CN106268642A - Bobbles shape zinc oxide/graphene composite adsorbent and preparation method and application - Google Patents
Bobbles shape zinc oxide/graphene composite adsorbent and preparation method and application Download PDFInfo
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- CN106268642A CN106268642A CN201610812992.7A CN201610812992A CN106268642A CN 106268642 A CN106268642 A CN 106268642A CN 201610812992 A CN201610812992 A CN 201610812992A CN 106268642 A CN106268642 A CN 106268642A
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Abstract
The invention discloses a kind of bobbles shape zinc oxide/graphene composite adsorbent and preparation method and application, use hydro-thermal method, using sodium tartrate as morphology control agent, with carbamide or hexamethylenetetramine as precipitant, utilize and under precipitant hot conditions, decompose produced alkaline environment, while graphene oxide electronation is become Graphene, realize bobbles shape zinc oxide particles in the in-situ deposition of graphenic surface and growth, the zinc oxide particles high uniformity of the bobbles shape obtaining high-specific surface area is dispersed in the compound adsorbent of graphenic surface, sodium tartrate make one-dimensional zinc oxide be assembled into have open, porous bobbles shape receives/microstructure unit, thus define abundant pore passage structure and adsorption potential；The specific surface area that Graphene is big, higher mechanical strength, chemical stability are beneficial to the recovery of compound adsorbent, process and recycle；To heavy metal ion Hg in water2+, Pb2+, As3+, Cr6+, Cd2+Advantages of good adsorption effect, be with a wide range of applications.
Description
Technical field
The invention belongs to adsorbent preparing technical field, be specifically related to a kind of bobbles shape zinc oxide/Graphene composite adsorption
Agent and preparation method and application.
Background technology
Fast development and the quickening of urbanization process, a large amount of mining and metallurgys, machine-building, chemical industry, electronics, instrument along with industry
The most directly discharge without suitable process etc. industry and mining sewage, cause serious Heavy-Metal-Contaminated Environments.Heavy metal pollution master
During water to be shown pollutes, some shows in air and solid waste, owing to heavy metal can between three mutually
Migrate, easily cause the indirect pollution of all kinds of environmental key-element.Heavy metal water pollutes and is different from the pollution of other kinds of water, due to weight
Metallic pollution can not can only be occurred the mutual conversion between various form, the harm thus resulted in the environment by environment degradable
Even more serious, deal with difficulty bigger.External of common occurrence about the event of heavy metal pollution, such as New Jersey ground
Lead, the contamination accident of chromium in lower water, " minamata disease " event that Japan's mercury pollution causes, " itai-itai " event that cadmium pollution causes.
Recent year is also to appear in the newspapers repeatly about the event of heavy metal pollution, such as the cadmium pollution thing in section waters, Longchuanjiang Chuxiong in 2004
Part, the arsenic contamination accident of yueyang, hunan in 2006, Yunnan Yang Zonghai arsenic contamination accident in 2008, Shanyang county vanadium tailings pollution
Event, training river, Sichuan in 2011 manganese ore water contamination accident, Ruichang, Jiangxi tap water copper staining event, the chromium slag contaminated thing of Qujing of Yunnan
Part etc., these great heavy metal pollution events cause serious harm to environment, the production of people and life.Along with country
To the ecological friendly and progressively promotion of the strategy of sustainable development and enforcement, solve heavy metal pollution the most efficiently, reclaim and profit
The emphasis of heavy metal pollution area research is become by heavy metal resources.The feature of heavy metal pollution mainly has: 1) toxicity has length
Phase persistence, and the organic compound that toxicity is higher can be changed under microbial action；2) bioconcentration.In the face of heavy metal
That pollutes increases the weight of day by day, and multiple processing method has been applied to remove the heavy metal ion in water, such as chemical precipitation method, electrolysis
Method, biophysics method, ion exchange etc., these methods achieve certain effect in processing heavy metal pollution, but also deposit
In problems, although as chemical precipitation method is simple, but sediment weight is big, and moisture content is high, easily causes secondary pollution, and some huge sum of money
Belong to after waste water processes and be difficult to reach discharge standard；Electrolysis be only applicable to process high concentration heavy metal wastewater thereby, when heavy metal from
When sub-concentration is low, power consumption is bigger；Biophysics method, ion exchange treating capacity are limited, and equipment cost is higher, limits this
A little methods are in the large-scale application of heavy metal-polluted water treatment field.
In the method that numerous heavy metal pollutions process, absorption method is widely used in as a kind of method easy, effective
Process the heavy metal ion in sewage.In recent years, scientific research personnel often by adsorbent nanorize or with other functional nanomaterials
Compound, thus improve the specific surface area of adsorbent, surface energy and chemical reactivity, and finally improve adsorbent for heavy metal
Adsorption capacity and the rate of adsorption.Oxide is the adsorbent that a class is conventional, and research shows, SiO2, Al2O3, TiO2, Fe2O3,
The nano-particle such as ZnO and corresponding nano composite material are used equally to the process of effluent containing heavy metal ions, adsorb compared to tradition
Agent, its adsorption capacity and the rate of adsorption all have significant improvement.Zinc oxide (ZnO) is as a kind of important inorganic nano material
Material, is widely used in the fields such as semi-conducting material, sensing material, catalyst, catalyst carrier, photoelectric material.As suction
Enclosure material is applied to the process aspect of heavy metal wastewater thereby also preferable performance.ZnO nanoparticle is being prepared and in application process,
Owing to surface can be higher, it is susceptible to the reunion of self, thus affects the performance of its performance, the most how to avoid ZnO nano
The reunion of particle self, improves its absorption property tool and is of great significance.The most conventional method mainly has two kinds: 1) system
Get everything ready/the micron composite structure of receiving of special appearance, pressed down by the cooperative effect between nanoscale and micro-meter scale and structure effect
Reunion between nanoparticle processed；2) by nanometer particle load to having the carrier surface of high-specific surface area, nanoparticle is improved
Dispersion, suppresses interparticle reunion, and then realizes the lifting of absorption property.
Graphene is because of its big theoretical specific surface area, high heat stability and chemical stability, and strong toughness and machinery are strong
Degree, is that the ideal preparing functional composite material constructs primitive.Can be with big table because of high surface when Graphene is used alone
Area makes graphene nanometer sheet interlayer be susceptible to secondary stacking, becomes the bottleneck limiting its large-scale application.
Summary of the invention
The present invention proposes to overcome shortcoming present in prior art, its objective is to provide a kind of bobbles shape oxygen
Change zinc/graphene composite adsorbent and preparation method and application.
The technical scheme is that
A kind of bobbles shape zinc oxide/graphene composite adsorbent, described adsorbent is the bobbles constructed by one-dimensional banding zinc oxide
Shape construction unit, the weight/mass percentage composition of zinc oxide is 30～80%, and the particle diameter of bobbles shape zinc oxide nano-particle is distributed as 2～5
M, the specific surface area of bobbles shape zinc oxide/graphene composite adsorbent is 120～360 m2/g。
The preparation method of a kind of bobbles shape zinc oxide/graphene composite adsorbent, comprises the following steps:
A, with graphite as raw material, use Hummer method synthesis graphene oxide, the graphene oxide prepared is distributed to water-soluble
In liquid, form stable graphene oxide suspension；
B, metal zinc salt is dissolved in step A gained graphene oxide suspension；Weigh certain mass sodium tartrate again and add it
In, obtain the graphene oxide suspension containing metal zinc salt；
C, configuration molar concentration are the precipitant solution of 0.05 M ~ 4 M, under the stirring condition of 500 revs/min ~ 2000 revs/min
Dropwise it is added drop-wise in the graphene oxide suspension containing metal zinc salt of step B gained；
D, step C gained suspension is proceeded in polytetrafluoroethylliner liner, under 90 ° of C ~ 180 ° C hydrothermal conditions, react 6 h
~ 72 h, reaction naturally cools to room temperature after terminating, centrifugal, washing, obtains bobbles shape zinc oxide/graphene composite adsorbent.
In described step A, in graphene oxide suspension, the mass concentration of graphene oxide is 0.1 g/L ~ 5 g/L.
In the described graphene oxide suspension containing zinc ion, the molar concentration of zinc salt is 0.01 M ~ 0.5 M.
In described step B, the acid ion of metal zinc salt is Cl-、SO4 2-、NO3 -、CH3COO-In any one.
Described sodium tartrate is 1:15 with the mol ratio of metal zinc salt.
Described precipitant is any one in carbamide or hexamethylenetetramine.
The application of a kind of bobbles shape zinc oxide/graphene composite adsorbent, is used for removing heavy metal ion in water, to Hg2+,
Pb2+, As3+, Cr6+, Cd2+Adsorption capacity respectively reach 120 ~ 380 mg/g, 180 ~ 560 mg/g, 200 ~ 520 mg/g, 90
~360 mg/g, 100~420 mg/g。
The invention has the beneficial effects as follows:
The present invention is with hexamethylenetetramine or carbamide as precipitant, and sodium tartrate is as morphology control agent, by simple hydro-thermal
The ZnO microsphere of the bobbles shape that method preparation is constructed by one-dimension zinc oxide nano belt, the collaborative effect between nanoscale and micro-meter scale
The stability of material should be improve, simultaneously the opening of bobbles shape zinc oxide with the reunion of structure effect suppression nanoscale zinc oxide
The formula structure of putting can expose more adsorption activity position；Utilize the alkaline environment that precipitant produces under high-temperature water heat condition,
Making in adsorbent preparation process, the preparation of bobbles shape zinc oxide and the electronation of graphene oxide are Tong Bu carried out, favorably
Disperse at the high uniformity of Graphene carrier surface in zinc oxide nano/microstructure unit, reduce the surface of graphene film Rotating fields
Chemical energy, suppresses the interstructural reunion of graphene sheet layer, obtains the zinc oxide/graphene composite material of high dispersive；Graphene carries
The introducing of body enhances the mechanically and chemically stability of composite, simultaneously facilitates the recycling and reuse of adsorbent, green ring
Protect, be suitable for heavy industrialization application.Present invention achieves the preparation of bobbles shape zinc oxide nano/microstructure unit and at graphite
The high uniformity dispersion of alkene carrier surface, obtains bobbles shape zinc oxide/graphene composite adsorbent, and preparation technology is simple, energy consumption
Low, preparation process is green non-poisonous and processing the prospect that is widely used in terms of heavy metal pollution in water.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the embodiment of the present invention 1 gained bobbles shape zinc oxide/graphene composite adsorbent；
Fig. 2 is the scanning electricity under the embodiment of the present invention 2 gained bobbles shape zinc oxide/graphene composite adsorbent different amplification
Mirror figure (a:3k amplification；B:50k amplification)；
Fig. 3 is the scanning electricity under the embodiment of the present invention 3 gained bobbles shape zinc oxide/graphene composite adsorbent different amplification
Mirror figure (a:3k amplification；B:40k amplification)；
Fig. 4 be in the embodiment of the present invention 4 gained bobbles shape zinc oxide/graphene composite adsorbent to Hg2+, Pb2+, As3+, Cr6+,
Cd2+Adsorption isothermal curve figure.
Detailed description of the invention
The preparation to bobbles shape zinc oxide/graphene composite adsorbent of the present invention below in conjunction with Figure of description and embodiment
Method and application thereof are described in detail:
As shown in Fig. 1 ~ 4, a kind of bobbles shape zinc oxide/graphene composite adsorbent, described adsorbent is to be aoxidized by one-dimensional banding
The pompon-like structure unit that zinc is constructed, the weight/mass percentage composition of zinc oxide is 30～80%, the grain of bobbles shape zinc oxide nano-particle
Footpath is distributed as 2～5 m, and the specific surface area of bobbles shape zinc oxide/graphene composite adsorbent is 120～360 m2/g。
The preparation method of a kind of bobbles shape zinc oxide/graphene composite adsorbent, comprises the following steps:
A, with graphite as raw material, use Hummer method synthesis graphene oxide, the graphene oxide prepared is distributed to water-soluble
In liquid, form stable graphene oxide suspension；
B, metal zinc salt is dissolved in step A gained graphene oxide suspension；Weigh certain mass sodium tartrate again and add it
In, obtain the graphene oxide suspension containing metal zinc salt；
C, configuration molar concentration are the precipitant solution of 0.05 M ~ 4 M, under the stirring condition of 500 revs/min ~ 2000 revs/min
Dropwise it is added drop-wise in the graphene oxide suspension containing metal zinc salt of step B gained；
D, step C gained suspension is proceeded in polytetrafluoroethylliner liner, under 90 ° of C ~ 180 ° C hydrothermal conditions, react 6 h
~ 72 h, reaction naturally cools to room temperature after terminating, centrifugal, washing, obtains bobbles shape zinc oxide/graphene composite adsorbent.
In described step A, in graphene oxide suspension, the mass concentration of graphene oxide is 0.1 g/L ~ 5 g/L.
In the described graphene oxide suspension containing zinc ion, the molar concentration of zinc salt is 0.01 M ~ 0.5 M.
In described step B, the acid ion of metal zinc salt is Cl-、SO4 2-、NO3 -、CH3COO-In any one.
Described sodium tartrate is 1:15 with the mol ratio of metal zinc salt.
Described precipitant is any one in carbamide or hexamethylenetetramine.
The application of a kind of bobbles shape zinc oxide/graphene composite adsorbent, is used for removing heavy metal ion in water, to Hg2+,
Pb2+, As3+, Cr6+, Cd2+Adsorption capacity respectively reach 120 ~ 380 mg/g, 180 ~ 560 mg/g, 200 ~ 520 mg/g, 90
~360 mg/g, 100~420 mg/g。
Embodiment 1
Accurately weighing the graphene oxide that 0.1 g uses Hummer method to prepare, ultrasonic disperse is formed in the aqueous solution of 60 mL
Suspension A；The zinc nitrate hexahydrate of precise 0.001 mol is dissolved in suspension A, and the concentration of zinc salt is 0.0167 M, then
Accurately weigh sodium tartrate according to the ratio that mol ratio is 1:15 of sodium tartrate Yu metal zinc salt, be dissolved in suspension A, ultrasonic
Suspension B is formed after disperseing 3 minutes；The another hexamethylenetetramine solution that concentration is 0.5 M configuring 20 mL, 500 ~ 2000
Rev/min stirring condition under be dropwise added drop-wise in suspension B, drip complete under 120 ° of C hydrothermal conditions react 24 hours, instead
Room temperature, sucking filtration, washing should be naturally cooled to after terminating, obtain bobbles shape zinc oxide/graphene composite adsorbent.Wherein, oxidation
The weight/mass percentage composition of zinc is 42%, and bobbles shape zinc oxide nano/micro structure is to be built into the ZnO grain of bobbles shape by 1-dimention nano band
Son, Average Particle Diameters is 3 m, there is substantial amounts of radioactive pore passage structure, composite nano adsorbent between ZnO nano-band
Specific surface area be 272 m2/g；
Above-mentioned 0.05 g bobbles shape zinc oxide/graphene composite adsorbent is dispersed in respectively containing Hg2+, Pb2+, As3+, Cr6+, Cd2+
Solution in, temperature be 30 ° of C isothermal vibration instrument in adsorb 24 hours.After reaching adsorption equilibrium, to Hg2+, Pb2+, As3+,
Cr6+, Cd2+Adsorption capacity be respectively 340 mg/g, 520 mg/g, 470 mg/g, 350 mg/g, 390 mg/g.
Embodiment 2
Accurately weighing the graphene oxide that 0.1 g uses Hummer method to prepare, ultrasonic disperse is formed in the aqueous solution of 60 mL
Suspension A；The zinc chloride of precise 0.001 mol is dissolved in suspension A, and the concentration of zinc salt is 0.0167 M, according still further to wine
Stone acid sodium accurately weighs sodium tartrate with the ratio that mol ratio is 1:15 of metal zinc salt, is dissolved in suspension A, ultrasonic disperse 3
Suspension B is formed after minute；The another urea liquid that concentration is 1 M configuring 20 mL, at the stirring condition of 500 ~ 2000 revs/min
Under be dropwise added drop-wise in suspension B, drip complete under 180 ° of C hydrothermal conditions react 6 hours, reaction terminate rear natural cooling
To room temperature, sucking filtration, washing, obtain bobbles shape zinc oxide/graphene composite adsorbent.Wherein, the weight/mass percentage composition of zinc oxide
Being 39%, bobbles shape zinc oxide nano/micro structure is to be built into the ZnO particle of bobbles shape by 1-dimention nano band, and Average Particle Diameters is
, there is substantial amounts of radioactive pore passage structure in 4 m, the specific surface area of composite nano adsorbent is 195 between ZnO nano-band
m2/g；
Above-mentioned 0.05 g bobbles shape zinc oxide/graphene composite adsorbent is dispersed in respectively containing Hg2+, Pb2+, As3+, Cr6+, Cd2+
Solution in, temperature be 30 ° of C isothermal vibration instrument in adsorb 24 hours.After reaching adsorption equilibrium, to Hg2+, Pb2+, As3+,
Cr6+, Cd2+Adsorption capacity be respectively 290 mg/g, 480 mg/g, 390 mg/g, 310 mg/g, 360 mg/g.
Embodiment 3
Accurately weighing the graphene oxide that 0.1 g uses Hummer method to prepare, ultrasonic disperse is formed in the aqueous solution of 60 mL
Suspension A；The Zinc diacetate dihydrate of precise 0.001 mol is dissolved in suspension A, and the concentration of zinc salt is 0.0167 M, then
Accurately weigh sodium tartrate according to the ratio that mol ratio is 1:15 of sodium tartrate Yu metal zinc salt, be dissolved in suspension A, ultrasonic
Suspension B is formed after disperseing 3 minutes；The another urea liquid that concentration is 2 M configuring 20 mL, 500 ~ 2000 revs/min stir
Dropwise being added drop-wise under the conditions of mixing in suspension B, drip complete reaction 12 hours under 150 ° of C hydrothermal conditions, reaction terminates the most certainly
So it is cooled to room temperature, sucking filtration, washing, obtains bobbles shape zinc oxide/graphene composite adsorbent.Wherein, the quality hundred of zinc oxide
Dividing content is 46%, and bobbles shape zinc oxide nano/micro structure is to be built into the ZnO particle of bobbles shape, mean diameter by 1-dimention nano band
Size is 5 m, there is substantial amounts of radioactive pore passage structure between ZnO nano-band, and the specific surface area of composite nano adsorbent is
320 m2/g；
Above-mentioned 0.05g bobbles shape zinc oxide/graphene composite adsorbent is dispersed in respectively containing Hg2+, Pb2+, As3+, Cr6+, Cd2+'s
In solution, temperature be 30 ° of C isothermal vibration instrument in adsorb 24 hours.After reaching adsorption equilibrium, to Hg2+, Pb2+, As3+, Cr6+,
Cd2+Adsorption capacity be respectively 360 mg/g, 530 mg/g, 490 mg/g, 330 mg/g, 410 mg/g.
Embodiment 4
Accurately weighing the graphene oxide that 0.1 g uses Hummer method to prepare, ultrasonic disperse is formed in the aqueous solution of 60 mL
Suspension A；The zinc nitrate hexahydrate of precise 0.0008 mol is dissolved in suspension A, and the concentration of zinc salt is 0.0133 M, then
Accurately weigh sodium tartrate according to the ratio that mol ratio is 1:15 of sodium tartrate Yu metal zinc salt, be dissolved in suspension A, ultrasonic
Suspension B is formed after disperseing 3 minutes；The another hexamethylenetetramine solution that concentration is 2 M configuring 20 mL, 500 ~ 2000
Rev/min stirring condition under be dropwise added drop-wise in suspension B, drip complete under 90 ° of C hydrothermal conditions react 24 hours, instead
Room temperature, sucking filtration, washing should be naturally cooled to after terminating, obtain bobbles shape zinc oxide/graphene composite adsorbent.Wherein, oxidation
The weight/mass percentage composition of zinc is 36%, and bobbles shape zinc oxide nano/micro structure is to be built into the ZnO grain of bobbles shape by 1-dimention nano band
Son, Average Particle Diameters is 5 m, there is substantial amounts of radioactive pore passage structure, composite nano adsorbent between ZnO nano-band
Specific surface area be 360 m2/g；
Above-mentioned 0.05 g bobbles shape zinc oxide/graphene composite adsorbent is dispersed in respectively containing Hg2+, Pb2+, As3+, Cr6+, Cd2+
Solution in, temperature be 30 ° of C isothermal vibration instrument in adsorb 24 hours.After reaching adsorption equilibrium, to Hg2+, Pb2+, As3+,
Cr6+, Cd2+Adsorption capacity be respectively 380 mg/g, 560 mg/g, 520 mg/g, 360 mg/g, 420 mg/g.
In zinc oxide/graphene composite adsorbent prepared by the present invention, zinc oxide particles is to be constructed by one-dimensional banding zinc oxide
Pompon-like structure unit, the weight/mass percentage composition of zinc oxide is 30～80%, the distribution of the particle diameter of bobbles shape zinc oxide nano-particle
Being 2～5 m, the specific surface area of bobbles shape zinc oxide/graphene composite adsorbent is 120～360 m2/g。
Use Japan's Shimadzu XRD-6000 type X-ray diffractometer to gained bobbles shape zinc oxide/Graphene in embodiment 1
Compound adsorbent carries out qualitative analysis, and result, as it is shown in figure 1, products therefrom occurs in that the characteristic diffraction peak corresponding to ZnO, does not has
, there is not the characteristic diffraction peak that graphene film Rotating fields stacking produces in the generation of other stray crystal phase.
Zeiss, Germany Supra 55 field emission scanning electron microscope (FESEM) is used to observe gained floss in embodiment 2
The pattern of spherical zinc oxide/graphene composite adsorbent, result as in figure 2 it is shown, by 1-dimention nano band be built into the receiving of bobbles shape/
Micro-ZnO particle, Average Particle Diameters is 3 m, there is substantial amounts of radioactive pore passage structure between ZnO nano-band.
Fig. 3 is the pattern of gained bobbles shape zinc oxide/graphene composite adsorbent in embodiment 3, in result and embodiment 2
Result is similar to, and is similarly obtained the bobbles shape ZnO nanoparticle that particle diameter is less, receive/the ZnO particle high uniformity of micro structure is dispersed in
The graphene sheet layer body structure surface of accordion.
Example 4 preparation bobbles shape zinc oxide/graphene composite adsorbent 0.05 g be dispersed in containing heavy metal from
Sub-Mn+Aqueous solution in, wherein Mn+For Hg2+, Pb2+, As3+, Cr6+, Cd2+Any one of, in the constant temperature that temperature is 30 ° of C
Concussion instrument adsorbs 24 hours, to Hg2+, Pb2+, As3+, Cr6+, Cd2+Adsorption capacity respectively reach 120 ~ 380 mg/g, 180 ~
560 mg/g, 200 ~ 520 mg/g, 90 ~ 360 mg/g, 100 ~ 420 mg/g.Fig. 4 shows the embodiment 4 spherical oxidation of medium staple
Zinc/graphene composite adsorbent is to Hg2+, Pb2+, As3+, Cr6+, Cd2+Adsorption isothermal curve figure.
The present invention is with hexamethylenetetramine or carbamide as precipitant, and sodium tartrate is as morphology control agent, by simply
The ZnO microsphere of the bobbles shape that hydro-thermal method preparation is constructed by one-dimension zinc oxide nano belt, the association between nanoscale and micro-meter scale
Suppress the reunion of nanoscale zinc oxide with effect and structure effect, improve the stability of material, simultaneously bobbles shape zinc oxide
Open architecture can expose more adsorption activity position；Utilize the alkaline ring that precipitant produces under high-temperature water heat condition
Border so that in adsorbent preparation process, the preparation of bobbles shape zinc oxide and the electronation of graphene oxide Tong Bu carry out, have
It is beneficial to zinc oxide nano/microstructure unit and disperses at the high uniformity of Graphene carrier surface, reduce the table of graphene film Rotating fields
Face chemical energy, suppresses the interstructural reunion of graphene sheet layer, obtains the zinc oxide/graphene composite material of high dispersive；Graphene
The introducing of carrier enhances the mechanically and chemically stability of composite, simultaneously facilitates the recycling and reuse of adsorbent, green
Environmental protection, is suitable for heavy industrialization application.
Claims (8)
1. bobbles shape zinc oxide/graphene composite adsorbent, it is characterised in that: described adsorbent is to be aoxidized by one-dimensional banding
The pompon-like structure unit that zinc is constructed, the weight/mass percentage composition of zinc oxide is 30～80%, the grain of bobbles shape zinc oxide nano-particle
Footpath is distributed as 2～5 m, and the specific surface area of bobbles shape zinc oxide/graphene composite adsorbent is 120～360 m2/g。
2. the preparation method of bobbles shape zinc oxide/graphene composite adsorbent, it is characterised in that: comprise the following steps:
A, with graphite as raw material, use Hummer method synthesis graphene oxide, the graphene oxide prepared is distributed to water-soluble
In liquid, form stable graphene oxide suspension；
B, metal zinc salt is dissolved in step A gained graphene oxide suspension；Weigh certain mass sodium tartrate again and add it
In, obtain the graphene oxide suspension containing metal zinc salt；
C, configuration molar concentration are the precipitant solution of 0.05 M ~ 4 M, under the stirring condition of 500 revs/min ~ 2000 revs/min
Dropwise it is added drop-wise in the graphene oxide suspension containing metal zinc salt of step B gained；
D, step C gained suspension is proceeded in polytetrafluoroethylliner liner, under 90 ° of C ~ 180 ° C hydrothermal conditions, react 6 h
~ 72 h, reaction naturally cools to room temperature after terminating, centrifugal, washing, obtains bobbles shape zinc oxide/graphene composite adsorbent.
The preparation method of a kind of bobbles shape zinc oxide/graphene composite adsorbent the most according to claim 2, its feature exists
In: in described step A, in graphene oxide suspension, the mass concentration of graphene oxide is 0.1 g/L ~ 5 g/L.
The preparation method of a kind of bobbles shape zinc oxide/graphene composite adsorbent the most according to claim 2, its feature exists
In: in the described graphene oxide suspension containing zinc ion, the molar concentration of zinc salt is 0.01 M ~ 0.5 M.
The preparation method of a kind of bobbles shape zinc oxide/graphene composite adsorbent the most according to claim 2, its feature exists
In: in described step B, the acid ion of metal zinc salt is Cl-、SO4 2-、NO3 -、CH3COO-In any one.
The preparation method of a kind of bobbles shape zinc oxide/graphene composite adsorbent the most according to claim 2, its feature exists
In: described sodium tartrate is 1:15 with the mol ratio of metal zinc salt.
The preparation method of a kind of bobbles shape zinc oxide/graphene composite adsorbent the most according to claim 2, its feature exists
In: described precipitant is any one in carbamide or hexamethylenetetramine.
8. the application of bobbles shape zinc oxide/graphene composite adsorbent, it is characterised in that: be used for removing in water heavy metal from
Son, to Hg2+, Pb2+, As3+, Cr6+, Cd2+Adsorption capacity respectively reach 120 ~ 380 mg/g, 180 ~ 560 mg/g, 200 ~
520 mg/g, 90~360 mg/g, 100~420 mg/g。
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