CN107224978B - Hydroxyl stannate cobalt/graphene composite photocatalyst preparation method and applications - Google Patents
Hydroxyl stannate cobalt/graphene composite photocatalyst preparation method and applications Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 26
- 239000010941 cobalt Substances 0.000 title claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 26
- 229940071182 stannate Drugs 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 125000005402 stannate group Chemical group 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 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 claims description 20
- 229940043267 rhodamine b Drugs 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 15
- 230000015556 catabolic process Effects 0.000 claims description 14
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910020212 Na2SnO3 Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 229910019043 CoSn Inorganic materials 0.000 abstract description 39
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 Hydroxy tin Chemical compound 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VSKDLKJOZFLQQZ-UHFFFAOYSA-M O[Sn] Chemical compound O[Sn] VSKDLKJOZFLQQZ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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Abstract
The invention discloses a kind of preparation method and applications of hydroxyl stannate cobalt/graphene composite photocatalyst, belong to inorganic catalysis material field.The present invention first prepares graphite oxide and CoSn (OH)6Powder, then be configured to solution, is transferred in reaction kettle after mixing and reacts in high temperature box furnace, and graphite oxide is reduced into graphene during this, and with CoSn (OH)6It is compound, then through centrifugation, washing, drying and grinding, CoSn (OH) is prepared6/ graphene composite photocatalyst.The present invention has the advantages that the cost of preparation is low, preparation process is simple, CoSn (OH)6It is uniform to be supported on particle diameter distribution on graphene, in 60nm-80nm range, obtained CoSn (OH)6For/graphene composite material as photochemical catalyst, light absorbing wide waveband is big to the utilization rate of visible light, and the compound probability of electron-hole pair is low in light-catalyzed reaction, and photocatalytic activity is high.
Description
Technical field
The invention belongs to inorganic catalysis material fields, and in particular to a kind of hydroxyl stannate cobalt/graphene composite photocatalyst
Preparation method and applications.
Background technique
In recent years, as industrialized process promotes and the progress of science and technology, socio-economic development is rapid, people's lives water
It is flat to significantly improve, but the following energy and environmental problem is increasingly significant.In order to solve this two hang-up, on the one hand, people
Class should be noted that energy saving, protection environment, and on the other hand, it is also an important ring that actively research, which searches out new clean energy resource,
Section.There are solar energy resources abundant on the earth, it not only can be by green, sufficient, environmental protection solar energy using photocatalysis technology
It is converted into electric energy and chemical energy, degradation of contaminant can also be directly used in.Therefore, photocatalysis technology is to solve the current social energy
The desirable route of shortage and problem of environmental pollution.Photocatalysis is the research hotspot of current chemistry, material and environmental area, application
It is in extensive range, such as sewage treatment, air cleaning, Solar use, antibacterial and self-cleaning function.Currently, common photocatalysis
Agent is TiO2With these unitary oxides and a variety of composite oxides such as ZnO, but these photochemical catalysts have it is some identical
Defect, mainly photo-generate electron-hole are high to the probability of recombination and too low to the utilization efficiency of light.
Graphene refers to close-packed arrays at the single layer of carbon atom of two-dimentional honeycomb crystal lattice.2004, Manchester was big
Two researcher Andre Geim and the Kostya Novoselov etc. learned successfully isolate graphene from graphite.Graphene
It is a kind of nano material with huge specific surface area, excellent electric conductivity and mechanical property, has at room temperature higher
Electron mobility.
And hydroxyl stannate salt material belongs to perovskite structure, stable structure, forbidden bandwidth and adsorption capacity with higher,
Photocatalysis organic matter degradation and sterilization aspect all embody important application prospect.Hydroxy tin acid salt is as a kind of forbidden bandwidth
Biggish semiconductor material, after illumination, the redox potential of the photo-generate electron-hole pair generated is also larger.Meanwhile belonging to
The CoSn (OH) of hydroxy compounds6Surface distribution there are many hydroxyl radical free radical so that the carrier mobility of this kind of compound
Rate is larger.Thus, before these excellent properties determine that hydroxy tin acid salt has very important application in terms of the photocatalysis
Scape.
Summary of the invention
It is urged in view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of hydroxyl stannate cobalt/graphene complex light
The preparation method and applications of agent.Hydroxyl stannate cobalt/graphene composite material produced by the present invention is absorbed as photochemical catalyst
The wide waveband of light, big to the utilization rate of visible light, the compound probability of electron-hole pair is low in light-catalyzed reaction, photocatalytic activity
Height, high catalytic efficiency.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of hydroxyl stannate cobalt/graphene composite photocatalyst, it is characterised in that: using hydrothermal synthesis
Method is by hydroxyl stannate cobalt (CoSn (OH)6) be supported on graphene, obtain CoSn (OH)6/ graphene composite photocatalyst,
Wherein CoSn (OH)6Partial size in 60nm-80nm range, specifically includes the following steps:
(1) synthesis of graphite oxide
Graphite powder and sodium nitrate solid powder are poured into the 98wt% concentrated sulfuric acid, keeps solution temperature at 0 DEG C, is sufficiently stirred
1h；It is slowly added to potassium permanganate solid later, 2h is sufficiently stirred, during which temperature control is being lower than 15 DEG C.；Heating after stirring completely
To 38 DEG C, it is stirred for 1h；Then solution is poured into deionized water, stirs 1h, temperature is controlled at 92 DEG C；It is cooling after having stirred,
It when being cooled to 60 DEG C, is added hydrogen peroxide solution (30wt%), so that solution becomes golden yellow；Finally, the slurry 5wt% that will be obtained
Hydrochloric acid centrifuge washing, repeatedly, until, without precipitating (pH close to 5), will be washed in the cleaning solution detected with barium chloride
The solid matter drying obtained afterwards, grinding is fine later, can obtain graphite oxide powder；
(2) hydroxyl stannate cobalt (CoSn (OH)6) synthesis
Weigh CoCl2·6H2O solid powder is added in the beaker equipped with deionized water, is stirred at room temperature, until complete
Fully dissolved obtains CoCl2Solution；By Na2SnO3·4H2O solid powder dissolves in deionized water, is added to CoCl obtained2
In solution, 2 ~ 10h is stirred under the conditions of 0 ~ 100 DEG C, is centrifuged taking precipitate, and wash 3 with deionized water and dehydrated alcohol respectively ~
6 times, baking oven is put under conditions of 70 ~ 120 DEG C, dry 6 ~ 18h；
(3) CoSn (OH)6The synthesis of/graphene
It weighs 0.02 ~ 0.06g graphite oxide to be added in the beaker for filling deionized water, 1 ~ 2h of ultrasound, obtains oxidation stone
Black solution；0.14 ~ 0.18g hydroxyl stannate cobalt (CoSn (OH) is weighed again6) powder, it makes it dissolve in hydrochloric acid solution, is then added
It is vigorously stirred into above-mentioned graphite oxide solution, until solution becomes penetrating, the solution being stirred is transferred in reaction kettle, is put
Enter 4 ~ 9h of reaction in high temperature box furnace, reaction temperature is 80 ~ 150 DEG C；After the reaction was completed, centrifuge washing；The solids that will be obtained
Matter is put into baking oven and dries, and then grinding is fine, and the CoSn (OH) is made6/ graphene composite photocatalyst.
CoCl in step (2)2·6H2O and Na2SnO3·4H2The molar ratio of O is 1:1.
The pH of hydrochloric acid solution described in step (3) is 2 ~ 6.
Obtained hydroxyl stannate cobalt/graphene composite photocatalyst is used for photocatalytic degradation rhodamine B solution, specific to grasp
Make as follows: taking 0.05g hydroxyl stannate cobalt/graphene composite photocatalyst, it is molten to be added to the rhodamine B that 80mL concentration is 10mg/L
In liquid, under conditions of xenon source is to excite light-catalyzed reaction (λ > 300nm), when light-catalyzed reaction carries out 60min, to Luo Dan
Bright B solution degradation rate reaches 29.3%；When light-catalyzed reaction carries out 180min, 50.8% is reached to rhodamine B solution degradation rate.
The beneficial effects of the present invention are:
(1) simple process of the present invention, low for equipment requirements, easy to implement, preparation cost is low；And it is made
CoSn(OH)6Even particle distribution, size uniformity, pattern are good；
(2) CoSn (OH)6It is uniform to be supported on particle diameter distribution on graphene, in 60nm-80nm range, obtained CoSn
(OH)6/ graphene composite material is big to the utilization rate of visible light as photochemical catalyst；
(3) at catalyst CoSn (OH)6The dosage of/graphene is 0.05g, is added to 80mL rhodamine B solution (10mg/
L it is excited using xenon source under conditions of light-catalyzed reaction (λ > 300nm) in), test obtains it and carries out in light-catalyzed reaction
After 60min, 180min, rhodamine B solution degradation rate is all significantly greater than with pure CoSn (OH)6Degradation as catalyst
Rate, photocatalysis performance is excellent, increases the utilization rate of visible light, and photocatalytic activity improves, when light-catalyzed reaction carries out 60min,
29.3% is reached to rhodamine B solution degradation rate；When light-catalyzed reaction carries out 180min, rhodamine B solution degradation rate is reached
50.8%。
Detailed description of the invention
Fig. 1 is the XRD spectra of photochemical catalyst prepared by embodiment 1 and comparative example 1, and a is the spectrogram of embodiment 1 in Fig. 1,
B is the spectrogram of comparative example 1 in Fig. 1；
Fig. 2 is the scanning electron microscopic picture of photochemical catalyst prepared by embodiment 1；
Fig. 3 is the performance picture of photocatalyst for degrading rhodamine B solution prepared by embodiment 1 and comparative example 1.
Specific embodiment
The present invention is further illustrated by the following examples, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
CoSn(OH)6The preparation process of/graphene composite photocatalyst the following steps are included:
(1) synthesis of graphite oxide
1g graphite powder and 0.5g sodium nitrate solid powder are added in the 23ml98wt% concentrated sulfuric acid, keep solution temperature 0
DEG C, 1h is sufficiently stirred.It is slowly added to 3g potassium permanganate (average every 5min 1g) later, 2h is sufficiently stirred, during which temperature control exists
Lower than 15 DEG C, it is preferably kept in 0 DEG C or so.38 DEG C are warming up to after stirring completely, is stirred for 1h.Then solution is poured into 100ml
In deionized water, 1h is stirred, temperature is controlled at 92 DEG C.It is cooling after having stirred, when being cooled to 60 DEG C, 24ml hydrogen peroxide (30 is added
Wt %) so that solution becomes golden yellow.Finally, by the hydrochloric acid centrifuge washing of obtained slurry 5wt%, repeatedly, until
Without precipitating (pH close to 5) in the cleaning solution detected with barium chloride, the solid matter obtained after washing is dried, is ground later
Finely, graphite oxide powder can be obtained.
(2) hydroxyl stannate cobalt (CoSn (OH)6) synthesis
Claim the CoCl of 10mmol2·6H2O solid powder is added in 100ml deionized water, is stirred at room temperature, until complete
Fully dissolved obtains CoCl2Solution；By the Na of 10mmol2SnO3·4H2O solid powder dissolves in 20ml deionized water, is added
To CoCl2Solution in, be stirred at room temperature 5h, be centrifuged taking precipitate, and wash 3 with deionized water and dehydrated alcohol respectively
It is secondary, baking oven is put under conditions of 100 DEG C, dry 12h.
(3) CoSn (OH)6The synthesis of/graphene
It weighs 0.02g graphite oxide to be added in the deionized water of 25mL, ultrasonic 1h obtains graphite oxide solution；Claim again
Take 0.18g CoSn (OH)6Powder dissolves it in the pH of 25mL as it is molten to be then added to above-mentioned graphite oxide in 4 hydrochloric acid
It is vigorously stirred in liquid, until solution becomes penetrating, the solution being stirred is transferred in reaction kettle, is put into high temperature box furnace
6h is reacted at 120 DEG C.After the reaction was completed, obtained solid matter is put into baking oven and dries by centrifuge washing, then grinding essence
Carefully, CoSn (OH) can be obtained6/ graphene composite photocatalyst.
CoSn obtained by embodiment 1 (OH)6/ graphene photo-catalyst grain diameter is in 60-80nm, in catalyst amount
For 0.05g, be added in 80mL rhodamine B solution (10mg/L), excited using xenon source light-catalyzed reaction (λ >
300nm), test obtain its light-catalyzed reaction carry out 60min when, 29.3% is reached to rhodamine B solution degradation rate, react into
When row 180min, 50.8% is reached to rhodamine B solution degradation rate.
Embodiment 2
CoSn(OH)6The preparation process of/graphene composite photocatalyst the following steps are included:
(1) synthesis of graphite oxide
1g graphite powder and 0.5g sodium nitrate solid powder are added to the 23ml98wt% concentrated sulfuric acid, keep solution temperature 0
DEG C, 1h is sufficiently stirred.It is slowly added to 3g potassium permanganate (average every 5min 1g) later, 2h is sufficiently stirred, during which temperature control exists
Lower than 15 DEG C, it is preferably kept in 0 DEG C or so.38 DEG C are warming up to after stirring completely, is stirred for 1h.Then solution is poured into 100ml
In deionized water, 1h is stirred, temperature is controlled at 92 DEG C.It is cooling after having stirred, when being cooled to 60 DEG C, 24ml hydrogen peroxide is added
(30wt%), so that solution becomes golden yellow.Finally, by the hydrochloric acid centrifuge washing of obtained slurry 5wt%, repeatedly, directly
Into the cleaning solution detected with barium chloride without precipitating (pH close to 5), the solid matter obtained after washing is dried, Zhi Houyan
Mill is fine, can obtain graphite oxide powder.
(2) hydroxyl stannate cobalt (CoSn (OH)6) synthesis
Claim the CoCl of 10mmol2·6H2O solid powder is added in 100ml deionized water, is stirred at room temperature, until complete
Fully dissolved obtains CoCl2Solution；By the Na of 10mmol2SnO3·4H2O solid powder dissolves in 20ml deionized water, is added
To CoCl2Solution in, be stirred at room temperature 5h, be centrifuged taking precipitate, and wash 3 with deionized water and dehydrated alcohol respectively
It is secondary, baking oven is put under conditions of 100 DEG C, dry 12h.
(3) CoSn (OH)6The synthesis of/graphene
It weighs 0.04g graphite oxide to be added in the deionized water of 25mL, ultrasonic 1h obtains graphite oxide solution；Claim again
Take 0.16g CoSn (OH)6Powder dissolves it in the pH of 25mL as it is molten to be then added to above-mentioned graphite oxide in 4 hydrochloric acid
It is vigorously stirred in liquid, until solution becomes penetrating, the solution being stirred is transferred in reaction kettle, is put into high temperature box furnace
4h is reacted at 150 DEG C.After the reaction was completed, obtained solid matter is put into baking oven and dries by centrifuge washing, then grinding essence
Carefully, CoSn (OH) can be obtained6/ graphene composite photocatalyst.
Embodiment 3
CoSn(OH)6The preparation process of/graphene composite photocatalyst the following steps are included:
(1) synthesis of graphite oxide
1g graphite powder and 0.5g sodium nitrate solid powder are added in the 23ml98wt% concentrated sulfuric acid, keep solution temperature 0
DEG C, 1h is sufficiently stirred.It is slowly added to 3g potassium permanganate (average every 5min 1g) later, 2h is sufficiently stirred, during which temperature control exists
Lower than 15 DEG C, it is preferably kept in 0 DEG C or so.38 DEG C are warming up to after stirring completely, is stirred for 1h.Then solution is poured into 100ml
In deionized water, 1h is stirred, temperature is controlled at 92 DEG C.It is cooling after having stirred, when being cooled to 60 DEG C, 24ml hydrogen peroxide is added
(30wt%), so that solution becomes golden yellow.Finally, by the hydrochloric acid centrifuge washing of obtained slurry 5wt%, repeatedly, directly
Into the cleaning solution detected with barium chloride without precipitating (pH close to 5), the solid matter obtained after washing is dried, Zhi Houyan
Mill is fine, can obtain graphite oxide powder.
(2) hydroxyl stannate cobalt (CoSn (OH)6) synthesis
Claim the CoCl of 10mmol2·6H2O solid powder is added in 100ml deionized water, is stirred at room temperature, until complete
Fully dissolved obtains CoCl2Solution；By the Na of 10mmol2SnO3·4H2O solid powder dissolves in 20ml deionized water, is added
To CoCl2Solution in, be stirred at room temperature 5h, be centrifuged taking precipitate, and wash 3 with deionized water and dehydrated alcohol respectively
It is secondary, baking oven is put under conditions of 100 DEG C, dry 12h.
(3) CoSn (OH)6The synthesis of/graphene
It weighs 0.06g graphite oxide to be added in the deionized water of 25mL, ultrasonic 1h obtains graphite oxide solution；Claim again
Take 0.14g CoSn (OH)6Powder dissolves it in the pH of 25mL as it is molten to be then added to above-mentioned graphite oxide in 4 hydrochloric acid
It is vigorously stirred in liquid, until solution becomes penetrating, the solution being stirred is transferred in reaction kettle, is put into high temperature box furnace
9h is reacted at 80 DEG C.After the reaction was completed, obtained solid matter is put into baking oven and dries by centrifuge washing, and then grinding is fine,
It can obtain CoSn (OH)6/ graphene composite photocatalyst.
Comparative example 1
Photochemical catalyst chemical formula: CoSn (OH)6, preparation process the following steps are included:
Hydroxyl stannate cobalt (CoSn (OH)6) synthesis
Claim the CoCl of 10mmol2·6H2O solid powder is added in 100ml deionized water, is stirred at room temperature, until complete
Fully dissolved obtains CoCl2Solution；By the Na of 10mmol2SnO3·4H2O solid powder dissolves in 20ml deionized water, is added
To CoCl2Solution in, be stirred at room temperature 5h, be centrifuged taking precipitate, and wash 3 with deionized water and dehydrated alcohol respectively
It is secondary, baking oven is put under conditions of 100 DEG C, dry 12h.
CoSn obtained by comparative example 1 (OH)6Photocatalyst granular partial size is in 60-80nm, in catalyst amount
0.05g is added in 80mL rhodamine B solution (10mg/L), and light-catalyzed reaction (λ > 300nm) is excited using xenon source,
Test obtains it when light-catalyzed reaction carries out 60min, reaches 0.13% to rhodamine B solution degradation rate, reaction carries out 180min
When, 6.5% is reached to rhodamine B solution degradation rate.
CoSn it is found that obtained is compared by degradation effect of the photochemical catalyst of embodiment 1 and comparative example 1 to rhodamine B
(OH)6CoSn (OH) of the catalytic activity of/graphene photo-catalyst compared to comparative example 16The catalytic activity of sample has significantly
It improves, photocatalytic degradation effect is good, and catalytic activity is high.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. a kind of preparation method of hydroxyl stannate cobalt/graphene composite photocatalyst, it is characterised in that: using the side of hydrothermal synthesis
Hydroxyl stannate cobalt is supported on graphene by method, obtains hydroxyl stannate cobalt/graphene composite photocatalyst, wherein hydroxyl stannate
The partial size of cobalt is in 60nm-80nm range；
The following steps are included:
(1) synthesis of graphite oxide；
(2) synthesis of hydroxyl stannate cobalt
Weigh CoCl2·6H2O solid powder is added in the beaker equipped with deionized water, is stirred at room temperature, until completely molten
Solution, obtains CoCl2Solution；By Na2SnO3·4H2O solid powder dissolves in deionized water, is added to CoCl obtained2Solution
In, 2 ~ 10h is stirred under the conditions of 0 ~ 100 DEG C, is centrifuged taking precipitate, and washed 3 ~ 6 times with deionized water and dehydrated alcohol respectively,
Baking oven is put under conditions of 70 ~ 120 DEG C, dry 6 ~ 18h；
(3) hydroxyl stannate cobalt/graphene synthesis
It weighs 0.02 ~ 0.06g graphite oxide to be added in the beaker for filling deionized water, it is molten to obtain graphite oxide by 1 ~ 2h of ultrasound
Liquid；0.14 ~ 0.18g hydroxyl stannate cobalt dust is weighed again, is made it dissolve in hydrochloric acid solution, and it is molten to be then added to above-mentioned graphite oxide
It is vigorously stirred in liquid, until solution becomes penetrating, the solution being stirred is transferred in reaction kettle, be put into high temperature box furnace anti-
4 ~ 9h is answered, reaction temperature is 80 ~ 150 DEG C；After the reaction was completed, centrifuge washing；Obtained solid matter is put into baking oven and is dried,
Then grinding is fine, and the hydroxyl stannate cobalt/graphene composite photocatalyst is made.
2. preparation method according to claim 1, it is characterised in that: the synthetic method of graphite oxide described in step (1)
Are as follows: graphite powder and sodium nitrate solid powder are poured into the 98wt% concentrated sulfuric acid, keeps solution temperature at 0 DEG C, 1h is sufficiently stirred；It
After be slowly added to potassium permanganate solid, 2h is sufficiently stirred, during which temperature control be lower than 15 DEG C；38 are warming up to after stirring completely
DEG C, it is stirred for 1h；Then solution is poured into deionized water, stirs 1h, temperature is controlled at 92 DEG C；It is cooling after having stirred, it is cooling
When to 60 DEG C, the hydrogen peroxide solution of 30wt% is added, so that solution becomes golden yellow；Finally, by the salt of obtained slurry 5wt%
Acid centrifuging washing, until, without precipitating, the solid matter obtained after washing being dried in the cleaning solution detected with barium chloride, it
Grinding is fine afterwards, and graphite oxide powder is made.
3. preparation method according to claim 1, it is characterised in that: CoCl in step (2)2·6H2O and Na2SnO3·
4H2The molar ratio of O is 1:1.
4. preparation method according to claim 1, it is characterised in that: the pH of hydrochloric acid solution described in step (3) is 2 ~ 6.
5. hydroxyl stannate cobalt/graphene complex light made from a kind of preparation method as described in any one of claim 1 ~ 4 is urged
The application of agent, it is characterised in that: the composite photo-catalyst is used for photocatalytic degradation rhodamine B solution.
6. application according to claim 5, it is characterised in that: take 0.05g hydroxyl stannate cobalt/graphene composite photocatalyst
Agent is added in the rhodamine B solution that 80mL concentration is 10mg/L, under conditions of xenon source is to excite light-catalyzed reaction,
When light-catalyzed reaction carries out 60min, 29.3% is reached to rhodamine B solution degradation rate；It is right when light-catalyzed reaction carries out 180min
Rhodamine B solution degradation rate reaches 50.8%.
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