CN109248674A - A kind of graphene-supported nano zero-valence zinc composite material and preparation method and application - Google Patents
A kind of graphene-supported nano zero-valence zinc composite material and preparation method and application Download PDFInfo
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- CN109248674A CN109248674A CN201811407779.3A CN201811407779A CN109248674A CN 109248674 A CN109248674 A CN 109248674A CN 201811407779 A CN201811407779 A CN 201811407779A CN 109248674 A CN109248674 A CN 109248674A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
Abstract
The present invention provides a kind of graphene-supported nano zero-valence zinc composite material and preparation method and application, the graphene-supported nano zero-valence zinc composite material includes graphene sheet layer and nano zero-valence zinc, the surface of the nano zero-valence zinc insertion graphene sheet layer.The present invention is that carrier prepares nano zero-valence zinc composite material using graphene, not only increase the dispersibility and stability of nano zero-valence zinc, graphene can also strengthening electronic transfer and pre-concentration pollutant, nano zero-valence zinc can also separate neighbouring graphene sheet layer, prevent graphene sheet layer from cluster occurs.Graphene sheet layer is mutually cooperateed with nano zero-valence zinc, and the partial size of nano zero-valence zinc particles is smaller in the composite material being prepared, and graphene sheet layer cluster degree is small, the ability with stronger reduction water body and/or organic contaminants in soil.
Description
Technical field
The invention belongs to Material Field, it is related to a kind of nano zero-valence metallic composite more particularly to a kind of graphene is negative
Carry nano zero-valence zinc composite material and preparation method and application.
Background technique
Due to dyestuff, the unreasonable discharge of wastewater from chemical industry and the production and application of pesticide, agrochemical, cause serious
Soil organic contamination.In recent years, research and application of the zero valent metal particles reduction technique in organic contamination improvement are more next
More, which is mainly used in azo dyestuff, nitryl aromatic race organic compound, organochlorine compound, nitrate and Asia
Nitrate, halogenated acetic acids, each heavy metal species, nitrosodimethylamine and pesticide etc..The zero-valent metal of most study is Fe, secondly
For Zn, Al, Sn etc. and its compound, some researches show that the reproducibility ratio Fe of Zn is strong, but the catalytic activity of common zeroth order zinc has
Limit is subject to certain restrictions using the application that organic pollutant of the common zeroth order zinc to high concentration high pollution carries out catalytic degradation.
106861670 A of CN discloses a kind of method for improving nano zero-valence zinc catalytic activity, the nanometer of this method preparation
Zeroth order zinc can be used for carrying out catalytic degradation to the organic pollutant of high concentration high pollution.Zinc powder is put into roll extrusion vibration mill by this method
It is ground, stress release is carried out to the zinc powder of processing in process of lapping, obtains nano zero-valence zinc.Nano zero-valence metal is due to it
The properties such as size is small, large specific surface area, surface-active height and the degradation rate for improving organic pollutant, overcome common zero
Valence metal active is low, the reaction time is long, is more suitable for the disadvantages of being reacted under the conditions of lower ph.
But there is also easily clusters, easy the disadvantages of being oxidized passivation for nano zero-valence metal.To solve these problems, blunt
Change nano zero-valence is metal-modified, load nano zero-valence is metal-modified and stabilizer is transformed the nano zero valence irons modification technologies such as nanometer and is answered
It transports and gives birth to.Graphene is widely closed in field of compound material due to its excellent calorifics, electricity and mechanical property
Note.Its unique two-dimensional surface laminated structure becomes Ideal adsorption agent material plus high specific surface area and load is received
A kind of ideal carrier of rice corpuscles.It is that carrier prepares nano zero-valence metallic composite using graphene, not only can be improved and receive
The dispersibility and stability of rice Zero-valent Iron, graphene are also possible to strengthening electronic transfer and pre-concentration pollutant；Metal nanoparticle
It can also play the role of separating neighbouring graphene sheet layer, prevent cluster.By the advantage phase coupling of graphene and nano zero valence iron
It closes, has a extensive future in terms of contaminated soil and water remediation and improvement.
104437364 A of CN discloses a kind of preparation method of graphene-supported nano zero-valence iron composite material and this is multiple
Condensation material adsorbs the regeneration method after pollutant, and this method by being chemisorbed on the surface GO, is then waiting iron ion
In ionic discharge room by ferric iron back be Zero-valent Iron, graphene-supported nano zero-valence iron composite material is made.But this method needs
Ferric iron is restored by plasma discharge room, to the more demanding of preparation condition and Preparation equipment, be unfavorable for big
Technical scale metaplasia produces.
The reproducibility ratio Fe of Zn is strong, but cluster easily occurs for nano zero-valence zincode, the reproducibility of the nano zero-valence zinc after cluster
It is not easy to express.CN 104479494 discloses a kind of graphene-based nano zero-valence zinc system coating and preparation method thereof, though this method
So nano zero-valence zinc is mixed with graphene, but zinc ion has only played thermal conducting agent in the coating that is prepared of this method
Effect.
Therefore, develop a kind of composite material that can play nano zero-valence zinc reduction, for improve contaminated soil and
The effect of pollution waters restoration and improvement has the function of positive.
Summary of the invention
It is multiple in view of the deficiencies of the prior art, the present invention intends to provide a kind of graphene-supported nano zero-valence zinc
Condensation material and its preparation method and application.It is that carrier prepares nano zero-valence zinc composite material using graphene, nano zero-valence zinc is inserted
Enter graphene film layer surface, nano zero-valence zinc plays the role of skeletal support, it is therefore prevented that the cluster of graphene sheet layer；Nano zero-valence
Zinc is easily oxidized and declines reproducibility, and graphene sheet layer can strengthening electronic transfer, make up nano zero-valence zinc and be easily oxidized
The shortcomings that, and graphene sheet layer can pre-concentration pollutant, prevent the cluster of nano zero-valence zinc, improve nano zero-valence zinc also
The ability of raw water body and/or organic contaminants in soil.Graphene sheet layer is mutually cooperateed with nano zero-valence zinc, and what is be prepared answers
The partial size of nano zero-valence zinc particles is smaller in condensation material, and graphene sheet layer cluster degree is small, have stronger reduction water body and/or
The ability of organic contaminants in soil.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of graphene-supported nano zero-valence zinc composite material, including graphene sheet layer
With nano zero-valence zinc, the surface of the nano zero-valence zinc insertion graphene sheet layer.
Cluster easily occurs for graphene sheet layer, and the present invention can slow down on the surface of nano zero-valence zinc insertion graphene sheet layer
The nano zero-valence zinc particles of the cluster degree of graphene sheet layer, insertion graphene film layer surface have obtained effective dispersion, stablize
Property is enhanced.Meanwhile graphene can strengthen the transfer of electronics in reduction process as carrier, it being capable of pre-concentration pollution
Object improves the ability of nano zero-valence zinc reduction water body and/or organic contaminants in soil.Graphene sheet layer and nano zero-valence zinc
It mutually cooperates with, the partial size of nano zero-valence zinc particles is smaller in the composite material being prepared, and graphene sheet layer cluster degree is small, tool
There is the ability of stronger reduction water body and/or organic contaminants in soil.
Preferably, the partial size of the nano zero-valence zinc particles be 1-150nm, such as can be 1nm, 10nm, 20nm,
30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 150nm, preferably
For 20-60nm.The partial size of nano zero-valence zinc particles is according to the liquid-solid ratio of graphene oxide, reducing agent in graphene oxide dispersion
Dripping quantity and reducing agent rate of addition and become, nano zero-valence zinc particles be inserted into graphene sheet layer surface, prevent graphite
Cluster, the ability for making graphene sheet layer preferably play electronics transfer and pre-concentration pollutant occur for alkene lamella.
Second aspect, the present invention provides the systems of graphene-supported nano zero-valence zinc composite material as described in relation to the first aspect
Preparation Method, the preparation method include the following steps:
(1) mixed oxidization graphene and deionized water, ultrasonic disperse obtain graphene oxide dispersion；
(2) mixed zinc salts solution and step (1) gained graphene oxide dispersion, are added dropwise reducing solution, solid after stirring
Liquid separation, obtains solid product；
(3) vacuum drying step (2) obtained solid product obtains graphene oxide-loaded nano zeroth order zinc composite material.
Zinc solution and reducing solution is added in the present invention in the graphene oxide dispersion that ultrasonic disperse is handled,
Zn in solution2+It is uniformly distributed in solution, graphene oxide and Zn2+After reducing agent restores, nano zero-valence zinc is straight
It connects and is carried between graphene sheet layer, play the role of supporting graphene sheet layer, it is therefore prevented that cluster occurs for graphene sheet layer.Stone
Nano zero-valence zinc is loaded between black alkene lamella can prevent nano zero-valence zinc cluster again, guarantee that nano zero-valence zinc can play itself
Reproducibility.The composite material reducing power that preparation method provided by the present invention is prepared is strong, can be used for water body or soil
Earth is repaired.
Preferably, the liquid-solid ratio of step (1) graphene oxide and deionized water is 4-8mL/g, such as be can be
4mL/g, 5mL/g, 6mL/g, 7mL/g or 8mL/g, preferably 5-6mL/g.
Preferably, step (2) described zinc salt includes zinc nitrate and/or zinc sulfate.
Preferably, Zn in step (2) described zinc solution2+Molar concentration be 1.5-2.5mmol/L, such as can be
1.5mmol/L、1.6mmol/L、1.7mmol/L、1.8mmol/L、1.9mmol/L、2mmol/L、2.1mmol/L、2.2mmol/
L, 2.3mmol/L, 2.4mmol/L or 2.5mmol/L, preferably 1.8-2.1mmol/L.
Preferably, the Zn in step (2) described zinc solution2+With the matter of the graphene in the graphene oxide dispersion
Amount is than being (1-50): 10, such as can be 1:10,5:10,10:10,20:10,30:1,40:10 or 50:10, preferably (2-
20):10。
Preferably, step (2) mixing is with stirring.
Preferably, step (2) the mixed time be 20-28h, such as can be 20h, 21h, 22h, 23h, for 24 hours,
25h, 26h, 27h or 28h, preferably 22-26h.
Preferably, step (2) the mixed temperature be 20-30 DEG C, such as can be 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C,
24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C or 30 DEG C, preferably 22-26 DEG C.
Preferably, the reducing agent in step (2) described reducing solution includes sodium borohydride and/or sodium citrate, preferably
For sodium borohydride.
Preferably, the molar concentration of reducing agent is 0.02-0.05mol/L in step (2) described reducing solution, such as can
To be 0.02mol/L, 0.03mol/L, 0.04mol/L or 0.05mol/L, preferably 0.04-0.05mol/L.
Preferably, Zn in step (2) described zinc solution2+Mass ratio with effective component in the reducing agent is 1:(6-
10) 1:6,1:7,1:8,1:9 or 1:10, preferably 1:(7-9 be can be, such as).
Preferably, the time of step (2) described stirring be 50-80min, such as can be 50min, 55min, 60min,
65min, 70min, 75min or 80min, preferably 60-70min.
Preferably, step (3) the vacuum drying temperature is 35-45 DEG C, such as can be 35 DEG C, 36 DEG C, 37 DEG C, 38
DEG C, 39 DEG C, 40 DEG C, 41 DEG C, 42 DEG C, 43 DEG C, 44 DEG C or 45 DEG C, preferably 38-42 DEG C.
Preferably, step (3) the vacuum drying time be 20-28h, such as can be 20h, 21h, 22h, 23h,
For 24 hours, 25h, 26h, 27h or 28h, preferably 22-26h.
Preferably, further include step (a) before step (1): preparing graphene oxide.
Preferably, the method that step (a) prepares graphene oxide is Hummer method.
As the optimal technical scheme for the preparation method that second aspect of the present invention provides, the preparation method includes following step
It is rapid:
(I) graphene oxide is prepared in Hummer method；
(II) according to the ratio mixed oxidization graphene and deionized water of liquid-solid ratio 4-8mL/g, ultrasonic disperse is aoxidized
Graphene dispersing solution；
(III) graphene oxide dispersion obtained by mixed zinc salts solution and step (II), the Zn in zinc solution2+With it is described
The mass ratio of graphene in graphene oxide dispersion is 1:10-5:1, and 20-28h is stirred at 20-30 DEG C, and 0.02- is added dropwise
The sodium borohydride solution and/or sodium citrate solution of 0.05mol/L is separated by solid-liquid separation after stirring 50-80min, obtains solid product,
The zinc salt includes zinc nitrate and/or zinc sulfate, Zn in the zinc solution2+Molar concentration be 1.5-2.5mmol/L, it is described
Zn in zinc solution2+Mass ratio with reducing agent in the reducing solution is 1:(6-10)；
(IV) vacuum drying step (III) obtained solid product 20-28h at 35-45 DEG C, obtains graphene oxide-loaded receive
Rice zeroth order zinc composite material.
The third aspect, the present invention provides graphene oxide-loaded nano zeroth order zinc composite materials as described in relation to the first aspect
Or the graphene oxide-loaded nano zeroth order zinc composite material that the preparation method as described in second aspect is prepared is for water body
Or the application of soil remediation.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
Nano zero-valence zinc particles are inserted into the table second of graphene sheet layer, and nano zero-valence zinc particles have obtained effective dispersion, received
The stability of rice zeroth order zinc is also enhanced, and load has the graphene sheet layer of nano zero-valence zinc to be also not easy cluster.Meanwhile
Graphene can strengthen the transfer of electronics in reduction process as carrier, compensate for nano zero-valence zinc be easily oxidized and caused by also
Originality decline defect, and graphene can pre-concentration pollutant, improve nano zero-valence zinc reduction water body and/or soil in
The ability of organic pollutant.Graphene sheet layer is mutually cooperateed with nano zero-valence zinc, nano zero-valence in the composite material being prepared
The partial size of zinc particles is smaller, and graphene sheet layer cluster degree is small, has stronger reduction water body and/or organic contaminants in soil
Ability.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture for the graphene oxide-loaded nano zeroth order zinc composite material that embodiment 1 is prepared.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
I graphene oxide) is prepared
Preparation example 1
This preparation example provides a kind of preparation method of graphene oxide, and the preparation method includes the following steps:
The concentrated sulfuric acid of 100mL98% is added in the beaker of 50mL, be then added 3.0g graphite powder (concentrated sulfuric acid and graphite
Mass ratio is 30:1-100:1) and 1.5g sodium nitrate (the mass ratio 2:1 of graphite powder and sodium nitrate), the mechanical stirring in ice-water bath
20-40min.Then 9.0g potassium permanganate slowly (mass ratio of potassium permanganate and graphite is 2:1-5:1) is added in mixture,
Mechanical stirring at temperature is controlled lower than 5 DEG C.Ice bath is removed, mixed liquor is moved on in the thermostat water bath that water temperature is 34-36 DEG C and is protected
30min is held, then 200mL ultrapure water is added thereto, mixed liquor is moved into 98 DEG C of thermostat water bath, 15min is kept.It will mix
It closes liquid to be diluted with warm water, the hydrogen peroxide (H of 25mL30% is added2O2Mass ratio with graphite is 4:1-12:1), filtering, distilled water
It is dried in vacuo 12h at washing 3 times, 70 DEG C, finally obtains the solid of brown, obtains graphene oxide, is freeze-dried spare.
II composite material) is prepared
Embodiment 1
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zeroth order zinc composite material, the preparation
Method includes the following steps:
(1) according to the ratio mixed oxidization graphene and deionized water of liquid-solid ratio 6mL/g, ultrasonic disperse obtains oxidation stone
Black alkene dispersion liquid；
(2) graphene oxide dispersion obtained by mixed nitrate zinc solution and step (1), the Zn in zinc nitrate solution2+With institute
The mass ratio for stating the graphene oxide in graphene oxide dispersion is 30:10, Zn in zinc nitrate solution2+Molar concentration be
2mmol/L stirs the sodium borohydride solution that 0.04mol/L is added dropwise for 24 hours at 25 DEG C, is separated by solid-liquid separation after stirring 60min, consolidate
Body product, Zn in the zinc nitrate solution2+Mass ratio with sodium borohydride in the sodium borohydride solution is 1:8；
Vacuum drying step (2) obtained solid product for 24 hours, obtains graphene oxide-loaded nano zeroth order zinc at (3) 40 DEG C
Composite material.
The graphene oxide is provided by preparation example 1, the graphene oxide-loaded nano zeroth order zinc composite wood being prepared
The transmission electron microscope picture of material is as shown in Figure 1, black particle is nano zero-valence zinc particles in Fig. 1.
Embodiment 2
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zeroth order zinc composite material, the preparation
Method includes the following steps:
(1) according to the ratio mixed oxidization graphene and deionized water of liquid-solid ratio 5mL/g, ultrasonic disperse obtains oxidation stone
Black alkene dispersion liquid；
(2) graphene oxide dispersion obtained by solution of zinc sulfate and step (1), the Zn in solution of zinc sulfate are mixed2+With institute
The mass ratio for stating the graphene oxide in graphene oxide dispersion is 10:10, Zn in solution of zinc sulfate2+Molar concentration be
1.5mmol/L stirs 28h at 20 DEG C, and the sodium borohydride solution of 0.03mol/L is added dropwise, and is separated by solid-liquid separation, obtains after stirring 70min
Solid product, Zn in the solution of zinc sulfate2+Mass ratio with sodium borohydride in the sodium borohydride solution is 1:7；
Vacuum drying step (2) obtained solid product 28h at (3) 35 DEG C, obtains graphene oxide-loaded nano zeroth order zinc
Composite material.
The graphene oxide is provided by preparation example 1.
Embodiment 3
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zeroth order zinc composite material, the preparation
Method includes the following steps:
(1) according to the ratio mixed oxidization graphene and deionized water of liquid-solid ratio 7mL/g, ultrasonic disperse obtains oxidation stone
Black alkene dispersion liquid；
(2) graphene oxide dispersion obtained by mixed nitrate zinc solution and step (1), the Zn in zinc nitrate solution2+With institute
The mass ratio for stating the graphene oxide in graphene oxide dispersion is 40:10, Zn in zinc nitrate solution2+Molar concentration be
2.5mmol/L stirs 20h at 30 DEG C, and the sodium borohydride solution of 0.05mol/L is added dropwise, and is separated by solid-liquid separation, obtains after stirring 80min
Solid product, Zn in the zinc nitrate solution2+Mass ratio with sodium borohydride in the sodium borohydride solution is 1:9；
Vacuum drying step (2) obtained solid product 20h at (3) 45 DEG C, obtains graphene oxide-loaded nano zeroth order zinc
Composite material.
The graphene oxide is provided by preparation example 1.
Embodiment 4
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zeroth order zinc composite material, the preparation
Method includes the following steps:
(1) according to the ratio mixed oxidization graphene and deionized water of liquid-solid ratio 4mL/g, ultrasonic disperse obtains oxidation stone
Black alkene dispersion liquid；
(2) graphene oxide dispersion obtained by mixed nitrate zinc solution and step (1), the Zn in zinc nitrate solution2+With institute
The mass ratio for stating the graphene oxide in graphene oxide dispersion is 1:10, Zn in zinc nitrate solution2+Molar concentration be
1.5mmol/L stirs the sodium citrate solution that 0.02mol/L is added dropwise for 24 hours at 25 DEG C, is separated by solid-liquid separation, obtains after stirring 50min
Solid product, Zn in the zinc nitrate solution2+Mass ratio with sodium citrate in the sodium citrate solution is 1:6；
Vacuum drying step (2) obtained solid product for 24 hours, obtains graphene oxide-loaded nano zeroth order zinc at (3) 40 DEG C
Composite material.
The graphene oxide is provided by preparation example 1.
Embodiment 5
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zeroth order zinc composite material, the preparation
Method includes the following steps:
(1) according to the ratio mixed oxidization graphene and deionized water of liquid-solid ratio 8mL/g, ultrasonic disperse obtains oxidation stone
Black alkene dispersion liquid；
(2) graphene oxide dispersion obtained by mixed nitrate zinc solution and step (1), the Zn in zinc nitrate solution2+With institute
The mass ratio for stating the graphene oxide in graphene oxide dispersion is 50:10, Zn in zinc nitrate solution2+Molar concentration be
2.5mmol/L stirs the sodium borohydride solution that 0.04mol/L is added dropwise for 24 hours at 25 DEG C, is separated by solid-liquid separation, obtains after stirring 70min
Solid product, Zn in the zinc nitrate solution2+Mass ratio with sodium borohydride in the sodium borohydride solution is 1:10；
Vacuum drying step (2) obtained solid product for 24 hours, obtains graphene oxide-loaded nano zeroth order zinc at (3) 40 DEG C
Composite material.
The graphene oxide is provided by preparation example 1.
Embodiment 6
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zeroth order zinc composite material, the preparation
Method is except the Zn in step (2) described zinc nitrate solution2+With the quality of the graphene oxide in the graphene oxide dispersion
Outside for 55:10, remaining is same as Example 1.
Embodiment 7
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zeroth order zinc composite material, the preparation
Method is except the Zn in step (2) described zinc nitrate solution2+Molar concentration be 1.2mmol/L outside, remaining with 1 phase of embodiment
Together.
Embodiment 8
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zeroth order zinc composite material, the preparation
Method is except the Zn in step (2) described zinc nitrate solution2+Molar concentration be 2.8mmol/L outside, remaining with 1 phase of embodiment
Together.
Comparative example 1
This comparative example provides a kind of nano zero-valence zinc being prepared such as 106861670 A specific embodiment of CN.
Comparative example 2
This comparative example provides a kind of commercially available zinc powder.
Comparative example 3
Present embodiments provide a kind of preparation method of graphene oxide-loaded nano zero-valent iron composite material, the preparation
Method is identical as the preparation method that the embodiment 1 of 104437364 A of CN provides.
It degrades, drops to the methyl orange solution of 20mg/L using embodiment 1-8 provided by the present application and comparative example 1-3
Revolving speed is set as 400rpm in solution preocess, the final concentration of graphene oxide-loaded nano zeroth order zinc composite material in methyl orange solution
For 2g/L, the final concentration of 2g/L of nano zero-valence zinc, the final concentration of 4g/L of commercially available zinc powder.Degrade methyl orange 60min with
When 120min, the degradation rate of methyl orange is as shown in table 1.
Table 1
As shown in Table 1, the common zinc powder that comparative example 2 provides is only capable of reaching to the degradation rate of methyl orange in 60min
The degradation rate of 35.4%, 120min only have 75.6%；The nano zero-valence zinc that comparative example 1 provides exists to the degradation rate of methyl orange
The degradation rate that 60%, 120min can be reached when 60min can reach 89.6%；Comparative example 3 provides graphene oxide-loaded
Nano zero-valence iron composite material 60min to being to the degradation rate of methyl orange when the degradation rate of methyl orange is 82.7%, 120min
91.6%；And the graphene oxide-loaded nano zeroth order zinc composite material that embodiment 1-5 is provided exists to the degradation rate of methyl orange
Degradation rate when can reach 92% or more, 120min when 60min is even more close to 100%.
Zn in zinc nitrate solution in embodiment 62+Mass ratio with graphene oxide in the graphene oxide dispersion is
55:10, the Zn in the case where the molar concentration of zinc nitrate solution is constant2+Quality increase, it is excessive after reducing agent restores
Nano zero-valence zinc cluster easily occurs so that be prepared composite material 60min when only have to the degradation rate of methyl orange
There was only 92.2% to the degradation rate of methyl orange when 86.7%, 120min.
Zn in embodiment 7 in step (2) described zinc nitrate solution2+Molar concentration be only 1.2mmol/L, in zinc nitrate
Zn in solution2+With the mass ratio of graphene oxide in the graphene oxide dispersion it is constant in the case where, zinc nitrate solution
Middle Zn2+Molar concentration reduce, the nano zero-valence zinc after reduction can not effectively insert the surface of graphene sheet layer, in turn
Nano zero-valence zinc can not effectively support graphene sheet layer, so that cluster easily occurs for graphene sheet layer, influence to the pre- of pollutant
Concentrated effect, the composite material 60min that Application Example 7 provides only have 92.1%, 120min to first the degradation rate of methyl orange
The degradation rate of base orange is down to 96.3% by 99.8%.
Zn in embodiment 8 in step (2) described zinc nitrate solution2+Molar concentration be only 2.8mmol/L, in zinc nitrate
Zn in solution2+With the mass ratio of graphene oxide in the graphene oxide dispersion it is constant in the case where, zinc nitrate solution
Middle Zn2+Molar concentration increase, cluster easily occurs for obtained nano zero-valence zinc after reduction, is not only not easy to be inserted into graphene film
The surface of layer, is also not easy to play reproducibility, 60min is down to 85.8%, 120min to first by 95.8% to the degradation rate of methyl orange
The degradation rate of base orange is down to 92.7% by 99.8%.
To sum up, the surface of nano zero-valence zinc particles insertion graphene sheet layer, nano zero-valence zinc particles have obtained effectively dividing
It dissipates, the stability of nano zero-valence zinc is also enhanced, and the graphene sheet layer inserted with nano zero-valence zinc is also not easy cluster.
Meanwhile graphene can strengthen the transfer of electronics in reduction process as carrier, can pre-concentration pollutant, the graphene of stacking
Lamella can prevent the cluster of nano zero-valence zinc, improve nano zero-valence zinc reduction water body and/or organic contaminants in soil
Ability.Graphene sheet layer is mutually cooperateed with nano zero-valence zinc, the partial size of nano zero-valence zinc particles in the composite material being prepared
Smaller, graphene sheet layer cluster degree is small, the ability with stronger reduction water body and/or organic contaminants in soil.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of graphene-supported nano zero-valence zinc composite material, including graphene sheet layer and nano zero-valence zinc, which is characterized in that
The surface of the nano zero-valence zinc insertion graphene sheet layer.
2. composite material according to claim 1, which is characterized in that the partial size of the nano zero-valence zinc is 1-150nm, excellent
It is selected as 20-60nm；
Preferably, the mass ratio of the graphene sheet layer and the nano zero-valence zinc is (1-50): 10, preferably (2-20): 10.
3. a kind of preparation method of graphene-supported nano zero-valence zinc composite material as claimed in claim 1 or 2, feature exist
In the preparation method includes the following steps:
(1) mixed oxidization graphene and deionized water, ultrasonic disperse obtain graphene oxide dispersion；
(2) mixed zinc salts solution and step (1) gained graphene oxide dispersion, are added dropwise reducing solution, solid-liquid point after stirring
From obtaining solid product；
(3) vacuum drying step (2) obtained solid product obtains graphene oxide-loaded nano zeroth order zinc composite material.
4. preparation method according to claim 3, which is characterized in that step (1) deionized water and graphene oxide
Liquid-solid ratio be 4-8mL/g, preferably 5-6mL/g.
5. preparation method according to claim 3 or 4, which is characterized in that step (2) described zinc salt include zinc nitrate and/
Or zinc sulfate；
Preferably, Zn in step (2) described zinc solution2+Molar concentration be 1.5-2.5mmol/L, preferably 1.8-
2.1mmol/L；
Preferably, the Zn in step (2) described zinc solution2+With the matter of the graphene oxide in the graphene oxide dispersion
Amount is than being (1-50): 10, preferably (2-20): 10；
Preferably, step (2) mixing is with stirring；
Preferably, step (2) the mixed time is 20-28h, preferably 22-26h；
Preferably, step (2) the mixed temperature is 20-30 DEG C, preferably 22-26 DEG C.
6. according to the described in any item preparation methods of claim 3-5, which is characterized in that in step (2) described reducing solution
Reducing agent include sodium borohydride and/or sodium citrate, preferably sodium borohydride；
Preferably, the molar concentration of reducing agent is 0.02-0.05mol/L in step (2) described reducing solution, preferably
0.04-0.05mol/L；
Preferably, Zn in step (2) described zinc solution2+Mass ratio with reducing agent in the reducing solution is 1:(6-
10), preferably 1:(7-9)；
Preferably, the time of step (2) described stirring is 50-80min, preferably 60-70min.
7. according to the described in any item preparation methods of claim 3-6, which is characterized in that step (3) the vacuum drying temperature
Degree is 35-45 DEG C, preferably 38-42 DEG C；
Preferably, step (3) the vacuum drying time is 20-28h, preferably 22-26h.
8. according to the described in any item preparation methods of claim 3-7, which is characterized in that further include step before step (1)
(a): preparing graphene oxide；
Preferably, the method that step (a) prepares graphene oxide is Hummer method.
9. according to the described in any item preparation methods of claim 4-8, which is characterized in that the preparation method includes following step
It is rapid:
(I) graphene oxide is prepared in Hummer method；
(II) deionized water is mixed according to the ratio of liquid-solid ratio 4-8mL/g and graphene oxide, ultrasonic disperse obtain graphite oxide
Alkene dispersion liquid；
(III) graphene oxide dispersion obtained by mixed zinc salts solution and step (II), the Zn in zinc solution2+With the oxidation
The mass ratio of graphene in graphene dispersing solution is (1-50): stirring 20-28h at 10,20-30 DEG C, 0.02- is added dropwise
The sodium borohydride solution and/or sodium citrate solution of 0.05mol/L is separated by solid-liquid separation after stirring 50-80min, obtains solid product,
The zinc salt includes zinc nitrate and/or zinc sulfate, Zn in the zinc solution2+Molar concentration be 1.5-2.5mmol/L, it is described
Zn in zinc solution2+Mass ratio with reducing agent in the reducing solution is 1:(6-10)；
(IV) vacuum drying step (III) obtained solid product 20-28h at 35-45 DEG C, obtains graphene oxide-loaded nano zero
Valence zinc composite material.
10. a kind of graphene oxide-loaded nano zeroth order zinc composite material as claimed in claim 1 or 2 is used for water body or soil
The application of reparation.
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