material according to claim 1, it is characterised in that: in step (1)
Solvent is water and/or alcohol, and wherein alcohol is methanol and/or ethyl alcohol, and the volume ratio of water and alcohol is 1:(4~10).
3. the preparation method of graphene multi-element metal composite material according to claim 1, it is characterised in that: in step (1)
The concentration of graphene oxide is 1~5g/L in graphene oxide dispersion.
4. the preparation method of graphene multi-element metal composite material according to claim 1, it is characterised in that: step (2) is also
Former agent is one of hydrazine hydrate, urea, sodium borohydride or a variety of, the mass ratio of reducing agent and graphene oxide be (0.1~
10):1。
5. the preparation method of graphene multi-element metal composite material according to claim 1, it is characterised in that: step (2) alkali
For sodium hydroxide and/or potassium hydroxide, the molar concentration of alkali is 1~4mol/L in mixed solution.
6. the preparation method of graphene multi-element metal composite material according to claim 1, it is characterised in that: step (2) gold
Belong to the mixture that salt is divalent metal salt and trivalent metal salt.
7. the preparation method of graphene multi-element metal composite material according to claim 6, it is characterised in that: divalent metal salt
For magnesium nitrate, nickel nitrate, copper nitrate, magnesium chloride, nickel chloride, copper chloride it is one or more；Trivalent metal salt be aluminum nitrate and/
Or aluminium chloride.
8. the preparation method of the graphene multi-element metal composite material of claim 6 or 7, it is characterised in that: in mixed solution
The molar concentration of divalent metal salt is 30~60mmol/L, and the molar concentration of trivalent metal salt is 10~20mmol/L.
9. the preparation method of graphene multi-element metal composite material according to claim 1, it is characterised in that: in step (3)
The temperature of high temperature hydro-thermal reaction is 50~200 DEG C.
10. graphene multi-element metal composite material prepared by preparation method described in claim 1 is degraded organic in water body disinfection
Application in object.
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| CN111604015A (en) * | 2020-06-07 | 2020-09-01 | 宁夏大学 | Preparation method of shell-core structure composite material with metal compound coated by nano carbon material |
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| CN113731467A (en) * | 2021-09-06 | 2021-12-03 | 湘潭大学 | Nitrogen-modified graphene-loaded copper oxide composite material and preparation method and application thereof |
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Application publication date: 20190716 |