CN109046386A - Manganese doped zinc sulphide/redox graphene composite material and preparation method and application - Google Patents
Manganese doped zinc sulphide/redox graphene composite material and preparation method and application Download PDFInfo
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- CN109046386A CN109046386A CN201810973469.1A CN201810973469A CN109046386A CN 109046386 A CN109046386 A CN 109046386A CN 201810973469 A CN201810973469 A CN 201810973469A CN 109046386 A CN109046386 A CN 109046386A
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- zinc sulphide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 129
- 239000011572 manganese Substances 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 85
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 85
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 84
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 56
- 239000011701 zinc Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 19
- 239000004246 zinc acetate Substances 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 229940071125 manganese acetate Drugs 0.000 claims description 11
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 5
- -1 Graphite alkene Chemical class 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- OKOYFIHZDKMHAM-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;manganese Chemical compound [Mn].OC(=O)CC(O)(C(O)=O)CC(O)=O OKOYFIHZDKMHAM-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 55
- 230000001699 photocatalysis Effects 0.000 abstract description 24
- 238000007146 photocatalysis Methods 0.000 abstract description 19
- 230000006798 recombination Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000654 additive Substances 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 7
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- 206010001497 Agitation Diseases 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
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- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 1
- 206010068150 Acoustic shock Diseases 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- VQWQYXBWRCCZGX-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O.CC(O)=O VQWQYXBWRCCZGX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 238000004043 dyeing Methods 0.000 description 1
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- 238000002003 electron diffraction Methods 0.000 description 1
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- 244000144992 flock Species 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
- 235000014872 manganese citrate Nutrition 0.000 description 1
- 229940097206 manganese citrate Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of manganese doped zinc sulphide/redox graphene composite material and preparation method and applications, the material includes redox graphene and the manganese doped zinc sulphide that is carried on redox graphene, the molar ratio of manganese and zinc is 0.2%~1% in manganese doped zinc sulphide, it counts in mass ratio, redox graphene is manganese doped zinc sulphide/redox graphene composite material 2%~10%.Preparation method includes: that soluble zinc salt, dissolvable sulfide, soluble manganese salt and ethylene glycol are configured to mixed solution；It will be mixed in gained mixed solution with graphene oxide water solution, carry out solvent thermal reaction, obtain manganese doped zinc sulphide/redox graphene composite material.Resulting manganese doped zinc sulphide/redox graphene composite structure is stable, photocatalysis efficiency is high, photocatalysis performance is good, photoproduction-electron hole pair recombination rate is low uniformly, within the scope of visible region for ingredient, can serve as photochemical catalyst of good performance.
Description
Technical field
The present invention relates to the technical field of inorganic nano composite material more particularly to a kind of manganese doped zinc sulphide/oxygen reductions
Graphite alkene composite material and preparation method and application.
Background technique
With the rapid development of social economy, the living standard of people is greatly improved, but also faces simultaneously
Increasingly severeer problem of environmental pollution.Water environment pollution, atmosphere pollution and Farmland Soil Pollution etc. at every moment affect
The health of people.By taking water pollution as an example, a large amount of discharges of various industrial wastewaters, such as weaving, dyeing waste water, organic matter
Content is high, and the inside has a large amount of noxious materials difficult to degrade, and conventional physisorphtion can only be Adsorption one therein
Divide polluter, higher cost.Common chemical method and bioanalysis is also because poor processing effect, reaction process condition are more demanding etc.
Reason and can not large-scale use, therefore, there is an urgent need to search out a kind of preferable method of economical and practical and treatment effect.
Nano semiconductor photocatalysis oxidation technique is because can be carried out the mutual conversion between solar energy and chemical energy, in the sun
The advantages that polluter in water body or air capable of being completely degraded into the substance of environmental sound under light, attracts increasingly
The sight of more researchers.Zinc sulphide is a kind of typical direct wide band gap semiconducter photochemical catalyst of II-VI race, in normal temperature and pressure
Lower property is stablized, cheap, is suitble to large-scale production, while also having good photocatalytic activity, is that one kind preferably has
Machine wastewater treatment material, while also because of its unique fluorescence physical characteristic, in solar battery, ultrathin display, induction detection
The fields such as device also extensive application.
But nano semiconductor material is also in the prevalence of the obstacle for hindering its large-scale application, first is that in the light of visible region
Responding ability is weaker, and in ultraviolet region light-catalyzed reaction can only occur for most of nano semiconductor material, and ultraviolet light only accounts for too
The 8.7% of sunlight, it is seen that light accounts for the 43% of sunlight, is unable to fully utilize solar energy resources.Second is that higher photoproduction-electronics is empty
Cave is to recombination rate, although can generate photo-generated carrier under semiconductor material illumination, higher recombination rate can not make activity
Electronics is transferred to material surface and carries out light-catalyzed reaction, reduces photocatalysis efficiency.
Although the photocatalysis effect of this material is usually in purple at present about the research of ZnS/rGO composite material
It is evaluated under outer light source, can not prove that it also has same photocatalysis performance under visible light source, even if visible
Catalytic action is carried out under light source, it is relatively low to the utilization rate of sunlight；Even if the material still can not incite somebody to action under ultraviolet source
Organic contamination is degradable, and photo-catalysis capability still needs to be promoted.Moreover, the existing preparation process for preparing ZnS/rGO composite material
Complexity, time-consuming, process flow is complicated.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of stable structure, ingredient uniformly,
The additive Mn vulcanization that photocatalysis efficiency is high within the scope of visible region, photocatalysis performance is good, photoproduction-electron hole pair recombination rate is low
Zinc/redox graphene composite material, also provide a kind of step is simple, process flow is short, at low cost manganese doped zinc sulphide/
The preparation method of redox graphene composite material.
In order to solve the above technical problems, the invention adopts the following technical scheme:
Manganese doped zinc sulphide/redox graphene composite material, including manganese doped zinc sulphide and redox graphene,
The manganese doped zinc sulphide is carried on the redox graphene, and the molar ratio of manganese and zinc is in the manganese doped zinc sulphide
0.2%~1%, it counts in mass ratio, the redox graphene is manganese doped zinc sulphide/redox graphene composite material
2%~10%.
The inventive concept total as one, the present invention also provides manganese doped zinc sulphide/redox graphene composite woods
The preparation method of material, includes the following steps:
(1) soluble zinc salt, dissolvable sulfide, soluble manganese salt and ethylene glycol are configured to mixed solution；
(2) graphene oxide water solution is added into mixed solution obtained by step (1), is then stirred to obtain dispersion
The even and sufficient mixed liquor of mixing；
(3) mixed liquor obtained by step (2) is placed in reaction kettle, is sufficiently reacted at 100 DEG C~180 DEG C, wait react knot
It is cooling after beam, then be separated by solid-liquid separation, resulting solid is washed, dried, is ground, manganese doped zinc sulphide/reduction is obtained
Graphene oxide composite material.
In above-mentioned manganese doped zinc sulphide/redox graphene composite material preparation method, it is preferable that described solvable
Property manganese salt be manganese acetate or manganese citrate；The soluble zinc salt is zinc acetate or zinc citrate, and the dissolvable sulfide is
Vulcanized sodium or potassium sulfide.
In above-mentioned manganese doped zinc sulphide/redox graphene composite material preparation method, it is preferable that the preparation
Are as follows: the soluble zinc salt, dissolvable sulfide, soluble manganese salt are dissolved in ethylene glycol respectively, magnetic agitation is carried out and surpasses
Acoustic shock is swung, then soluble Zn salting liquid, dissolvable sulfide solution and the soluble manganese salting liquid sufficiently dissolved may be used
Dissolubility manganese salt solution is added in soluble Zn salting liquid, then is slowly added to dissolvable sulfide solution under stirring conditions,
It is sufficiently mixed under agitation, obtains mixed solution.
In above-mentioned manganese doped zinc sulphide/redox graphene composite material preparation method, it is preferable that the mixing
In solution, the soluble zinc salt, soluble manganese salt, dissolvable sulfide molar concentration rate be 0.002~0.01: 1: 1~
2；The molar concentration of the dissolvable sulfide is 0.01mol/L~0.02mol/L.
In above-mentioned manganese doped zinc sulphide/redox graphene composite material preparation method, it is preferable that the oxidation
The concentration of graphene solution is 1mg/mL~5mg/mL；It counts by volume, the mixed solution and graphene oxide water solution
Volume ratio is 60~90: 3~30.
In above-mentioned manganese doped zinc sulphide/redox graphene composite material preparation method, it is preferable that the mixing
In solution, the soluble zinc salt, soluble manganese salt, dissolvable sulfide molar concentration rate be 0.002~0.01: 1:
1.002~1.1；The molar concentration of the dissolvable sulfide is 0.012mol/L~0.02mol/L；The graphene oxide is molten
The concentration of liquid is 2mg/mL~4mg/mL；The volume ratio of the mixed solution and the graphene oxide is 85: 4.7~25.6.
In above-mentioned manganese doped zinc sulphide/redox graphene composite material preparation method, it is preferable that the step
(3) in, the reaction time is 8h~12h；The reaction temperature is 100 DEG C~180 DEG C, preferably 110 DEG C~150 DEG C.
In above-mentioned manganese doped zinc sulphide/redox graphene composite material preparation method, it is preferable that the step
(2) in, the time of the stirring is 30min~60min；In the step (3), the cleaning is to be washed using water and dehydrated alcohol
It washs 2~3 times；The drying is dry 6h~8h at 50 DEG C~70 DEG C.
As a general technical idea, the present invention also provides above-mentioned manganese doped zinc sulphide/redox graphenes
Composite material or the manganese doped zinc sulphide as made from above-mentioned preparation method/redox graphene composite material are used for photocatalysis
Agent.
Compared with the prior art, the advantages of the present invention are as follows:
1, the photoresponse of the visible region of composite material of the invention is very capable, and photoproduction-electron hole pair recombination rate is low,
Photocatalysis efficiency under visible light is high, photocatalysis performance is very strong.
2, the present invention, using ethylene glycol as reaction dissolvent, passes through solvent heat using zinc acetate, vulcanized sodium and manganese acetate as raw material
Method can a step fabricated in situ go out Mn-ZnS/rGO composite material, preparation method is simple, and process flow is short, and required time is short, reaction
Temperature is lower, less energy consumption.
3, using material manganese element uniform doping prepared by the method for the present invention, manganese doped zinc sulphide is equably carried on also
On former graphene oxide, and the binding ability of manganese doped zinc sulphide and graphene oxide is strong, and it is steady to be formed by composite structure
Fixed, photocatalysis performance is strong.
4, composite material of the invention all has extremely strong photocatalysis in visible region, that is, 420nm or more wave-length coverage
Performance can make full use of solar energy resources, be more energy-saving and environmentally friendly.It is compound i.e. by a small amount of additive Mn and small amounts graphene
The photocatalysis efficiency of material can be made to greatly promote, especially when the molar ratio of manganese in composite material and zinc be 0.22%, graphite oxide
When the mass fraction of alkene is 10%, catalytic performance under visible light is very strong, almost can be by 10mg/L methylene in 50min
Base indigo plant (MB) solution is degradable, and degradation rate reaches 96.35%, and in 125min, degradation rate can reach 100%.
Detailed description of the invention
Fig. 1 is that manganese doped zinc sulphide/redox graphene composite sample X prepared in Examples 1 to 5 is penetrated
Ray diffraction diagram spectrum.
Fig. 2 is the Raman spectrogram of material sample prepared by embodiment 5 and comparative example 1~2.
Fig. 3 is the ultraviolet-visible diffuse reflectance spectrum of material sample prepared by Examples 1 to 5 and comparative example 1~2.
Fig. 4 is the photocatalytic degradation curve graph of material sample prepared by Examples 1 to 5 and comparative example 1~2.
Fig. 5 is the rate of photocatalytic oxidation figure of material sample prepared by Examples 1 to 5 and comparative example 1~2.
Fig. 6 is the rate of photocatalytic oxidation figure of material sample prepared by Examples 1 to 2 and comparative example 1~2.
Fig. 7 is manganese doped zinc sulphide/redox graphene composite sample SEM figure prepared by embodiment 5.
Fig. 8 is manganese doped zinc sulphide/redox graphene composite sample TEM photo prepared by embodiment 5
Fig. 9 is manganese doped zinc sulphide/redox graphene composite sample HRTEM photo prepared by embodiment 5.
Figure 10 is manganese doped zinc sulphide/redox graphene composite sample Selected area electron prepared by embodiment 5
Diffraction pattern.
Figure 11 is manganese doped zinc sulphide/area redox graphene composite sample Qu Dian SEM prepared by embodiment 5
Figure and EDS energy spectrum diagram.
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
The present invention is with Zn (Ac)2·2H2O is zinc source, Na2S·9H2O is sulphur source, Mn (Ac)2·4H2O is manganese source, with second two
Graphene oxide water solution is added as reaction dissolvent in alcohol, has visible light catalytic performance good by solvent-thermal method fabricated in situ
Mn-ZnS/rGO composite photo-catalyst, it is specific the preparation method is as follows:
(1) it takes 0.998mmol zinc acetate and 1mmol vulcanized sodium to be dissolved in the ethylene glycol solution of certain volume respectively, weighs
0.002mmol manganese acetate is dissolved in the ethylene glycol solution of certain volume, by above-mentioned three kinds of solution magnetic agitations 30min~60min
Ultrasonic vibration 30min~60min again afterwards, dissolves zinc acetate, vulcanized sodium, manganese acetate sufficiently in ethylene glycol.
(2) it takes the acetic acid manganese solution of certain volume to be added in zinc acetate solution, keeps the molar ratio in zinc source shared by manganese source
About 0.22% (1: 449) is slowly added to sodium sulfide solution under conditions of with stirring, sufficiently adds certain body after complexing
Product graphene oxide water solution obtains mixed liquor, the mass fraction for choosing composite material shared by graphene oxide is respectively 2%,
4%, 6%, 8%, 10%.In the present invention, by the way that zinc acetate, vulcanized sodium and manganese acetate are dissolved in ethylene glycol solution respectively,
Each solution is subjected to mixed dissolution again, is conducive to the uniformity for improving solution, is conducive to the uniformity for improving subsequent reactions.This step
In rapid, it has been investigated that, if graphene oxide is directly dissolved in ethylene glycol solution, graphene can be lost oxygen-containing during being reduced
Functional group makes its dispersibility in ethylene glycol be deteriorated, to agglomeration occur, and uses graphene oxide water solution then
It can dexterously solve the problems, such as this, can be conducive to improve the dispersibility of graphene oxide during the reaction, improve final multiple
The uniformity of condensation material, and then improve photocatalysis performance.
(3) mixed liquor obtained by step (2) is transferred in 200ml reaction kettle, is reacted under conditions of 100 DEG C~180 DEG C
8h~12h, cooled to room temperature, is washed 3 times with dehydrated alcohol and deionized water, respectively in 60 DEG C of baking oven after reaction
Interior dry 6h.
In the present invention, the doping of a small amount of Mn ion introduces impurity energy level, increases donor level between valence band and conduction band and leads
Band-gap energy is caused to reduce, so that absorbing band edge occurs red shift, the doping of excessive Mn ion can change original lattice types, form structure
Defect constitutes photo-generate electron-hole to complex centre, absorbs band edge and blue shift occurs, the doping of Mn is 0.2%~1%, is had
Good doping effect, when mole doping of Mn is 0.22%, effect is best.
Embodiment 1
A kind of manganese doped zinc sulphide of the invention/redox graphene composite material, including manganese doped zinc sulphide and also
Former graphene oxide, manganese doped zinc sulphide are carried on redox graphene, the molar ratio of manganese and zinc in manganese doped zinc sulphide
It is 0.22%, counts in mass ratio, the additive amount of graphene oxide is manganese doped zinc sulphide/redox graphene composite material
2%.The raw material of composite material includes manganese acetate, zinc acetate, ethylene glycol and graphene oxide, the molar ratio of Mn and Zn in raw material
It is 1: 449, the molar ratio of zinc acetate and manganese acetate is 449: 500, is counted in mass ratio, and the additive amount of graphene oxide is composite wood
The 2% of material.
A kind of preparation method of the manganese doped zinc sulphide of above-mentioned the present embodiment/redox graphene composite material, including
Following steps:
(1) zinc acetate (Zn (Ac) of precise 219.04mg2·2H2) and the vulcanized sodium (Na of 240mg O2S·9H2O)
It is added separately in the conical flask for filling 40ml ethylene glycol solution, the manganese acetate (Mn (Ac) of precise 4.9mg2·4H2O) add
Enter into the conical flask for filling 50ml ethylene glycol solution and be named as A, above-mentioned three is distinguished into magnetic agitation 60min and ultrasound is shaken
Swinging 30min dissolves it sufficiently.It takes 5ml solution A to be added in zinc acetate solution, is slowly added to sulphur under conditions of with stirring
Change sodium solution, allows three that 60min is sufficiently complexed, obtain mixed solution.
(2) it measures the graphene oxide water solution that 4.7ml concentration is 2mg/ml and is added to mixed solution obtained by step (1)
In, stirring 60min, which is continuesd to mix, so that solution is fully dispersed and is complexed completely obtains mixed liquor.
(3) mixed liquor obtained by step (2) is transferred in the reaction kettle that capacity is 200ml, it is abundant when temperature is 140 DEG C
React 8h.After reaction, cooled to room temperature outwells the clear ethylene glycol solution in top, and product is poured into 50ml centrifugation
Washing fullys shake in effective deionized water, is centrifuged 1 minute under conditions of 3500rpm, outwells supernatant, obtains lower section and precipitates sample
Product add dehydrated alcohol and washing fully shake, so that sediment becomes suspension, continue centrifugation 1 under conditions of 3500rpm
Minute, it repeats the above process twice, the centrifugation time of last time is set as 5 minutes, and obtained product is placed in surface plate
In, and final product is 6 hours dry in the drying box that set temperature is 60 DEG C, it is ground after sample is completely dried using agate
Alms bowl is fully ground into powdered substance, is put into 5ml constant volume tube and is sealed.
Embodiment 2
A kind of manganese doped zinc sulphide of the invention/redox graphene composite material vulcanizes with the additive Mn of embodiment 1
Zinc/redox graphene composite material is substantially identical, and difference is, counts in mass ratio, and the additional amount of graphene oxide is multiple
The 4% of condensation material.
A kind of preparation method of the manganese doped zinc sulphide of above-mentioned the present embodiment/redox graphene composite material, with reality
The preparation method applied in example 1 is essentially identical, and difference is only that: the volume of the graphene oxide water solution measured in step (2) is
9.6ml。
Embodiment 3
A kind of manganese doped zinc sulphide of the invention/redox graphene composite material vulcanizes with the additive Mn of embodiment 1
Zinc/redox graphene composite material is substantially identical, and difference is, counts in mass ratio, and the additional amount of graphene oxide is multiple
The 6% of condensation material.
A kind of preparation method of the manganese doped zinc sulphide of above-mentioned the present embodiment/redox graphene composite material, with reality
The preparation method applied in example 1 is essentially identical, and difference is only that: the volume of the graphene oxide water solution measured in step (2) is
14.7ml。。
Embodiment 4
A kind of manganese doped zinc sulphide of the invention/redox graphene composite material vulcanizes with the additive Mn of embodiment 1
Zinc/redox graphene composite material is substantially identical, and difference is, counts in mass ratio, and the additional amount of graphene oxide is multiple
The 8% of condensation material.
A kind of preparation method of the manganese doped zinc sulphide of above-mentioned the present embodiment/redox graphene composite material, with reality
The preparation method applied in example 1 is essentially identical, and difference is only that: the volume of the graphene oxide water solution measured in step (2) is
20ml。
Embodiment 5
A kind of manganese doped zinc sulphide of the invention/redox graphene composite material vulcanizes with the additive Mn of embodiment 1
Zinc/redox graphene composite material is substantially identical, and difference is, counts in mass ratio, and the additional amount of graphene oxide is multiple
The 10% of condensation material.
A kind of preparation method of the manganese doped zinc sulphide of above-mentioned the present embodiment/redox graphene composite material, with reality
The preparation method applied in example 1 is essentially identical, and difference is only that: the volume of the graphene oxide water solution measured in step (2) is
25.6ml。
XRD spectrum such as Fig. 1 in manganese doped zinc sulphide/redox graphene composite sample in Examples 1 to 5
It is shown, occur apparent ZnS characteristic peak in each map, but miscellaneous phase do not occur, shows that Mn is adulterated successfully.
Crystallite dimension is calculated using using Scherer (Scherrer) formula D=K λ/(β * Cos θ), wherein D is that crystal grain is big
It is small, unit nm；K value is 0.89；λ is the incident wavelength of X-ray diffractometer.CuKa light source is used during Experimental Characterization,
Therefore λ=0.154056；The half-peak breadth of diffraction maximum when β value causes corresponding X-ray diffraction lines to broaden for grain size difference
(FWHM)；θ is the corresponding scanning angle of (111) crystal face；By calculating, crystallite dimension such as the following table 1 institute of each sample is finally obtained
Show:
Table 1
| Sample | ZnS | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| β | 3.45 | 3.48 | 3.19 | 3.12 | 3 | 2.98 |
| Cosθ | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 |
| D(nm) | 2.6 | 2.58 | 2.81 | 2.88 | 2.99 | 3.01 |
As can be seen from Table 1, ZnS is compared, the crystallite dimension of the composite material of embodiment 1 slightly reduces, but with oxidation
Graphene adds increased increase, and the partial size of composite material increases instead, this is because Mn ionic radius is slightly less than Zn ion half
Diameter causes the particle size of Mn-ZnS composite material slightly to reduce after adulterating Mn, but difference is little, this further demonstrates that Mn mixes
Material lattice is entered；With the increase of graphene oxide content in composite material, since single-layer graphene oxide is in reaction process
In when being reduced into graphene oxide layer structure be destroyed and fall off accumulation, while Mn-ZnS was restored in graphene oxide
It is grown in journey using it as substrate, particle size is caused to increased.
The zinc sulphide in manganese doped zinc sulphide/redox graphene composite sample, comparative example 1 in embodiment 5
Material is with the Raman spectrum of the Mn doped zinc sulphide material in comparative example 2 as shown in Fig. 2, it can be seen from the figure that comparing bright sulfur
Change Zinc material and manganese doped zinc sulphide material, the manganese doped zinc sulphide/redox graphene composite material for adding 10%GO goes out
The apparent peak D and the peak G are showed, D peak intensity is greater than G peak intensity, and graphene oxide is in 1350cm-1With 1590cm-1Nearby respectively
It will appear the peak D and the peak G, wherein D peak intensity is less than G peak intensity, and this phenomenon in Fig. 2 occur is due to adding graphene oxide
Later, redox graphene is reduced by ethylene glycol solution during the reaction, a large amount of oxygen-containing officials originally in graphene oxide
While energy group is reduced, manganese ion, zinc ion and sulphion carry out growth formation using grapheme material as substrate, on its surface
Mn-ZnS, while sp3Carbon atom in hybrid structure can be transformed into sp2Hybrid structure causes the fault of construction in composite material to increase
Add, and sp2State can introduce a large amount of unsaturated pi bonds, form the shallow gesture capture trap of electron-hole pair, be conducive to improve electronics-sky
The separative efficiency in cave pair.The sp regenerated2Hybrid structure region reduces, to increase the peak intensity ratio of D/G, this also into
One step illustrates that Mn-ZnS has successfully been loaded on grapheme material.
Comparative example 1
The material of this comparative example is zinc sulphide materials.The raw material for preparing of zinc sulphide materials includes zinc acetate, vulcanized sodium and second
The molar ratio of glycol, zinc acetate and vulcanized sodium is 1: 1.
In this comparative example, the preparation method of zinc sulphide materials includes:
(1) zinc acetate (Zn (Ac) of precise 219.48mg2·2H2) and the vulcanized sodium (Na of 240mg O2S·9H2O)
It is added separately in the conical flask for filling 40ml ethylene glycol solution, by said two devices difference magnetic agitation 60min and ultrasonic vibration
30min dissolves it sufficiently.Slowly sodium sulfide solution is added in zinc acetate solution under conditions of with stirring, the two is allowed to fill
Divide complexing 60min, obtains mixed solution.
(2) mixed solution obtained by step (1) is transferred in the reaction kettle that capacity is 200ml, is filled when temperature is 140 DEG C
Divide reaction 8h.After reaction, cooled to room temperature outwells the clear ethylene glycol solution in top, by product pour into 50ml from
Washing fullys shake in the effective deionized water of the heart, is centrifuged 1 minute under conditions of 3500rpm, outwells supernatant, obtains lower section precipitating
Sample adds dehydrated alcohol and washing fullys shake so that sediment becomes suspension, continue under conditions of 3500rpm from
It the heart 1 minute, repeats the above process twice, the centrifugation time of last time is set as 5 minutes, and obtained product is placed in surface
In ware, and final product is 6 hours dry in the drying box that set temperature is 60 DEG C, agate is used after sample is completely dried
Mortar is fully ground into powdered substance, is put into 5ml constant volume tube and is sealed.
Comparative example 2
Material in this comparative example is manganese doped zinc sulphide material, and wherein the molar ratio of manganese and zinc is 0.22%.Additive Mn
The raw material for preparing of zinc sulphide materials includes manganese acetate, zinc acetate, vulcanized sodium and ethylene glycol, and in the raw material, Mn and Zn's rubs
, than being 1: 449, the molar ratio of zinc acetate and vulcanized sodium is 449: 500 for you.
In this comparative example, the preparation method of manganese doped zinc sulphide material includes:
(1) zinc acetate (Zn (Ac) of precise 219.04mg2·2H2) and the vulcanized sodium (Na of 240mg O2S·9H2O)
It is added separately in the conical flask for filling 40ml ethylene glycol solution, the manganese acetate (Mn (Ac) of precise 4.9mg2·4H2O) add
Enter into the conical flask for filling 50ml ethylene glycol solution and be named as A, above-mentioned three is distinguished into magnetic agitation 60min and ultrasound is shaken
Swinging 30min dissolves it sufficiently.It takes 5ml solution A to be added in zinc acetate solution, is slowly added to sulphur under conditions of with stirring
Change sodium solution, allows three that 60min is sufficiently complexed, obtain mixed solution.
(2) mixed solution obtained by step (1) is transferred in the reaction kettle that capacity is 200ml, is filled when temperature is 140 DEG C
Divide reaction 8h.After reaction, cooled to room temperature outwells the clear ethylene glycol solution in top, by product pour into 50ml from
Washing fullys shake in the effective deionized water of the heart, is centrifuged 1 minute under conditions of 3500rpm, outwells supernatant, obtains lower section precipitating
Sample adds dehydrated alcohol and washing fullys shake so that sediment becomes suspension, continue under conditions of 3500rpm from
It the heart 1 minute, repeats the above process twice, the centrifugation time of last time is set as 5 minutes, and obtained product is placed in surface
In ware, and final product is 6 hours dry in the drying box that set temperature is 60 DEG C, agate is used after sample is completely dried
Mortar is fully ground into powdered substance, is put into 5ml constant volume tube and is sealed.
Embodiment 6
The photo absorption performance for investigating manganese doped zinc sulphide/redox graphene composite material of the present invention, includes the following steps:
The material in manganese doped zinc sulphide/redox graphene composite material and comparative example 1~2 in Example 1~5
Material, concentration of degrading under visible light as photochemical catalyst are the methylene blue solution (MB) of 10mg/L, take a sample every 25min
Its absorbance value is measured in maximum absorption wave strong point.
The material in manganese doped zinc sulphide/redox graphene composite material and comparative example 1~2 in Examples 1 to 5
Ultraviolet-visible diffuse reflectance spectrum as shown in figure 3, it may be seen that the visible light absorption capacity of Mn doped zinc sulphide material is greater than
The absorbability of zinc sulphide materials, it can also be seen that with the increase of graphene oxide additive amount, the visible light of composite photo-catalyst
Absorbability constantly enhances.Near 420nm, it is added to the visible absorption intensity of 8%GO and 10%GO composite material just
Plan and control is better than it in the absorption maximum intensity of ultraviolet region, and with wave-length coverage red shift, the two visible absorption intensity is still protected
Hold slow increase.
According to the data in Fig. 3, using photon energy hv as horizontal axis, (Ahv)1/2Curve graph is made for the longitudinal axis, is then inhaled in light
It receives side and finds point of contact, cross the point of contact fitting a straight line, the intercept with X-axis is the forbidden bandwidth of the direct band-gap semicondictor.Its
Middle hv=1240/ λ, λ are corresponding wavelength, and the forbidden bandwidth size for finally obtaining each group sample is as shown in table 2:
Table 2
Table 2 is the forbidden bandwidth of the sample of different GO adding proportions, it can be seen that, the doping of Mn reduces band gap from table
Can, when graphene oxide incorporation is less, band-gap energy increases instead, this is because when graphene oxide incorporation is less, manganese
Certain journey inevitably is caused to graphene oxide conjugated system when the structure composite of doped zinc sulphide and graphene oxide
The destruction of degree；With the increase of graphene oxide adding proportion, the band-gap energy value of sample is being gradually decreased, this can reduce electronics
Energy needed for being illuminated by the light excitation transition, promotes the generation of photo-generate electron-hole pair, improves the photocatalytic of composite material
Energy.
In embodiment 6, using the manganese doped zinc sulphide in Examples 1 to 5/redox graphene composite sample and
The photocatalytic degradation curve of material sample in comparative example 1~2 is as shown in figure 4, by-In (A/A0) with time t (min) do scatterplot
Scheme simultaneously fitting a straight line, the rate of photocatalytic oxidation curve of available each section material, corresponding degradation rate figure such as Fig. 5 institute
Show, since comparative example 1~2 in Fig. 5 and the difference of Examples 1 to 2 data are unobvious, it is independent right that this partial data has been carried out
Than as shown in Figure 6.It can be seen that Mn doped zinc sulphide material compared to zinc sulphide materials from Fig. 4, Fig. 5 and Fig. 6
Most degradation rate value when 125min is higher, the former degradation rate is 51.94%, and the latter is 48.87%, and the disposal efficiency mentions
6.3% is risen, this illustrates that Mn ion doping can change its crystallinity or defective locations in zinc sulfide semiconductor lattice, is formed
Shallow gesture capture trap extends the service life of carrier, although ion doping can promote photocatalysis performance, promoting effect is not
It is especially high, this is because it is the compound point quickening electricity for becoming photo-generated carrier that the relative effect of ion doping, which depends on it on earth,
Son-hole pair is compound, or as the medium of charge transfer, extends the recombination time of electron-hole pair.From Fig. 5 and
Fig. 6 can significantly find out, with the increase of the additive amount of graphene oxide, the photocatalysis performance of composite material is improved, oxidation
When the additive amount of graphene is 10%, the photocatalysis performance of composite material is best.However 2%GO composite property < is not added
GO composite material, this is because graphene oxide and manganese doped zinc sulphide compound tense are inevitably conjugated graphene oxide
System causes a degree of destruction, reduces the electric conductivity of grapheme material, when the additive amount of graphene oxide is less, also
Interaction force between former graphene oxide and manganese doped zinc sulphide is weaker, cannot play synergistic effect, be unable to fully benefit
With the good characteristic of grapheme material.
To slope, that is, photocatalytic degradation speed of each straight line of the composite material for using different graphene oxides compound in Fig. 5
Rate size, specific value see the table below 3, it was obvious that, the additive amount of graphene oxide is 2% obtained composite material
The degradation rate value of sample is minimum, is 0.0033molL-1·min-1；The drop for the sample that graphene oxide additive amount is 10%
It is maximum to solve rate value, is 0.05844molL-1·min-1, it is 17.7 times of 2%rGO sample degradation rate, in a certain range
Interior, the degradation rate of each group sample increases with the increase of graphene oxide additive amount.Composite material in embodiment five exists
Almost can be degradable by 10mg/L methylene blue (MB) solution in 50min, degradation rate reaches 96.35%, in 125min
When, degradation rate can reach 100%.
Table 3
The SEM figure of 5 gained sample of embodiment is as shown in Figure 7, it can be seen that redox graphene is in particle exterior surface shape
At fold (SEM figure), TEM photo, HRTEM photo and selective electron diffraction figure difference it is as shown in Figure 8,9, 10.
Fig. 8 can be seen that composite material is nano material, and black redox graphene material adulterates ZnS nanoparticle with Mn
Son mutually flocks together, this is because GO Mn during being reduced adulterates ZnS nanoparticle and grown as substrate
It is formed, and then loaded in graphene sheet layer, so that Mn doping ZnS nanoparticle is tightly combined with redox graphene,
Binding force between the two is strong, stable structure.It can see this layer structure in figure, with the increasing of graphene adding proportion
Greatly, the nano particle form of composite material is not substantially change.Fig. 9 is the HRTEM photo of composite material, the lattice item of the inside
Line corresponds to the different crystal faces of Mn doping ZnS, a thin layer of fibrous material i.e. oxygen reduction that lattice fringe is surrounded by
Graphite alkene, this illustrates that Mn doping ZnS nanoparticle has successfully loaded in graphene-structured, and the SAED photo in Figure 10 can
To clearly see 3 diffraction rings, brightness is successively successively decreased from the inside to the outside, is spread out respectively with (111) of ZnS, (220), (311) crystal face
It is corresponding to penetrate ring, belongs to a cube ZnS crystalline structure, illustrates that the main matter of composite material is still nanometer ZnS.
EDS energy spectrum analysis is carried out to element species contained by 5 composite material of embodiment and content, take the SEM in region scheme and
EDS energy spectrum diagram is as shown in figure 11.Table 4 is the first sample point each element mass fraction and relative atom content in Figure 11, in conjunction with
It is found that comparing with manganese doped zinc sulphide material, C element mass fraction obviously increases data in the following table 4, has reached 16.67%, O
Constituent content also increased, and reach 5.22%, this is because introduce graphene oxide, Zn element and S element
Relative atom content is 24.84% and 22.99% respectively, and molar ratio is remained unchanged close to 1: 1, but Zn is opposite with S element
Atom content reduces 44% with 43% respectively, and the content of C element increases nearly 500%, this is because the mistake that GO is reduced
Become the substrate of building composite material in journey, manganese doped zinc sulphide carries out growth synthesis on it, so for same
The ratio of the material of quality, C element and O element increases the reduction for meaning Zn element Yu S element ratio.
Table 4
| Element | C K (K electron) | O K | S K | Mn K | Zn K |
| Wt% | 16.67 | 5.22 | 24.3 | 0.3 | 53.51 |
| At% | 42.11 | 9.9 | 22.99 | 0.16 | 24.84 |
In addition, 1KeV nearby can clearly be seen the presence of Mn element, mass fraction 0.3%, at another in Figure 11
Taking its mass fraction of a region is 0.26%, although Mn constituent content is lower, the content of two sample points is suitable, illustrates this yuan
Element is uniformly dispersed in the composite, the feature occurred in addition to 0.8KeV nearby absorbs oxygen in air and carbon dioxide
Outside peak, has no other impurity peaks and exist, resulting materials purity is high.It is analyzed by the molar ratio to above-mentioned element, it can be with
The object phase main body for determining prepared sample is still zinc sulphide materials, and is successfully combined with each other with graphene.
Although the present invention is disclosed as above with preferred embodiment, however, it is not intended to limit the invention.It is any to be familiar with ability
The technical staff in domain, without deviating from the scope of the technical scheme of the present invention, all using the technology contents pair of the disclosure above
Technical solution of the present invention makes many possible changes and modifications or equivalent example modified to equivalent change.Therefore, all
Without departing from the content of technical solution of the present invention, according to the present invention technical spirit any simple modification made to the above embodiment,
Equivalent variations and modification, all shall fall within the protection scope of the technical scheme of the invention.
Claims (10)
1. manganese doped zinc sulphide/redox graphene composite material, which is characterized in that including manganese doped zinc sulphide and oxygen reduction
Graphite alkene, the manganese doped zinc sulphide are carried on the redox graphene, manganese and zinc in the manganese doped zinc sulphide
Molar ratio be 0.2%~1%, count in mass ratio, the redox graphene be manganese doped zinc sulphide/reduction-oxidation graphite
The 2%~10% of alkene composite material.
2. manganese doped zinc sulphide/redox graphene composite material preparation method, which comprises the steps of:
(1) soluble zinc salt, dissolvable sulfide, soluble manganese salt and ethylene glycol are configured to mixed solution；
(2) graphene oxide water solution is added into mixed solution obtained by step (1), be then stirred be uniformly dispersed and
Mix sufficient mixed liquor；
(3) mixed liquor obtained by step (2) is placed in reaction kettle, is sufficiently reacted at 100 DEG C~180 DEG C, to after reaction
It is cooling, then be separated by solid-liquid separation, resulting solid is washed, dried, is ground, manganese doped zinc sulphide/reduction-oxidation is obtained
Graphene composite material.
3. preparation method according to claim 2, which is characterized in that the solubility manganese salt is manganese acetate or citric acid
Manganese；The soluble zinc salt is zinc acetate or zinc citrate, and the dissolvable sulfide is vulcanized sodium or potassium sulfide.
4. preparation method according to claim 2, which is characterized in that the preparation are as follows: by the soluble zinc salt, solvable
Property sulfide and soluble manganese salt be dissolved in ethylene glycol respectively, carry out magnetic agitation and ultrasonic vibration, what is sufficiently dissolved can
Then soluble manganese salting liquid is added to solvable by soluble zinc salt solution, dissolvable sulfide solution and soluble manganese salting liquid
Property zinc solution in, then be slowly added to dissolvable sulfide solution under stirring conditions, under agitation sufficiently complexing, obtain
To mixed solution.
5. according to preparation method described in claim 2~4 any one, which is characterized in that in the mixed solution, it is described can
Soluble zinc salt, soluble manganese salt, dissolvable sulfide molar concentration rate be 0.002~0.01: 1: 1~2；The solubility sulphur
The molar concentration of compound is 0.01mol/L~0.02mol/L.
6. according to preparation method described in claim 2~4 any one, which is characterized in that the graphene oxide solution
Concentration is 1mg/mL~5mg/mL；It counts by volume, the volume ratio of the mixed solution and graphene oxide water solution is 60~
90:3~30.
7. according to preparation method described in claim 2~4 any one, which is characterized in that in the mixed solution, it is described can
Soluble zinc salt, soluble manganese salt, dissolvable sulfide molar concentration rate be 0.002~0.01: 1: 1.002~1.1；It is described can
The molar concentration of dissolubility sulfide is 0.012mol/L~0.02mol/L；The concentration of the graphene oxide solution is 2mg/mL
~4mg/mL；The volume ratio of the mixed solution and the graphene oxide is 85: 4.7~25.6.
8. according to preparation method described in claim 2~4 any one, which is characterized in that described anti-in the step (3)
It is 8h~12h between seasonable；The reaction temperature is 100 DEG C~180 DEG C.
9. according to preparation method described in claim 2~4 any one, which is characterized in that described to stir in the step (2)
The time mixed is 30min~60min；In the step (3), the cleaning is using water and dehydrated alcohol washing 2~3 times；Institute
It states dry for 6h~8h dry at 50 DEG C~70 DEG C.
10. manganese doped zinc sulphide as described in claim 1/redox graphene composite material or such as claim 2~9 times
Manganese doped zinc sulphide/redox graphene composite material made from preparation method described in meaning one is used for photochemical catalyst.
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| CN109794263A (en) * | 2019-03-25 | 2019-05-24 | 东华大学 | The preparation method and application of ZnS/GO porous microsphere nano material |
| CN112142096A (en) * | 2020-08-11 | 2020-12-29 | 中国科学院福建物质结构研究所 | Zinc sulfide composite electrode material prepared by zinc-containing ionic liquid |
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