CN106268642B - Bobbles shape zinc oxide/graphene composite adsorbent and the preparation method and application thereof - Google Patents
Bobbles shape zinc oxide/graphene composite adsorbent and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of bobbles shape zinc oxide/graphene composite adsorbents and the preparation method and application thereof, using hydro-thermal method, using sodium tartrate as pattern controlling agent, using urea or hexamethylenetetramine as precipitating reagent, utilize alkaline environment caused by decomposition under precipitating reagent hot conditions, while by graphene oxide electronation at graphene, realize bobbles shape zinc oxide particles in-situ deposition on the surface of graphene and growth, obtain the compound adsorbent of the zinc oxide particles high uniformity dispersion of the bobbles shape of high-specific surface area on the surface of graphene, sodium tartrate is assembled into one-dimensional zinc oxide with open, porous bobbles shape receives/microstructure unit, so as to form cellular structure abundant and adsorption potential；The big specific surface area of graphene, higher mechanical strength, chemical stability are conducive to recycling, processing and the recycling of compound adsorbent；To heavy metal ion Hg in water2+, Pb2+, As3+, Cr6+, Cd2+Adsorption effect it is good, be with a wide range of applications.
Description
Technical field
The invention belongs to adsorbent preparation technical fields, and in particular to a kind of bobbles shape zinc oxide/graphene composite adsorption
Agent and the preparation method and application thereof.
Background technique
With the rapid development of industry with the quickening of urbanization process, a large amount of mining and metallurgys, machine-building, chemical industry, electronics, instrument
Etc. industry and mining sewage without processing just direct emission appropriate, cause serious Heavy-Metal-Contaminated Environments.Heavy metal pollution master
It shows in water pollution, some shows in atmosphere and solid waste, since heavy metal can be between three mutually
Migration, easily causes the indirect pollution of all kinds of environmental elements.Heavy metal water pollution is different from other kinds of water pollution, due to weight
By environment degradable mutually converting between various forms cannot can only occur in the environment for metallic pollution, thus caused by endanger
It is even more serious, it is bigger to deal with difficulty.Foreign countries are commonplace about the event of heavy metal pollution, such as New Jersey
It is lauched the contamination accident of middle lead, chromium, " minamata disease " event caused by Japanese mercury pollution, " itai-itai " event caused by cadmium pollution.
The domestic event about heavy metal pollution is also to appear in the newspapers repeatly in recent years, the cadmium pollution thing in such as Longchuanjiang Chuxiong in 2004 section waters
Part, the arsenic pollution event of yueyang, hunan in 2006, Yunnan Yang Zonghai arsenic pollution event in 2008, Shanyang county vanadium tailings pollution
Event, river manganese ore water contamination accident, Jiangxi Ruichang tap water Cu-W ore deposit event, the chromium slag contaminated thing of Qujing of Yunnan are trained in Sichuan within 2011
Part etc., these great heavy metal pollution events cause serious harm to environment, people's production and life.With country
To the ecological friendly and strategy of sustainable development gradually promotion and implementation, heavy metal pollution, recycling and benefit how are efficiently solved
Become the emphasis of heavy metal pollution area research with heavy metal resources.The characteristics of heavy metal pollution mainly has: 1) toxicity has length
Phase duration, and the stronger organic compound of toxicity can be converted under microbial action；2) bioconcentration.In face of heavy metal
The increasingly exacerbation of pollution, a variety of processing methods have been applied to the heavy metal ion in water removal, 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 sediment weight is big as chemical precipitation method is simple, moisture content is high, easily causes secondary pollution, and some huge sum of moneys
It is difficult to reach discharge standard after belonging to wastewater treatment；Electrolysis method be only applicable to processing 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
Large-scale application of a little methods in heavy metal-polluted water treatment field.
In the method for numerous heavy metal pollutions processing, absorption method is widely used in as a kind of easy, effective method
Handle the heavy metal ion in sewage.In recent years, scientific research personnel often by adsorbent nanosizing or with other function nano material
It is compound, to 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 a kind of common adsorbent, studies have shown that SiO2, Al2O3, TiO2, Fe2O3,
The nano particles such as ZnO and corresponding nanocomposite are used equally for the processing of effluent containing heavy metal ions, adsorb compared to tradition
Agent, adsorption capacity and the rate of adsorption have significant improvement.Zinc oxide (ZnO) is as a kind of important inorganic nano material
Material, is widely used in the fields such as semiconductor material, sensing material, catalyst, catalyst carrier, photoelectric material.As suction
The processing aspect that enclosure material is applied to heavy metal wastewater thereby also has preferable performance.ZnO nanoparticle in preparation and application process,
Since surface can be relatively high, it is easy to happen the reunion of itself, to influence the performance of its performance, therefore how to avoid ZnO nano
The reunion of particle itself improves its absorption property and has a very important significance.There are mainly two types of currently used methods: 1) making
Standby/the micron composite structure of receiving with special appearance, the synergistic effect and structure effect passed through between nanoscale and micro-meter scale press down
Reunion between nanoparticle processed；2) nanometer particle load is improved into nanoparticle to the carrier surface with high-specific surface area
Dispersion degree inhibits interparticle reunion, and then realizes the promotion of absorption property.
For graphene because of its big theoretical specific surface area, high thermal stability and chemical stability, strong toughness and machinery are strong
Degree is to prepare the ideal of functional composite material to construct primitive.Because high surface can be with big table when graphene is used alone
Area makes graphene nanometer sheet interlayer be easy to happen secondary stacking, becomes the bottleneck for limiting its large-scale application.
Summary of the invention
The present invention is proposed to overcome disadvantage existing in the prior art, and the purpose is to provide a kind of bobbles shape oxygen
Change zinc/graphene composite adsorbent and the preparation method and application thereof.
The technical scheme is that
A kind of bobbles shape zinc oxide/graphene composite adsorbent, the adsorbent are constructed by one-dimensional band-like zinc oxide
The mass percentage of pompon-like structure unit, zinc oxide is 30~80%, and the particle diameter distribution of bobbles shape zinc oxide nano-particle is
2~5 μm, bobbles shape zinc oxide/graphene composite adsorbent specific surface area is 120~360 m2/g。
A kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent, comprising the following steps:
A, using graphite as raw material, graphene oxide is synthesized using Hummer method, the graphene oxide prepared is distributed to
In aqueous solution, stable graphene oxide suspension is formed；
B, metal zinc salt is dissolved in graphene oxide suspension obtained by step A；Certain mass sodium tartrate is weighed again to add
Enter wherein, obtains the graphene oxide suspension of the zinc salt containing metal；
C, the precipitant solution that configuration molar concentration is the M of 0.05 M ~ 4, in 500 revs/min ~ 2000 revs/min of stirring bar
It is added drop-wise to dropwise under part in the graphene oxide suspension of the resulting zinc salt containing metal of step B；
D, suspension obtained by step C is transferred in polytetrafluoroethylliner liner, is reacted under 90 °C ~ 180 °C hydrothermal conditions
The h of 6 h ~ 72, cooled to room temperature, centrifugation, washing obtain bobbles shape zinc oxide/graphene composite adsorption after reaction
Agent.
The mass concentration of graphene oxide is the g/L of 0.1 g/L ~ 5 in graphene oxide suspension in the step A.
The molar concentration of zinc salt is the M of 0.01 M ~ 0.5 in the graphene oxide suspension containing zinc ion.
The acid ion of metal zinc salt is Cl in the step B-、SO4 2-、NO3 -、CH3COO-In any one.
The molar ratio of the sodium tartrate and metal zinc salt is 1:15.
The precipitating reagent is any one in urea or hexamethylenetetramine.
A kind of application of bobbles shape zinc oxide/graphene composite adsorbent, for going heavy metal ion in water removal, 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 beneficial effects of the present invention are:
The present invention is using hexamethylenetetramine or urea as precipitating reagent, and sodium tartrate is as pattern controlling agent, by simple
The ZnO microsphere for the bobbles shape that hydro-thermal method preparation is constructed by one-dimension zinc oxide nanobelt, the association between nanoscale and micro-meter scale
The reunion for inhibiting nanoscale zinc oxide with effect and structure effect, improves the stability of material, while bobbles shape zinc oxide
Open architecture can expose more adsorption activity positions；The alkaline ring generated under high temperature hydrothermal condition using precipitating reagent
Border has so that the preparation of bobbles shape zinc oxide is synchronous with the electronation of graphene oxide to be carried out in adsorbent preparation process
High uniformity conducive to zinc oxide nano/microstructure unit in graphene carrier surface disperses, and reduces the table of graphene sheet layer structure
Face chemical energy inhibits the interstructural reunion of graphene sheet layer, obtains zinc oxide/graphene composite material of high dispersive；Graphene
The introducing of carrier enhances the mechanically and chemically stability of composite material, while being convenient for the recycling and reuse of adsorbent, green
Environmental protection is suitble to heavy industrialization application.The present invention realizes the preparation of bobbles shape zinc oxide nano/microstructure unit and its in stone
The high uniformity of black alkene carrier surface disperses, and obtains bobbles shape zinc oxide/graphene composite adsorbent, and preparation process is simple, energy
Consume that low, preparation process is green non-poisonous and the prospect that is widely used in terms of heavy metal pollution in processing water.
Detailed description of the invention
Fig. 1 is 1 gained bobbles shape zinc oxide of the embodiment of the present invention/graphene composite adsorbent X-ray diffractogram；
Fig. 2 is sweeping under 2 gained bobbles shape zinc oxide of the embodiment of the present invention/graphene composite adsorbent different amplification
Retouch electron microscope (a:3k amplification factor；B:50k amplification factor)；
Fig. 3 is sweeping under 3 gained bobbles shape zinc oxide of the embodiment of the present invention/graphene composite adsorbent different amplification
Retouch electron microscope (a:3k amplification factor；B:40k amplification factor)；
Fig. 4 is gained bobbles shape zinc oxide/graphene composite adsorbent in the embodiment of the present invention 4 to Hg2+, Pb2+, As3+,
Cr6+, Cd2+Adsorption isothermal curve figure.
Specific embodiment
With reference to the accompanying drawings of the specification and preparation of the embodiment to bobbles shape zinc oxide/graphene composite adsorbent of the present invention
Method and its application are described in detail:
As shown in Fig. 1 ~ 4, a kind of bobbles shape zinc oxide/graphene composite adsorbent, the adsorbent is by one-dimensional band-like
The pompon-like structure unit that zinc oxide is constructed, the mass percentage of zinc oxide are 30~80%, bobbles shape zinc oxide nano-particle
Particle diameter distribution be 2~5 μm, bobbles shape zinc oxide/graphene composite adsorbent specific surface area be 120~360 m2/g。
A kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent, comprising the following steps:
A, using graphite as raw material, graphene oxide is synthesized using Hummer method, the graphene oxide prepared is distributed to
In aqueous solution, stable graphene oxide suspension is formed；
B, metal zinc salt is dissolved in graphene oxide suspension obtained by step A；Certain mass sodium tartrate is weighed again to add
Enter wherein, obtains the graphene oxide suspension of the zinc salt containing metal；
C, the precipitant solution that configuration molar concentration is the M of 0.05 M ~ 4, in 500 revs/min ~ 2000 revs/min of stirring bar
It is added drop-wise to dropwise under part in the graphene oxide suspension of the resulting zinc salt containing metal of step B；
D, suspension obtained by step C is transferred in polytetrafluoroethylliner liner, is reacted under 90 °C ~ 180 °C hydrothermal conditions
The h of 6 h ~ 72, cooled to room temperature, centrifugation, washing obtain bobbles shape zinc oxide/graphene composite adsorption after reaction
Agent.
The mass concentration of graphene oxide is the g/L of 0.1 g/L ~ 5 in graphene oxide suspension in the step A.
The molar concentration of zinc salt is the M of 0.01 M ~ 0.5 in the graphene oxide suspension containing zinc ion.
The acid ion of metal zinc salt is Cl in the step B-、SO4 2-、NO3 -、CH3COO-In any one.
The molar ratio of the sodium tartrate and metal zinc salt is 1:15.
The precipitating reagent is any one in urea or hexamethylenetetramine.
A kind of application of bobbles shape zinc oxide/graphene composite adsorbent, for going heavy metal ion in water removal, 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
The graphene oxide that 0.1 g uses the preparation of Hummer method is accurately weighed, ultrasonic disperse is in the aqueous solution of 60 mL
Form suspension A；The zinc nitrate hexahydrate of 0.001 mol of precise is dissolved in suspension A, and the concentration of zinc salt is 0.0167
M accurately weighs sodium tartrate according still further to the ratio that the molar ratio of sodium tartrate and metal zinc salt is 1:15, is dissolved in suspension A,
Suspension B is formed after ultrasonic disperse 3 minutes；The hexamethylenetetramine solution that the concentration of 20 mL of another configuration is 0.5 M, 500 ~
It is added drop-wise in suspension B dropwise under 2000 revs/min of stirring condition, it is small that the reaction 24 under 120 °C of hydrothermal conditions is added dropwise
When, cooled to room temperature, filters, washing, obtains bobbles shape zinc oxide/graphene composite adsorbent after reaction.Wherein,
The mass percentage of zinc oxide is 42%, and bobbles shape zinc oxide nano/micro-structure is to be built into bobbles shape by 1-dimention nano band
ZnO particle, Average Particle Diameters are 3 μm, there is a large amount of radioactive cellular structure between ZnO nano-band, and composite Nano is inhaled
Attached dose of specific surface area is 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 is to adsorb 24 hours in 30 °C of isothermal vibration instrument.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
The graphene oxide that 0.1 g uses the preparation of Hummer method is accurately weighed, ultrasonic disperse is in the aqueous solution of 60 mL
Form suspension A；The zinc chloride of 0.001 mol of precise is dissolved in suspension A, and the concentration of zinc salt is 0.0167 M, then is pressed
Sodium tartrate is accurately weighed according to the ratio that the molar ratio of sodium tartrate and metal zinc salt is 1:15, is dissolved in suspension A, ultrasound point
Suspension B is formed after dissipating 3 minutes；The urea liquid that the concentration of 20 mL of another configuration is 1 M, in 500 ~ 2000 revs/min of stirring
Under the conditions of be added drop-wise in suspension B dropwise, be added dropwise under 180 °C of hydrothermal conditions and react 6 hours, it is natural after reaction
It is cooled to room temperature, filters, washs, obtain bobbles shape zinc oxide/graphene composite adsorbent.Wherein, the quality percentage of zinc oxide
Content is 39%, and bobbles shape zinc oxide nano/micro-structure is the ZnO particle that bobbles shape is built by 1-dimention nano band, and average grain diameter is big
Small is 4 μm, there is a large amount of radioactive cellular structure between ZnO nano-band, and the specific surface area of composite nano adsorbent is
195 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 is to adsorb 24 hours in 30 °C of isothermal vibration instrument.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
The graphene oxide that 0.1 g uses the preparation of Hummer method is accurately weighed, ultrasonic disperse is in the aqueous solution of 60 mL
Form suspension A；The Zinc diacetate dihydrate of 0.001 mol of precise is dissolved in suspension A, and the concentration of zinc salt is 0.0167
M accurately weighs sodium tartrate according still further to the ratio that the molar ratio of sodium tartrate and metal zinc salt is 1:15, is dissolved in suspension A,
Suspension B is formed after ultrasonic disperse 3 minutes；The urea liquid that the concentration of 20 mL of another configuration is 2 M, at 500 ~ 2000 revs/min
Stirring condition under be added drop-wise in suspension B dropwise, be added dropwise and reacted 12 hours under 150 °C of hydrothermal conditions, reaction terminates
Cooled to room temperature afterwards filters, washing, obtains bobbles shape zinc oxide/graphene composite adsorbent.Wherein, the matter of zinc oxide
Measuring percentage composition is 46%, and bobbles shape zinc oxide nano/micro-structure is the ZnO particle that bobbles shape is built by 1-dimention nano band, average
Particle size is 5 μm, there is a large amount of radioactive cellular structure, the specific surface of composite nano adsorbent between ZnO nano-band
Product 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+Solution in, temperature is to adsorb 24 hours in 30 °C of isothermal vibration instrument.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
The graphene oxide that 0.1 g uses the preparation of Hummer method is accurately weighed, ultrasonic disperse is in the aqueous solution of 60 mL
Form suspension A；The zinc nitrate hexahydrate of 0.0008 mol of precise is dissolved in suspension A, and the concentration of zinc salt is 0.0133
M accurately weighs sodium tartrate according still further to the ratio that the molar ratio of sodium tartrate and metal zinc salt is 1:15, is dissolved in suspension A,
Suspension B is formed after ultrasonic disperse 3 minutes；The hexamethylenetetramine solution that the concentration of 20 mL of another configuration is 2 M, 500 ~
It is added drop-wise in suspension B dropwise under 2000 revs/min of stirring condition, it is small that the reaction 24 under 90 °C of hydrothermal conditions is added dropwise
When, cooled to room temperature, filters, washing, obtains bobbles shape zinc oxide/graphene composite adsorbent after reaction.Wherein,
The mass percentage of zinc oxide is 36%, and bobbles shape zinc oxide nano/micro-structure is to be built into bobbles shape by 1-dimention nano band
ZnO particle, Average Particle Diameters are 5 μm, there is a large amount of radioactive cellular structure between ZnO nano-band, and composite Nano is inhaled
Attached dose of specific surface area is 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 is to adsorb 24 hours in 30 °C of isothermal vibration instrument.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.
Zinc oxide particles are constructed by one-dimensional band-like zinc oxide in zinc oxide/graphene composite adsorbent prepared by the present invention
Pompon-like structure unit, the mass percentage of zinc oxide is 30~80%, the particle diameter distribution of bobbles shape zinc oxide nano-particle
It is 2~5 μm, bobbles shape zinc oxide/graphene composite adsorbent specific surface area is 120~360 m2/g。
Using Japanese Shimadzu XRD-6000 type X-ray diffractometer to gained bobbles shape zinc oxide/graphene in embodiment 1
Compound adsorbent carries out qualitative analysis not to be had as a result as shown in Figure 1, the characteristic diffraction peak corresponding to ZnO occurs in products therefrom
The generation of other stray crystal phases does not occur the characteristic diffraction peak of graphene sheet layer structure stacking generation.
Gained suede in embodiment 2 is observed using 55 field emission scanning electron microscope of Zeiss, Germany Supra (FESEM)
The pattern of spherical zinc oxide/graphene composite adsorbent, as a result as shown in Fig. 2, by 1-dimention nano band be built into the receiving of bobbles shape/
Micro- ZnO particle, Average Particle Diameters are 3 μm, there is a large amount of radioactive cellular structure between ZnO nano-band.
Fig. 3 is gained bobbles shape zinc oxide/graphene composite adsorbent pattern in embodiment 3, as a result and in embodiment 2
As a result similar, it is similarly obtained the lesser bobbles shape ZnO nanoparticle of partial size, receive/the ZnO particle high uniformity of micro-structure is dispersed in
The graphene sheet layer body structure surface of accordion.
Example 4 prepare bobbles shape zinc oxide/0.05 g of graphene composite adsorbent be dispersed in containing heavy metal from
Sub- Mn+Aqueous solution in, wherein Mn+For Hg2+, Pb2+, As3+, Cr6+, Cd2+Any one of, the constant temperature for being 30 °C in temperature
It is adsorbed 24 hours in concussion instrument, 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 spherical oxidation of 4 medium staple of embodiment
Zinc/graphene composite adsorbent is to Hg2+, Pb2+, As3+, Cr6+, Cd2+Adsorption isothermal curve figure.
The present invention is using hexamethylenetetramine or urea as precipitating reagent, and sodium tartrate is as pattern controlling agent, by simple
The ZnO microsphere for the bobbles shape that hydro-thermal method preparation is constructed by one-dimension zinc oxide nanobelt, the association between nanoscale and micro-meter scale
The reunion for inhibiting nanoscale zinc oxide with effect and structure effect, improves the stability of material, while bobbles shape zinc oxide
Open architecture can expose more adsorption activity positions；The alkaline ring generated under high temperature hydrothermal condition using precipitating reagent
Border has so that the preparation of bobbles shape zinc oxide is synchronous with the electronation of graphene oxide to be carried out in adsorbent preparation process
High uniformity conducive to zinc oxide nano/microstructure unit in graphene carrier surface disperses, and reduces the table of graphene sheet layer structure
Face chemical energy inhibits the interstructural reunion of graphene sheet layer, obtains zinc oxide/graphene composite material of high dispersive；Graphene
The introducing of carrier enhances the mechanically and chemically stability of composite material, while being convenient for the recycling and reuse of adsorbent, green
Environmental protection is suitble to heavy industrialization application.
Claims (7)
1. a kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent, it is characterised in that: the following steps are included:
A, using graphite as raw material, graphene oxide is synthesized using Hummer method, the graphene oxide prepared is distributed to water-soluble
In liquid, stable graphene oxide suspension is formed；
B, metal zinc salt is dissolved in graphene oxide suspension obtained by step A；Certain mass sodium tartrate is weighed again, and it is added
In, obtain the graphene oxide suspension of the zinc salt containing metal；
C, the precipitant solution that configuration molar concentration is the M of 0.05 M ~ 4, under 500 revs/min ~ 2000 revs/min of stirring condition
It is added drop-wise in the graphene oxide suspension of the resulting zinc salt containing metal of step B dropwise；
D, suspension obtained by step C is transferred in polytetrafluoroethylliner liner, reacts 6 h under 90 °C ~ 180 °C hydrothermal conditions
~ 72 h, cooled to room temperature, centrifugation, washing obtain bobbles shape zinc oxide/graphene composite adsorbent after reaction；
The bobbles shape zinc oxide/graphene composite adsorbent is the pompon-like structure unit constructed by one-dimensional band-like zinc oxide,
The mass percentage of zinc oxide is 30~80%, and the particle diameter distribution of bobbles shape zinc oxide nano-particle is 2~5 μm, bobbles shape
Zinc oxide/graphene composite adsorbent specific surface area is 120~360 m2/g。
2. a kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent according to claim 1, feature exist
In: the mass concentration of graphene oxide is the g/L of 0.1 g/L ~ 5 in graphene oxide suspension in the step A.
3. a kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent according to claim 1, feature exist
In: the molar concentration of zinc salt is the M of 0.01 M ~ 0.5 in the graphene oxide suspension of the zinc salt containing metal.
4. a kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent according to claim 1, feature exist
In: the acid ion of metal zinc salt is Cl in the step B-、SO4 2-、NO3 -、CH3COO-In any one.
5. a kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent according to claim 1, feature exist
In: the molar ratio of the sodium tartrate and metal zinc salt is 1:15.
6. a kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent according to claim 1, feature exist
In: the precipitating reagent is any one in urea or hexamethylenetetramine.
7. prepared by a kind of preparation method of bobbles shape zinc oxide/graphene composite adsorbent according to claim 1
Bobbles shape zinc oxide/graphene composite adsorbent application, it is characterised in that: for going heavy metal ion in water removal, 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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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580716A (en) * | 2012-01-18 | 2012-07-18 | 黑龙江大学 | Method for synthesizing zinc oxide/graphene composite by solvothermal method |
| CN104118902A (en) * | 2014-07-25 | 2014-10-29 | 济南大学 | Zinc oxide microspheres and preparation method thereof |
| CN104258810A (en) * | 2014-09-29 | 2015-01-07 | 扬州大学 | Adsorbing agent based on ferroferric oxide and graphene and preparation method of adsorbing agent |
| CN104801292A (en) * | 2015-04-22 | 2015-07-29 | 哈尔滨工业大学 | Preparation method for zinc oxide hollow nanosphere/graphene composite material |
| CN105561965A (en) * | 2015-12-31 | 2016-05-11 | 宿州学院 | Preparation method of flower shaped ZnO/graphene composite microsphere |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580716A (en) * | 2012-01-18 | 2012-07-18 | 黑龙江大学 | Method for synthesizing zinc oxide/graphene composite by solvothermal method |
| CN104118902A (en) * | 2014-07-25 | 2014-10-29 | 济南大学 | Zinc oxide microspheres and preparation method thereof |
| CN104258810A (en) * | 2014-09-29 | 2015-01-07 | 扬州大学 | Adsorbing agent based on ferroferric oxide and graphene and preparation method of adsorbing agent |
| CN104801292A (en) * | 2015-04-22 | 2015-07-29 | 哈尔滨工业大学 | Preparation method for zinc oxide hollow nanosphere/graphene composite material |
| CN105561965A (en) * | 2015-12-31 | 2016-05-11 | 宿州学院 | Preparation method of flower shaped ZnO/graphene composite microsphere |
Non-Patent Citations (1)
| Title |
|---|
| Graphene oxide used as a surfactant to induce the flower-like ZnO microstructures: growth mechanism and enhanced photocatalytic properties;Yao Chengli，et al.;《Crystal Research &Technology》;20141211;第49卷(第12期);982-989 |
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