CN106622294A - Preparation method of graphene-based composite Sb2S3 photocatalyst - Google Patents
Preparation method of graphene-based composite Sb2S3 photocatalyst Download PDFInfo
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- CN106622294A CN106622294A CN201611269903.5A CN201611269903A CN106622294A CN 106622294 A CN106622294 A CN 106622294A CN 201611269903 A CN201611269903 A CN 201611269903A CN 106622294 A CN106622294 A CN 106622294A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052959 stibnite Inorganic materials 0.000 title abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011975 tartaric acid Substances 0.000 claims abstract description 18
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 12
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 32
- 229910052787 antimony Inorganic materials 0.000 claims description 29
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 29
- 238000005987 sulfurization reaction Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 18
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Natural products SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 239000004201 L-cysteine Substances 0.000 claims description 8
- 235000013878 L-cysteine Nutrition 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 3
- 125000000415 L-cysteinyl group Chemical group O=C([*])[C@@](N([H])[H])([H])C([H])([H])S[H] 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 229940007424 antimony trisulfide Drugs 0.000 description 28
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 15
- 238000007146 photocatalysis Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- -1 hydroxy diol Chemical group 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a preparation method of a graphene-based composite Sb2S3 photocatalyst. The method comprises the steps as follows: firstly, graphene oxide is added to ethylene glycol and subjected to ultrasonic stripping, SbCl3 is then added and stirred to be dissolved, tartaric acid is added and stirred continuously until the tartaric acid is completely dissolved, a sulfur source is added, magnetic stirring is performed to fully mix the substances, and stirring reflux is performed at 120-180 DEG C for 12-18 hours. A product is naturally cooled to the room temperature after completion of the reaction and is separated, washed and dried, and the graphene-based composite Sb2S3 photocatalyst is obtained. The photocatalyst has good composite effect and high photocatalytic activity of visible light, and the preparation method has the advantages of simple production process, safe production process and low implementation cost, facilitates large-scale industrial production, and can be widely used in preparation of graphene-based composites.
Description
Technical field
The present invention relates to a kind of preparation of composite, more particularly to a kind of preparation of composite visible light catalysis material,
Relate in particular to a kind of method that employing circumfluence method prepares Graphene composite sulfuration antimony photocatalyst.
Background technology
Antimony trisulfide (Sb2S3) it is a kind of typical binary sulfide, it is a kind of common(V represents the 5th master
Race, VI represents the 6th main group, and A is As, Sb, Bi；B is S, Se, Te) semi-conducting material of type layer structure, its crystal structure category
In rhombic system, the anisotropy with height.Each antimony atoms or each sulphur atom are fixed on three opposite types atom groups
Into banding paradigmatic structure in, the SbS of this structure connection composition chain lock shape square conical3Or SSb3Construction unit, it is this special
Crystal structure unit cause antimony trisulfide easily to grow into one-dimensional, the two-dimentional micro nano structure of different-shape.Antimony trisulfide has very
High heliosensitivity and excellent thermoelectricity capability, are a kind of less direct band-gap semicondictor materials of band gap, its band gap
For 1.5～2.2eV, visible ray and the near infrared region of sunlight power spectrum are covered.Antimony trisulfide also has strong light absorpting ability,
Visible ray inhales the absorptance of scope and is up to 105cm-1.These unique performances make antimony trisulfide be largely used to solaode,
Visible-light photocatalyst, thermo-electric cooling device, lithium ion battery, photoelectronic device etc..But, antimony trisulfide is urged as visible ray light
During agent, as many other photocatalysts, photo-generate electron-hole is there is to easily compound defect, cause quantum
Efficiency is low, photocatalysis efficiency is low.Therefore, suppression antimony trisulfide the compound of photo-generate electron-hole pair during light-catalyzed reaction is
Improve the effective way of its photocatalysis efficiency.
Graphene is with sp by carbon atom2What the monoatomic layer of hydridization connection was constituted, be the most thin two dimension having now been found that
Material.This special structure makes Graphene all many-sided with many special excellent in electricity, optics, calorifics and mechanics etc.
Property, particularly its there is excellent electric conductivity and electron transmission ability.Graphene is a kind of zero clearance semi-metallic, its
The big π keys for existing enable pi-electron to move freely, and valence band and conduction band can produce the overlap of fraction, and between its atom
Active force is strong, drag minimization of the electronics in transmitting procedure and be not susceptible to scattering, thus its conductive capability is strong, electron mobility
200000cm can be up to2·V-1·s-1, electrical conductivity is up to 106S/m.In addition, Graphene also possesses huge specific surface area, its
Theoretical specific surface area is up to 2600m2/g.Therefore, if the semi-conducting materials such as Graphene and antimony trisulfide are combined, stone can not only be utilized
The advantage that black alkene conductive capability is strong, electron mobility is high, the electronics for exciting is moved to rapidly in graphene film Rotating fields and not
It is the surface for resting on catalyst, reduces the probability of electronics and hole-recombination, and the huge ratio that can possess using Graphene
Surface area, improves its photocatalysis efficiency.
Currently, both at home and abroad relevant circumfluence method prepares the research of Graphene composite sulfuration antimony photocatalyst seldom, its known document
Also rarely seen one (Chinese patent:The A of CN 105289657), the method for the patent report is using graphene oxide, SbCl3, sulfur
Powder is raw material, and sodium borohydride is reducing agent, and adjacent hydroxy diol is solvent, prepares graphene-sulfur antimony nanometer rods with circumfluence method and answers
Closing light catalyst.But the method is during composite photo-catalyst is prepared, the sodium borohydride of addition can be with sulphur powder fast reaction
And generate H2S, so that one side H2S can be to environment, another aspect H2S can rapidly and SbCl3React and be unfavorable for sulfur
Change the oriented growth of antimony rod, the pattern of rod is poor, and its fast reaction also results in Graphene and is deteriorated with the composite effect of antimony trisulfide.Separately
Outward, the improper impurity that can also in the product introduce S of process regulation.Therefore, there is poor product quality, the size of rod in the method
Skewness, environmental pollution is serious, preparation condition is harsh and is difficult to the defect for controlling, production cost is high.The present invention adopts oxygen
Graphite alkene (GO), SbCl3, sulphur source be raw material, tartaric acid is compounding ingredient, and ethylene glycol is solvent, and with circumfluence method graphite is prepared for
Alkene composite sulfuration antimony photocatalyst.During the course of the reaction, SbCl3First with winestone acid reaction, Sb (III)-tartaric acid coordination compound is generated
(coordination compound is dissolved in ethylene glycol), then the coordination compound again with sulphur source react, generate antimony trisulfide micron bar.Due to Sb (III)-winestone
Sour coordination compound controls Sb as forerunner's physical ability3+Rate of release, so as to control Sb2S3The growth rate of crystal, makes Sb2S3Can be very
Well oriented growth is into antimony trisulfide micron bar.Meanwhile, graphene oxide becomes Graphene and (or is oxygen reduction fossil by sulphur source reduction
Black alkene, RGO), and compound with the antimony trisulfide micron bar for generating become composite photo-catalyst.By to the visible of composite photo-catalyst
Light photocatalysis performance is investigated, and is as a result shown, the visible light photocatalysis active of product is high, and it can make full use of sunlight to ring
Border pollutant carry out photocatalytic degradation.The synthetic method has no both at home and abroad document report, with novelty and creativeness.
The content of the invention
It is an object of the invention to provide a kind of simple production process, production process safety, low production cost, material are multiple
Close the preparation method of the Graphene composite sulfuration antimony photocatalyst that effect is good, visible light photocatalysis active is high.
The purpose of the present invention is realized in the following way：
A kind of preparation method of Graphene composite sulfuration antimony photocatalyst, comprises the steps：
A () is added graphene oxide in ethylene glycol, ultrasound is peeled off 1～3 hour, is configured to the oxygen of 0.5～2mg/mL
Graphite alkene-ethylene glycol dispersion liquid；
B () adds SbCl in graphene oxide-ethylene glycol dispersion liquid3, SbCl3Consumption be in every milliliter of dispersion liquid plus
Enter 0.02～0.03mmol SbCl3, after stirring and dissolving, tartaric acid being added, the amount for adding tartaric material is SbCl3Material
2～4 times of amount, continue stirring and are completely dissolved to tartaric acid, obtain mixed liquor；
C () adds sulphur source in mixed liquor, the amount of the material of the sulphur source is SbCl32～3 times of the amount of material, magnetic force
Stirring 20～60 minutes so as to be sufficiently mixed, be then stirred at reflux 12～18 hours at 120～180 DEG C；
(d) reaction terminate after naturally cool to room temperature, centrifugation obtains black precipitate, black precipitate is spent respectively from
Sub- water and dehydrated alcohol replace supersound washing, and Graphene composite sulfuration antimony photocatalyst is obtained after being dried.
Described sulphur source is L-Cysteine or thiourea.
The present invention has the advantages that：
(1) present invention prepares Graphene composite sulfuration antimony photocatalyst by circumfluence method, with simple production process, production
Process safety, response parameter are easily controlled, low production cost and be easily achieved the advantage of large-scale industrial production.
(2) composite photo-catalyst prepared by the present invention, on the one hand its specific surface area is big, strong to the absorbability of visible ray,
On the other hand its electron mobility is high, photo-generate electron-hole to can be easily separated, therefore, its visible light photocatalysis active is high, its energy
Sunlight is made full use of to carry out photocatalytic degradation, efficiency high, low cost to environmental pollutants.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of Graphene composite sulfuration antimony photocatalyst prepared by embodiment 1.
Fig. 2 is scanning electron microscope (SEM) figure of Graphene composite sulfuration antimony photocatalyst prepared by embodiment 1.
Fig. 3 is scanning electron microscope (SEM) figure of Graphene composite sulfuration antimony photocatalyst prepared by embodiment 2.
Fig. 4 is scanning electron microscope (SEM) figure of Graphene composite sulfuration antimony photocatalyst prepared by embodiment 3.
Fig. 5 is scanning electron microscope (SEM) figure of Graphene composite sulfuration antimony photocatalyst prepared by embodiment 4.
Fig. 6 is scanning electron microscope (SEM) figure of antimony trisulfide micron bar prepared by comparative example.
Fig. 7 is the photocatalytic degradation effect of antimony trisulfide micron bar prepared by comparative example and Graphene composite sulfuration antimony photocatalyst
Fruit is schemed.Wherein e is antimony trisulfide micron bar, and a, b, c, d are respectively stone prepared by embodiment 4, embodiment 1, embodiment 3, embodiment 2
Black alkene composite sulfuration antimony photocatalyst, abscissa represents degradation time, and vertical coordinate represents degradation rate.
Specific embodiment
Below by embodiment, the present invention is further illustrated, but protection scope of the present invention is not by the cited case
Limit.
Embodiment 1
A () weighs 60mg graphene oxides and is added in 60mL ethylene glycol, ultrasound is peeled off 2 hours, is configured to 1mg/mL oxygen
Graphite alkene-ethylene glycol dispersion liquid；
B () adds 0.27g SbCl in graphene oxide-ethylene glycol dispersion liquid3(add equivalent in every milliliter of dispersion liquid
Enter 0.02mmol SbCl3), after stirring and dissolving, (amount of its material is SbCl to add 0.45g tartaric acid3The 2.5 of the amount of material
Times), continue stirring and be completely dissolved to tartaric acid, obtain mixed liquor；
C () adds 0.29g L-Cysteine in mixed liquor, the amount of the material of L-Cysteine is SbCl3The amount of material
2 times, then magnetic agitation 30 minutes so as to be sufficiently mixed is stirred at reflux 12 hours at 180 DEG C；
(d) reaction terminate after naturally cool to room temperature, centrifugation obtains black precipitate, black precipitate is spent respectively from
Sub- water and dehydrated alcohol alternating supersound washing are each 3 times, and Graphene composite sulfuration antimony photocatalyst product is obtained after being dried.
X-ray diffraction (XRD) figure of gained Graphene composite sulfuration antimony photocatalyst product is as shown in Figure 1.By Fig. 1 with
Sb2S3Standard card (JCPDS No.42-1393) control know, the position of all diffraction maximums all matches with standard card, and
Diffraction maximum peak shape is sharp, and diffracted intensity is higher, and the antimony trisulfide for illustrating the orthorhombic crystal phase that product is well-crystallized is supported on Graphene
On lamella, but the diffraction maximum of Graphene is can't see, this is the piece Intercalation reaction antimony trisulfide micron bar due to Graphene, makes lamella
Spacing is uneven, and so as to have impact on piling up in order for graphene sheet layer, it is unordered that it is piled up.
Embodiment 2
A () weighs 30mg graphene oxides and is added in 60mL ethylene glycol, ultrasound is peeled off 1 hour, is configured to 0.5mg/mL
Graphene oxide-ethylene glycol dispersion liquid；
B () adds 0.27g SbCl in graphene oxide-ethylene glycol dispersion liquid3(add equivalent in every milliliter of dispersion liquid
Enter 0.02mmol SbCl3), after stirring and dissolving, (amount of its material is SbCl to add 0.54g tartaric acid33 times of the amount of material),
Continue to stir and be completely dissolved to tartaric acid, obtain mixed liquor；
C () adds 0.27g thiourea in mixed liquor, the amount of the material of thiourea is SbCl33 times of the amount of material, magnetic force is stirred
Mix 45 minutes so as to be sufficiently mixed, be then stirred at reflux 14 hours at 160 DEG C；
(d) reaction terminate after naturally cool to room temperature, centrifugation obtains black precipitate, black precipitate is spent respectively from
Sub- water and dehydrated alcohol alternating supersound washing are each 3 times, and Graphene composite sulfuration antimony photocatalyst product is obtained after being dried.
Embodiment 3
A () weighs 100mg graphene oxides and is added in 50mL ethylene glycol, ultrasound is peeled off 3 hours, is configured to 2mg/mL oxygen
Graphite alkene-ethylene glycol dispersion liquid；
B () adds 0.34g SbCl in graphene oxide-ethylene glycol dispersion liquid3(add equivalent in every milliliter of dispersion liquid
Enter 0.03mmol SbCl3), after stirring and dissolving, (amount of its material is SbCl to add 0.90g tartaric acid34 times of the amount of material),
Continue to stir and be completely dissolved to tartaric acid, obtain mixed liquor；
C () adds 0.45g L-Cysteine in mixed liquor, the amount of the material of L-Cysteine is SbCl3The amount of material
2.5 times, then magnetic agitation 60 minutes so as to be sufficiently mixed is stirred at reflux 16 hours at 140 DEG C；
(d) reaction terminate after naturally cool to room temperature, centrifugation obtains black precipitate, black precipitate is spent respectively from
Sub- water and dehydrated alcohol alternating supersound washing are each 3 times, and Graphene composite sulfuration antimony photocatalyst product is obtained after being dried.
Embodiment 4
A () weighs 75mg graphene oxides and is added in 50mL ethylene glycol, ultrasound is peeled off 2 hours, is configured to 1.5mg/mL
Graphene oxide-ethylene glycol dispersion liquid；
B () adds 0.29g SbCl in graphene oxide-ethylene glycol dispersion liquid3(add equivalent in every milliliter of dispersion liquid
Enter 0.025mmol SbCl3), after stirring and dissolving, (amount of its material is SbCl to add 0.38g tartaric acid32 times of the amount of material),
Continue to stir and be completely dissolved to tartaric acid, obtain mixed liquor；
C () adds 0.19g thiourea in mixed liquor, the amount of the material of thiourea is SbCl32 times of the amount of material, magnetic force is stirred
Mix 20 minutes so as to be sufficiently mixed, be then stirred at reflux 18 hours at 120 DEG C；
(d) reaction terminate after naturally cool to room temperature, centrifugation obtains black precipitate, black precipitate is spent respectively from
Sub- water and dehydrated alcohol alternating supersound washing are each 3 times, and Graphene composite sulfuration antimony photocatalyst product is obtained after being dried.
Comparative example
It is to be contrasted Graphene composite sulfuration antimony photocatalyst and the photocatalysis performance of antimony trisulfide micron bar, in experiment
During, in addition to graphene oxide is not added with, antimony trisulfide micron bar being prepared with composite photo-catalyst identical method is prepared, its is concrete
Step is：
A () adds 0.27g SbCl in 60mL ethylene glycol3(equivalent to addition 0.02mmol in every milliliter of ethylene glycol
SbCl3), after stirring and dissolving, (amount of its material is SbCl to add 0.45g tartaric acid32.5 times of the amount of material), continue to stir extremely
Tartaric acid is completely dissolved, and obtains mixed liquor；
B () adds 0.29g L-Cysteine in mixed liquor, the amount of the material of L-Cysteine is SbCl3The amount of material
2 times, then magnetic agitation 30 minutes so as to be sufficiently mixed is stirred at reflux 12 hours at 180 DEG C；
(c) reaction terminate after naturally cool to room temperature, centrifugation obtains black precipitate, black precipitate is spent respectively from
Sub- water and dehydrated alcohol alternating supersound washing are each 3 times, and antimony trisulfide micron bar is obtained after being dried.
Photocatalysis performance is tested：
It is target degradation product to antimony trisulfide micron bar and the visible light photocatalysis performance of composite with rhodamine B (RhB)
Investigated.Weigh 60mg photocatalysts to be added in the rhodamine B solution for filling 100mL 10mg/L, in the dark ultrasound point
Scattered 10min, then magnetic agitation 30min in the dark, make rhodamine B reach adsorption equilibrium in catalyst surface, take the centrifugation of 5mL sample liquids
Separate and remove after solid catalyst, its suction is tested at the maximum absorption wavelength 554nm of RhB with ultraviolet-visible spectrophotometer
Luminosity is simultaneously as initial absorbance A of the liquid that is degraded0(concentration of correspondence RhB is C0).Then it is light source to Luo Dan with 300W xenon lamps
Bright B solution carries out Photocatalytic Activity for Degradation experiment (top of xenon lamp is away from reaction liquid level 15cm), while magnetic agitation, every
20min samples 5mL, and centrifugation takes the supernatant and its absorbance A is determined at Same Wavelengthx(concentration of correspondence RhB is Cx),
And calculate the degradation rate X of rhodamine B：
X=(C0-C)/C0=(A0-Ax)/A0× 100%.
The scanning electricity of Graphene composite sulfuration antimony photocatalyst prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4
Sub- microscope (SEM) figure is respectively as shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5.As seen from the figure, the antimony trisulfide micron bar in product is except load
Outside graphene film surface, be also inserted between graphene sheet layer (graphene film is very thin and transparent shape, it may be clearly seen that
The antimony trisulfide micron bar of insertion piece interlayer), graphene film is good with the composite effect of antimony trisulfide micron bar.Embodiment 1, embodiment 2,
In composite photo-catalyst prepared by embodiment 3, embodiment 4 length of antimony trisulfide micron bar be respectively 5.2～18.2 μm it is (micro-
Rice), 2.6～9.2 μm, 5.0～12.5 μm, 3.2～9.7 μm；Diameter be respectively 0.6～1.9 μm, 0.7～1.5 μm, 0.4～
2.2 μm, 0.4～1.3 μm.
Scanning electron microscope (SEM) figure of the antimony trisulfide micron bar prepared by comparative example is as shown in Figure 6.Can be with from Fig. 6
Find out, what prepared antimony trisulfide was made up of the micron bar of long 2.9～20.6 μm, 0.4～1.8 μm of diameter.
Visible light photocatalysis performance test is carried out to photocatalyst product, as a result as shown in Figure 7.As seen from Figure 7, it is right
Antimony trisulfide micron bar prepared by ratio (is obtained after the visible light photocatalysis active of product e) is relatively low, and it is compound with Graphene
Graphene composite sulfuration antimony photocatalyst product (embodiment 4, embodiment 1, embodiment 3, the products obtained therefrom of embodiment 2 be respectively a,
B, c, visible light photocatalysis active d) are significantly improved, the composite photo-catalyst (photocatalysis of product a) wherein obtained in embodiment 4
Activity is highest.
Claims (2)
1. a kind of preparation method of Graphene composite sulfuration antimony photocatalyst, it is characterised in that comprise the steps：
A () is added graphene oxide in ethylene glycol, ultrasound is peeled off 1～3 hour, is configured to the oxidation stone of 0.5～2mg/mL
Black alkene-ethylene glycol dispersion liquid；
B () adds SbCl in graphene oxide-ethylene glycol dispersion liquid3, SbCl3Consumption be in every milliliter of dispersion liquid add
0.02～0.03mmol SbCl3, after stirring and dissolving, tartaric acid being added, the amount for adding tartaric material is SbCl3The amount of material
2～4 times, continue stir be completely dissolved to tartaric acid, obtain mixed liquor；
C () adds sulphur source in mixed liquor, the amount of the material of the sulphur source is SbCl32～3 times of the amount of material, magnetic agitation 20
～60 minutes so as to be sufficiently mixed, then it is stirred at reflux 12～18 hours at 120～180 DEG C；
D () reaction naturally cools to room temperature after terminating, centrifugation obtains black precipitate, black precipitate is distinguished into deionized water
Replace supersound washing with dehydrated alcohol, Graphene composite sulfuration antimony photocatalyst is obtained after being dried.
2. the preparation method of Graphene composite sulfuration antimony photocatalyst according to claim 1, it is characterised in that：Described
Sulphur source is L-Cysteine or thiourea.
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| CN108579767A (en) * | 2018-05-04 | 2018-09-28 | 南开大学 | It is grown on the Sb of graphene surface2S3Nanometer sheet and its preparation method and application |
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| CN108579767A (en) * | 2018-05-04 | 2018-09-28 | 南开大学 | It is grown on the Sb of graphene surface2S3Nanometer sheet and its preparation method and application |
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| CN112133899A (en) * | 2020-09-27 | 2020-12-25 | 南开大学 | Preparation method of tin-antimony sulfide/graphene composite material and application of tin-antimony sulfide/graphene composite material in sodium ion battery cathode |
| CN112133899B (en) * | 2020-09-27 | 2023-03-03 | 南开大学 | Preparation method of tin-antimony sulfide/graphene composite material and application of tin-antimony sulfide/graphene composite material in sodium ion battery cathode |
| CN113436898A (en) * | 2021-07-08 | 2021-09-24 | 新余学院 | Thin film electrode material for dye-sensitized solar cell and preparation method thereof |
| CN113436898B (en) * | 2021-07-08 | 2022-06-07 | 新余学院 | Thin film electrode material for dye-sensitized solar cell and preparation method thereof |
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