CN104667950A - Method for preparing graphene-SnIn4S8 nano composite photocatalyst at low temperature by adopting coprecipitation method - Google Patents
Method for preparing graphene-SnIn4S8 nano composite photocatalyst at low temperature by adopting coprecipitation method Download PDFInfo
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- CN104667950A CN104667950A CN201510066028.XA CN201510066028A CN104667950A CN 104667950 A CN104667950 A CN 104667950A CN 201510066028 A CN201510066028 A CN 201510066028A CN 104667950 A CN104667950 A CN 104667950A
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Abstract
The invention relates to a method for preparing a graphene-SnIn4S8 nano composite photocatalyst at low temperature by adopting a coprecipitation method. The method is characterized by comprising the following steps: preparing graphene oxide by utilizing a modified Hummers method, and reducing the graphene oxide by utilizing 80% hydrazine hydrate to obtain reduced graphene oxide; dissolving raw materials such as tin chloride, indium chloride and thioacetamide in an organic alcohol solution, mixing the reduced graphene oxide which is prepared in advance, and preparing the graphene-SnIn4S8 nano composite photocatalyst bonded in chemical bonds by utilizing a low-temperature co-precipitation method. The method has characteristics that the reaction temperature is low, the reaction time is short, the prepared graphene-SnIn4S8 nano composite photocatalyst is relatively large in specific surface area and narrow in energy gap, photo-generated electrons can be effectively separated from electron holes, the stability is high, the regeneration performance is good, and the light absorption activity and the light catalytic activity are relatively strong under the visible light.
Description
Technical field
The present invention relates to a kind of photochemical catalyst preparation method, a kind of coprecipitation low-temperature growth has the Graphene-SnIn of visible response and high catalysis mineralization ability
4s
8the method of nano composite photo-catalyst.
Background technology
Synthetic dyestuffs have been widely used in many industries, as weaving, and printing and dyeing, cosmetics, oil, leather etc., and by industrial wastewater discharge in water environment.Dyestuff has carcinogenic and mutagenesis character, must cause potential environment and health risk.Therefore, before waste water from dyestuff is discharged into environment, the dyestuff how removed in waste water becomes extremely important.So far, absorption, flotation biological treatment, chemical oxidation, electrochemical treatments and heterogeneous photocatalysis technology have been used to remove the dyestuff in waste water, it is one of best-of-breed technology removing Wastewater Dyes that the advantages such as wherein heterogeneous photocatalysis technology has stronger oxidation resistance, the operating temperature of appropriateness become.
Ternary sulfide semiconductor has the advantage that band gap is narrow and stability is high, receives much concern in recent years.Wherein artificial gold indium (SnIn
4s
8) there is cubic spinel structure and Fd3m space symmetr group, be typical ternary sulfur family compound semiconductor, in photocatalysis field, there is potential using value.But, for a single SnIn
4s
8semiconductor, less specific area and faster electron-hole recombination velocity limit its photocatalysis efficiency.Therefore, to SnIn
4s
8it is very important that photochemical catalyst carries out its photo-quantum efficiency of modification raising.
Material with carbon element is considered to a kind of novel metalloid material being expected to be widely used in Environmental capacity field, and representative material is Graphene.Bidimensional (2D) the cycle honeycomb lattice structure that Graphene is made up of carbon hexatomic ring, the basic structural unit of Graphene is benzene hexatomic ring the most stable in organic material, is current optimal two-dimension nano materials.Graphene has great specific area, the character such as lower production cost and excellent electric conductivity simultaneously, is applicable to and catalysis material compound very much, improves its photocatalysis performance, form high performance composite.Graphene improves photocatalysis efficiency mainly from the viewpoint of four.(1) due to the electric conductivity that Graphene is excellent, SnIn
4s
8excite the electronics of generation can not assemble around it, well inhibit the compound in light induced electron and hole.(2) Graphene and SnIn
4s
8chemical bond interacts, and changes SnIn
4s
8original energy gap, makes it demonstrate photocatalytic activity at visible region, increases the utilization rate to visible ray.(3) laminated structure of Graphene has the abundant functional group in huge specific area and surface, can adsorb a large amount of pollutants, can provide desirable reaction site, thus be conducive to the carrying out of degradation reaction for light-catalyzed reaction.(4) relatively costly, the easy stripping and endanger environment in course of reaction of metal material price.If can with Graphene to SnIn
4s
8modify, realize the efficient catalytic to goal response, will effectively reduce the cost of pollutant catabolic gene process and improve the environmental safety of processing procedure.Comprehensively above-mentioned, adopt Graphene and SnIn
4s
8photocatalysis technology combines and is with a wide range of applications.
Summary of the invention
Pure SnIn
4s
8specific area little, and the quick compound of photo-generate electron-hole, which results in the shortcomings such as its photocatalysis efficiency is low, the object of the invention is to for existing deficiency, propose the RGO-SnIn that coprecipitation low-temperature growth has visible response and catalysis mineralization ability
4s
8the method of nano composite photo-catalyst.This RGO-SnIn
4s
8the energy gap of nano composite photo-catalyst is narrow, has stronger light absorption and photocatalysis mineralization ability under visible light, and has higher stability and power of regeneration.
The present invention is achieved by the following technical solutions.A kind of coprecipitation low-temperature growth have visible response and high catalysis mineralization ability Graphene-SnIn
4s
8the method of nano composite photo-catalyst, its step is as follows: first prepare graphene oxide by the Hummers method of modification, then reduced with the hydrazine hydrate of 80% by graphite oxide, obtain redox graphene (RGO).Then with stannic chloride, inidum chloride and thioacetamide are as raw material, they are dissolved in Organic Alcohol solution, add the RGO prepared in advance simultaneously, react under water bath with thermostatic control condition and certain stir speed (S.S.), after reaction terminates, reactant deionized water and absolute ethyl alcohol are washed three times respectively, and products therefrom is 80
ounder C, drying 12 hours, finally grinds, obtains RGO-SnIn
4s
8nano-composite photocatalyst material.
The mol ratio of described stannic chloride, inidum chloride and thioacetamide is for being 1:4:8 ~ 12.
Described Organic Alcohol is for being methyl alcohol, ethanol, isopropyl alcohol, propyl alcohol, butanols, amylalcohol, isoamyl alcohol, 2-hexanol or ethylene glycol
The temperature of described water bath with thermostatic control is for being 55 ~ 95
oc.
The described water bath with thermostatic control time is for being 4 ~ 10 hours.
Described Graphene and SnIn
4s
8mol ratio be 1:100 ~ 1:5.
Degraded target contaminant is industrial dye.
The present invention prepares RGO-SnIn
4s
8the advantage of nano composite photo-catalyst:
(1) preparation method of the present invention is low-temperature co-precipitation method, and temperature is low, and preparation time is short.
(2) RGO-SnIn of coprecipitation low-temperature growth of the present invention
4s
8nano composite photo-catalyst has larger specific area, and energy gap is narrow, can effectively make photo-generate electron-hole be separated, and has stronger light absorption and photocatalysis mineralization ability under visible light, and has higher stability and regenerability.
Accompanying drawing explanation
The RGO-SnIn of Fig. 1 prepared by embodiments of the invention 1
4s
8nano composite photo-catalyst (a) and simple SnIn
4s
8the XRD collection of illustrative plates of comparative sample (b), as seen from the figure, RGO-SnIn
4s
8with pure SnIn
4s
8x ray diffracting data be consistent with the indium sulfide tin phase (PDF#42-1305) of standard, show that the load of Graphene does not affect the crystalline phase of indium sulfide tin.Do not occur that the diffraction maximum of Graphene shows, because Graphene is inserted in indium sulfide tin, to have upset the regularly arranged of Graphene.
The RGO-SnIn of Fig. 2 prepared by embodiments of the invention 1
4s
8nano composite photo-catalyst (a) and pure SnIn
4s
8(b) photochemical catalyst to the curve of adsorption kinetics of the red B of Luo Ming, as seen from the figure, RGO-SnIn
4s
8the saturated extent of adsorption of composite photo-catalyst is 4.24 mg/g, pure SnIn
4s
8saturated extent of adsorption be 2.10 mg/g, and just reach adsorption equilibrium at about 40 min.
The RGO-SnIn of Fig. 3 prepared by embodiments of the invention 1
4s
8nano composite photo-catalyst (a) and pure SnIn
4s
8the kinetic curve of the red B of (b) photocatalyst for degrading Luo Ming, as seen from the figure, RGO-SnIn
4s
8the catalytic activity of composite photo-catalyst is far away higher than pure SnIn
4s
8.
The RGO-SnIn of Fig. 4 prepared by embodiments of the invention 1
4s
8nano composite photo-catalyst (a) and pure SnIn
4s
8nitrogen adsorption-the desorption isotherm of (b), as seen from the figure, RGO-SnIn
4s
8with pure SnIn
4s
8nitrogen adsorption-desorption isotherm all belong to IUPAC classification in IV type, H3 hysteresis loop, but RGO-SnIn
4s
8the specific area of composite photo-catalyst is 35.23m
2/ g, pure SnIn
4s
8specific area be 23.35 m
2/ g, RGO-SnIn
4s
8the specific area of nano composite photo-catalyst is greater than pure SnIn
4s
8specific area,
The RGO-SnIn of Fig. 5 prepared by embodiments of the invention 1
4s
8the mineralising figure of nano composite photo-catalyst rhodamine B degradation solution under visible light, as seen from the figure, RGO-SnIn
4s
8composite photo-catalyst is degraded Luo Mingdan B solution under visible light, and the clearance of TOC in solution can be made in 70min to reach more than 70%.
Detailed description of the invention
Below implement to be intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
(1) take graphite powder as raw material, adopt Hummers method synthesis graphene oxide, then reduce with the hydrazine hydrate of 80%, obtain redox graphene.
(2) by 2.0 mmol stannic chlorides, 8.0 mmol inidum chlorides, 12 mmol thioacetamides, to join in 50 mL ethanolic solutions and be stirred to solution transparent after add 0.2 mmol Graphene, then carry out ultrasonic 30 min.
(3) transferred to by solution in the there-necked flask of 100 mL, add condensation reflux unit, and stir with suitable speed, bath temperature is 55
oc, water bath time is 4 hours.
(4) the sample suction filtration after water-bath is also washed three times with deionized water and ethanol, gained sample is 80
odrying 12 hours under C.Then take out, naturally cool, grinding.Products therefrom is RGO-SnIn
4s
8nano composite photo-catalyst.
Embodiment 2
(1) take graphite powder as raw material, adopt Hummers method synthesis graphene oxide, then reduce with the hydrazine hydrate of 80%, obtain redox graphene.
(2) by 2.0 mmol stannic chlorides, 8.0 mmol inidum chlorides, 24 mmol thioacetamides, to join in 50 mL ethylene glycol solutions and be stirred to solution transparent after add 0.1mmol Graphene, then carry out ultrasonic 30min.
(3) transferred to by solution in the there-necked flask of 100 mL, add condensation reflux unit, and stir with suitable speed, bath temperature is 95
oc, water bath time is 10 hours.
(4) the sample suction filtration after water-bath is also washed three times with deionized water and ethanol, gained sample is 80
odrying 12 hours under C.Then take out, naturally cool, grinding.Products therefrom is RGO-SnIn
4s
8nano composite photo-catalyst.
Embodiment 3
(1) take graphite powder as raw material, adopt Hummers method synthesis graphene oxide, then reduce with the hydrazine hydrate of 80%, obtain redox graphene.
(2) by 2.0 mmol stannic chlorides, 8.0 mmol inidum chlorides, 12 mmol thioacetamides, to join in 50 mL butanol solutions and be stirred to solution transparent after add 0.06mmol Graphene, then carry out ultrasonic 30min.
(3) transferred to by solution in the there-necked flask of 100 mL, add condensation reflux unit, and stir with suitable speed, bath temperature is 55
oc, water bath time is 10 hours.
(4) the sample suction filtration after water-bath is also washed three times with deionized water and ethanol, gained sample is 80
odrying 12 hours under C.Then take out, naturally cool, grinding.Products therefrom is RGO-SnIn
4s
8nano composite photo-catalyst.
Embodiment 4
(1) take graphite powder as raw material, adopt Hummers method synthesis graphene oxide, then reduce with the hydrazine hydrate of 80%, obtain redox graphene.
(2) by 2.0 mmol stannic chlorides, 8.0 mmol inidum chlorides, 15 mmol thioacetamides, to join in 50 mL amyl alcohol solution and be stirred to solution transparent after add 0.01mmol Graphene, then carry out ultrasonic 30min.
(3) transferred to by solution in the there-necked flask of 100 mL, add condensation reflux unit, and stir with suitable speed, bath temperature is 80
oc, water bath time is 8 hours.
(4) the sample suction filtration after water-bath is also washed three times with deionized water and ethanol, gained sample is 80
odrying 12 hours under C.Then take out, naturally cool, grinding.Products therefrom is RGO-SnIn
4s
8nano composite photo-catalyst.
Embodiment 5
(1) take graphite powder as raw material, adopt Hummers method synthesis graphene oxide, then reduce with the hydrazine hydrate of 80%, obtain redox graphene.
(2) by 2.0 mmol stannic chlorides, 8.0 mmol inidum chlorides, 20 mmol thioacetamides, to join in 50 mL aqueous isopropanols and to stir, transparent to solution.
(3) transferred to by solution in the there-necked flask of 100 mL, add condensation reflux unit, and stir with suitable speed, bath temperature is 80
oc, water bath time is 5 hours.
(4) the sample suction filtration after water-bath is also washed three times with deionized water and ethanol, gained sample is 80
odrying 12 hours under C.Then take out, naturally cool, grinding.Products therefrom is SnIn
4s
8photochemical catalyst.
Claims (6)
1. a coprecipitation low-temperature growth Graphene-SnIn
4s
8the method of nano composite photo-catalyst, is characterized in that step is as follows: first prepare graphene oxide by the Hummers method of modification, then reduced by graphene oxide with the hydrazine hydrate of 80%, obtain redox graphene; Then with stannic chloride, inidum chloride and thioacetamide are as raw material, they are dissolved in Organic Alcohol solution, add the redox graphene prepared in advance simultaneously, react under water bath with thermostatic control condition and certain stir speed (S.S.), after reaction terminates, reactant deionized water and absolute ethyl alcohol are washed three times respectively, and products therefrom is 80
ounder C, drying 12 hours, finally grinds, obtains Graphene-SnIn
4s
8nano-composite photocatalyst material.
2. coprecipitation low-temperature growth Graphene-Snaccording to claim 1
4s
8the method of nano composite photo-catalyst, is characterized in that: the mol ratio of stannic chloride, inidum chloride and thioacetamide is for being 1:4:6 ~ 12.
3. coprecipitation low-temperature growth Graphene-Snaccording to claim 1
4s
8the method of nano composite photo-catalyst, is characterized in that: described Organic Alcohol is methyl alcohol, ethanol, isopropyl alcohol, propyl alcohol, butanols, amylalcohol, isoamyl alcohol, 2-hexanol or ethylene glycol.
4. coprecipitation low-temperature growth Graphene-Snaccording to claim 1
4s
8the method of nano composite photo-catalyst, is characterized in that: water bath with thermostatic control temperature is for being 55 ~ 95
oc.
5. coprecipitation low-temperature growth Graphene-Snaccording to claim 1
4s
8the method of nano composite photo-catalyst, is characterized in that: the water bath with thermostatic control time is for being 4 ~ 10 hours.
6. coprecipitation low-temperature growth Graphene-Snaccording to claim 1
4s
8the method of nano composite photo-catalyst, is characterized in that: Graphene and SnIn
4s
8mol ratio be 1:100 ~ 1:5.
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| CN107754817A (en) * | 2017-10-12 | 2018-03-06 | 湖南大学 | Ternary metal sulfide/redox graphene composite and its preparation method and application |
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| CN108404959A (en) * | 2018-03-09 | 2018-08-17 | 台州职业技术学院 | A kind of rodlike g-C3N4@SnIn4S8Composite photo-catalyst and preparation method thereof |
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| CN107754817A (en) * | 2017-10-12 | 2018-03-06 | 湖南大学 | Ternary metal sulfide/redox graphene composite and its preparation method and application |
| CN107754817B (en) * | 2017-10-12 | 2020-03-27 | 湖南大学 | Ternary metal sulfide/reduced graphene oxide composite material and preparation method and application thereof |
| CN108144596A (en) * | 2017-12-29 | 2018-06-12 | 常州大学 | A kind of controllable 3DOM-TiO of window2Photochemical catalyst preparation method |
| CN108404959A (en) * | 2018-03-09 | 2018-08-17 | 台州职业技术学院 | A kind of rodlike g-C3N4@SnIn4S8Composite photo-catalyst and preparation method thereof |
| CN108404959B (en) * | 2018-03-09 | 2021-01-12 | 台州职业技术学院 | Rod-like g-C3N4@SnIn4S8Composite photocatalyst and preparation method thereof |
| CN108404994A (en) * | 2018-03-16 | 2018-08-17 | 常州大学 | A kind of preparation method of the phthalocyanine-sensitized indium sulfide tin composite visible light catalyst of nitro cobalt |
| CN109261166A (en) * | 2018-08-16 | 2019-01-25 | 华南理工大学 | A kind of preparation of the flower-like nanometer material of tin dope indium sulfide and its application in photo catalytic reduction |
| CN109286011A (en) * | 2018-09-28 | 2019-01-29 | 哈尔滨理工大学 | A kind of preparation method of stannic disulfide/vertical graphene nanometer sheet array electrode |
| CN109225297A (en) * | 2018-09-29 | 2019-01-18 | 台州学院 | A kind of composite catalyst QDs-SISCN and its preparation method and application |
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Application publication date: 20150603 |