CN109794263A - The preparation method and application of ZnS/GO porous microsphere nano material - Google Patents
The preparation method and application of ZnS/GO porous microsphere nano material Download PDFInfo
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- CN109794263A CN109794263A CN201910226710.9A CN201910226710A CN109794263A CN 109794263 A CN109794263 A CN 109794263A CN 201910226710 A CN201910226710 A CN 201910226710A CN 109794263 A CN109794263 A CN 109794263A
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Abstract
The invention discloses a kind of preparation method of ZnS/GO porous microsphere nano material and its applications in wastewater by photocatalysis.The preparation method is that: the mixed solution containing zinc source and sulphur source is poured into the polytetrafluoroethylene (PTFE) equipped with graphene oxide sheet and is done in the reaction kettle of liner, then carries out closed, is put into reacting furnace and carries out heating reaction, obtain ZnS/GO porous microsphere nano material；The mixed solution containing zinc source and sulphur source the preparation method comprises the following steps: by Zn (CH3COO)2·2H2O, which is add to deionized water, to be completely dissolved, and is then added and Zn (CH3COO)2·2H2The hypo of the amount of O same substance is uniformly mixed, then cetyl trimethylammonium bromide is added in mixed liquor.The ZnS/GO porous microsphere nano material that the present invention synthesizes has excellent photocatalysis performance, can be used as photochemical catalyst, act on weaving liquid waste processing, decompose colored dyes etc..
Description
Technical field
The present invention relates to a kind of preparation method and applications of efficient nano material, belong to materials science field.
Background technique
Light-catalysed power source solar energy reserves are abundant, inexhaustible, nexhaustible, and will not generate exhaust gas
Environment is polluted, therefore photocatalysis is received more and more attention in material, environment and chemical field.Light-catalysed application is also suitable
Extensively, such as highdensity electric energy and chemical energy can be converted solar energy into, and may be directly applied to produce hydrogen energy source
With degradation of contaminant (especially organic pollutant) etc..But with the intensification of research, it has been found that most photocatalysis material
Material itself has very big forbidden bandwidth, can only absorb the ultraviolet light within 420nm, limits material to the absorption region of light,
In addition to this, photo-excited electron is also easy to again compound with hole, reduces photocatalysis efficiency.Therefore current for inhibition light
The recombination in excitation electronics and hole is particularly important with the research for reducing forbidden bandwidth, wherein more and more researchers will
Sight invests this emerging nano material of graphene, and graphene can effectively improve the material disadvantage small to the absorption region of light,
And then improve photocatalysis efficiency.
Graphene has sizable specific surface area, so graphene composite material can be improved the absorption to pollutant；
The light transmittance of graphene is up to 97.7%, enhances light adsorption strength and light abstraction width；Furthermore the excellent electronics of graphene moves
Shifting rate and carrier properties improve the transmission and separation of photoexcited charge.Therefore doped graphene can improve general half well
The deficiencies of conductor material visible-light utilization rate is low and the excitation electron-hole probability of recombination is high.
Zinc sulphide (ZnS) is a kind of important II-VI group semiconducting compound, and having 3.72-3.77eV, (cubic phase is
3.72eV, hexagonal wurtzite are mutually 3.77eV) direct band gap and 40meV exciton binding energy.Due to these excellent performances,
Zinc oxide is widely used in various high-tech applications, such as light emitting diode, sensor, infrared window, photocatalysis, electroluminescent hair
Optical device etc..In recent years, since industrial development is rapid, environmental pollution has become main problem concerned by people, especially by giving up
Water pollution caused by water discharge and clothing factory's waste dyestuff.Therefore, it is necessary to a kind of effective methods come these toxic chemicals of degrading
And waste dyestuff.The photocatalytic degradation of organic dyestuff is one of control water pollution most efficient method.In this respect, zinc oxide is recognized
To be most effective photochemical catalyst, it to be used for degradable organic pollutant.Zinc sulphide mainly uses hydro-thermal method to be synthetically prepared it,
And influence of the differential responses system to final product pattern is studied by changing reaction condition, synthesize the variform oxygen of tool
Change zinc nanocrystals, as photocatalyst applications in waste water control, decomposition colored dyes etc..
Summary of the invention
Problem to be solved by this invention is: providing the preparation method and use of a kind of ZnS/GO porous microsphere nano material
On the way, which can be used as photochemical catalyst, acts on waste water control, decomposes colored dyes.
To solve the above-mentioned problems, the present invention provides a kind of preparation method of ZnS/GO porous microsphere nano material,
It is characterized in that, the mixed solution containing zinc source and sulphur source is poured into the polytetrafluoroethylene (PTFE) equipped with graphene oxide (GO) piece and does liner
Reaction kettle in, then carry out closed, be put into reacting furnace and carry out heating reaction, obtain ZnS/GO porous microsphere nano material；
The mixed solution containing zinc source and sulphur source the preparation method comprises the following steps: by Zn (CH3COO)2·2H2O has been add to deionized water
Then fully dissolved is added and Zn (CH3COO)2·2H2The hypo of the amount of O same substance is uniformly mixed, then
Cetyl trimethylammonium bromide is added in mixed liquor.
Preferably, the graphene oxide sheet the preparation method comprises the following steps: graphite powder, sodium nitrate are dissolved in the concentrated sulfuric acid, use
Magnetic stirring apparatus stirs evenly solution in ice-water bath, then by KMnO4It is added in mixed liquor, is protected at 20 DEG C several times
2h is held, 2h is then stirred at 35 DEG C, then dilute mixed solution with deionized water, is vigorously stirred 0.5h at 90 DEG C；By H2O2It is slow
Slowly it is added in solution and stirs evenly；With hydrochloric acid solution and deionized water cleaning mixture repeatedly, remaining sulfate radical is removed
Ion；Mixed liquor is freeze-dried under -60 DEG C of vacuum condition, GO powder is obtained by grinding, is scattered in anhydrous second
In alcohol, obtains uniform suspension and be coated on undeposited silicon chip；Finally silicon chip is placed in quartzy furnace, in 1 hour
Temperature is transferred to 650 DEG C, then naturally cools to room temperature to get graphene oxide sheet.
It is highly preferred that the weight ratio of the graphite powder and sodium nitrate is 1:1；The mass concentration of the concentrated sulfuric acid is 98wt%；Stone
Black alkene and KMnO4Weight ratio be 1:2~3；H2O2Mass concentration be 30wt%, graphene and H2O2Ratio be 1g:(6~
7.5)mL。
Preferably, Zn (CH in the mixed solution containing zinc source and sulphur source3COO)2·2H2The quality of O and deionized water
Volume ratio is 1g:5mL；Zn(CH3COO)2·2H2The mass ratio of O and cetyl trimethylammonium bromide is 16:1.
Preferably, the temperature in the reacting furnace is 120 DEG C, reaction time 16h.
The present invention also provides ZnS/GO made from a kind of preparation method of above-mentioned ZnS/GO porous microsphere nano material is more
Application of the hole microsphere nano material as photochemical catalyst in wastewater by photocatalysis is specifically used for weaving treating waste liquid, decomposes
Colored dyes.
The present invention uses cetyl trimethylammonium bromide as surfactant, has synthesized porous microsphere using hydro-thermal method
ZnS/GO nano material, and have studied the optimal conditions of synthesis process.
When CTAB concentration increases, the configuration of surface of zinc oxide is changed into rice shape Zinc oxide nanoparticle by nm wall,
Then become porous sphere.In addition, the sample surfaces roughness of preparation reduces, and dispersibility is gradually with the raising of reaction temperature
Increase.
Compared with prior art, the beneficial effects of the present invention are: when CTAB dosage is 0.04g, reaction temperature is 120 DEG C
When, the ZnS/GO porous microsphere of preparation has better catalytic performance, degradable various dyestuffs than other samples.First in 50 minutes
The degradation rate of base orange is up to 97.6%, and the degradation rate of methylene blue is up to 97.1%.
The ZnS/GO porous microsphere nano material that the present invention synthesizes has excellent photocatalysis performance, can be used as photocatalysis
Agent acts on weaving liquid waste processing, decomposes colored dyes etc..
Detailed description of the invention
The SEM picture of ZnS/GO porous microsphere nano material different proportion made from the respectively embodiment 1 of Fig. 1,2；
Fig. 3 is the SEM picture of ZnS/GO made from comparative example 1；
Fig. 4 is the SEM picture of ZnS/GO made from comparative example 2；
Fig. 5 is the X-ray energy spectrum analysis of ZnS/GO porous microsphere nano material made from embodiment 1；
Fig. 6 is the uv-visible absorption spectroscopy of ZnS/GO porous microsphere nano material made from embodiment 1；
Fig. 7 is the ultraviolet-visible spectrum of ZnS/GO porous microsphere nano material degradation of methylene blue made from embodiment 1；
Fig. 8 is the ultraviolet-visible spectrum of the degradation methyl orange of ZnS/GO porous microsphere nano material made from embodiment 1.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment 1
A kind of preparation method of ZnS/GO porous microsphere nano material, specific steps are as follows:
(1) it prepares the mixed solution containing zinc source and sulphur source: using electronic balance precise 0.659gZn
(CH3COO)2·2H2Deionized water is added in beaker, the amount for adding same substance to being completely dissolved is stirred with glass bar by O
Hypo, acquired solution is uniformly mixed.The cetyl trimethylammonium bromide of 0.04g is added thereto.
Half an hour is stirred to uniform using magnetic stirrer, obtains the mixed solution containing zinc source and sulphur source.
(2) 2g graphite powder and 2g sodium nitrate are dissolved in 40mL sulfuric acid (98wt%).Solution is existed with magnetic stirring apparatus
It is stirred 30 minutes in ice-water bath.Then by the KMnO of 6g4(99.5wt%) is divided into 6 parts, is slowly added in mixed liquor, at 20 DEG C
2h is kept, then stirs 2h at 35 DEG C.Mixed solution is diluted with 160mL deionized water again, is vigorously stirred 0.5h at 90 DEG C.
Hereafter, by the H of 12mL2O2(30wt%) is added slowly in solution and stirs evenly.With 0.5mol/L hydrochloric acid solution and deionization
Water washs mixed solution repeatedly, removes remaining sulfate ion.Then it is freeze-dried, passes through under -60 DEG C of vacuum condition
Grinding obtains GO powder, is scattered in dehydrated alcohol, obtains uniform suspension and be coated on undeposited silicon chip.Finally
Silicon chip is placed in high quartz furnace, temperature is transferred to 650 DEG C in 1 hour.When being cooled back to room temperature, graphite oxide is obtained
Alkene (GO) piece.
(3) it will be mixed containing the solution in zinc source and sulphur source, pour into the polytetrafluoroethylene (PTFE) equipped with graphene oxide (GO) piece and do
It in the autoclave of liner, then carries out closed, is put into the reacting furnace of high temperature and pressure and carries out 120 DEG C of heating reaction, react
Time is 16h, obtains ZnS/GO porous microsphere nano material, as shown in Figure 1, 2.
Fig. 5 is the X-ray energy spectrum analysis (abbreviation EDS spectrum) of ZnS/GO porous microsphere nano material, is not examined in EDS spectrum
Other impurity peaks are measured, show that the ZnS/GO porous microsphere nano material of synthesis has high-purity.
Fig. 6 is the uv-visible absorption spectroscopy of ZnS/GO porous microsphere nano material, can clearly find ZnS/GO
Porous microsphere has very strong absorption band, and absorption maximum is located at 323nm, and surface ZnS/GO porous microsphere is to extraneous and black light
Absorption be significant.
Fig. 7 is the ultraviolet-visible spectrum of ZnS/GO porous microsphere nano material degradation of methylene blue, illustrates that the hole ZnS/GO is micro-
Ball nano material has good photocatalysis performance to methylene blue.
Fig. 8 is the ultraviolet-visible spectrum of ZnS/GO porous microsphere nano material degradation methyl orange, illustrates the hole ZnS/GO microballoon
Nano material has good photocatalysis performance to methyl orange.
Comparative example 1
This comparative example the difference from embodiment 1 is that, reaction temperature in the step (3) is 160 DEG C, remaining condition
It is constant, the SEM picture of resulting ZnS/GO microsphere nano material as shown in figure 3, the hole for the surface that reaction generates disappears,
But there is adhesions between ball and ball.
Comparative example 2
This comparative example the difference from embodiment 1 is that, reaction temperature in the step (3) is 180 DEG C, remaining condition
Constant, the SEM picture of resulting ZnS/GO microsphere nano material is as shown in figure 4, without viscous between the surface that reaction generates
It closes, preferably, spherome surface is smooth for dispersibility.
Claims (6)
1. a kind of preparation method of ZnS/GO porous microsphere nano material, which is characterized in that by the mixing containing zinc source and sulphur source
Solution pours into the polytetrafluoroethylene (PTFE) equipped with graphene oxide sheet and does in the reaction kettle of liner, then carries out closed, is put into reacting furnace
In carry out heating reaction, obtain ZnS/GO porous microsphere nano material；The preparation of the mixed solution containing zinc source and sulphur source
Method are as follows: by Zn (CH3COO)2·2H2O, which is add to deionized water, to be completely dissolved, and is then added and Zn (CH3COO)2·2H2O
The hypo of the amount of same substance is uniformly mixed, then cetyl trimethylammonium bromide is added in mixed liquor
?.
2. the preparation method of ZnS/GO porous microsphere nano material as described in claim 1, which is characterized in that the oxidation
Graphene film the preparation method comprises the following steps: graphite powder, sodium nitrate are dissolved in the concentrated sulfuric acid, with magnetic stirring apparatus by solution in ice-water bath
It stirs evenly, then by KMnO4It is added in mixed liquor several times, 2h is kept at 20 DEG C, 2h is then stirred at 35 DEG C, then
Mixed solution is diluted with deionized water, is vigorously stirred 0.5h at 90 DEG C；By H2O2It is added slowly in solution and stirs evenly；
With hydrochloric acid solution and deionized water cleaning mixture repeatedly, remaining sulfate ion is removed；Vacuum by mixed liquor at -60 DEG C
Under the conditions of be freeze-dried, by grinding obtain GO powder, be scattered in dehydrated alcohol, obtain uniform suspension and be coated in not
On the silicon chip of deposition；Finally silicon chip is placed in quartzy furnace, temperature is transferred to 650 DEG C in 1 hour, then naturally cool to
Room temperature is to get graphene oxide sheet.
3. the preparation method of ZnS/GO porous microsphere nano material as claimed in claim 2, which is characterized in that it is highly preferred that
The weight ratio of the graphite powder and sodium nitrate is 1:1；The mass concentration of the concentrated sulfuric acid is 98wt%；Graphene and KMnO4Weight
Than for 1:2~3；H2O2Mass concentration be 30wt%, graphene and H2O2Ratio be 1g:(6~7.5) mL.
4. the preparation method of ZnS/GO porous microsphere nano material as described in claim 1, which is characterized in that described to contain zinc
Zn (CH in the mixed solution of source and sulphur source3COO)2·2H2O and the mass volume ratio of deionized water are 1g:5mL；Zn
(CH3COO)2·2H2The mass ratio of O and cetyl trimethylammonium bromide is 16:1.
5. the preparation method of ZnS/GO porous microsphere nano material as described in claim 1, which is characterized in that the reacting furnace
Interior temperature is 120 DEG C, reaction time 16h.
6. ZnS/ made from the preparation method of ZnS/GO porous microsphere nano material described in a kind of claim 1-5 any one
Application of the GO porous microsphere nano material as photochemical catalyst in wastewater by photocatalysis.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110304650A (en) * | 2019-06-17 | 2019-10-08 | 哈尔滨理工大学 | A kind of preparation and application of zinc sulfide nano ball array/foamy graphite alkene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983272A (en) * | 2016-10-26 | 2018-05-04 | 中国科学院化学研究所 | Sulfide encapsulated particles and preparation method and application |
| CN108212223A (en) * | 2018-02-05 | 2018-06-29 | 山东佳星环保科技有限公司 | The preparation method of the harmless titanium dioxide graphene catalysis material of novel non-toxic |
| CN109046386A (en) * | 2018-08-24 | 2018-12-21 | 秦天 | Manganese doped zinc sulphide/redox graphene composite material and preparation method and application |
| CN109160494A (en) * | 2018-09-13 | 2019-01-08 | 东华大学 | A kind of preparation method of ball top shape CdSe nano material |
-
2019
- 2019-03-25 CN CN201910226710.9A patent/CN109794263A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983272A (en) * | 2016-10-26 | 2018-05-04 | 中国科学院化学研究所 | Sulfide encapsulated particles and preparation method and application |
| CN108212223A (en) * | 2018-02-05 | 2018-06-29 | 山东佳星环保科技有限公司 | The preparation method of the harmless titanium dioxide graphene catalysis material of novel non-toxic |
| CN109046386A (en) * | 2018-08-24 | 2018-12-21 | 秦天 | Manganese doped zinc sulphide/redox graphene composite material and preparation method and application |
| CN109160494A (en) * | 2018-09-13 | 2019-01-08 | 东华大学 | A kind of preparation method of ball top shape CdSe nano material |
Non-Patent Citations (1)
| Title |
|---|
| LINGWEI LI ET AL.: ""Facile synthesis and characterization of GO/ZnS nanocomposite with highly efficient photocatalytic activity"", 《ELECTRONIC MATERIALS LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110304650A (en) * | 2019-06-17 | 2019-10-08 | 哈尔滨理工大学 | A kind of preparation and application of zinc sulfide nano ball array/foamy graphite alkene |
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