CN108355678A - A kind of compound micron bouquet of artificial gold-bismuth tungstate and its preparation method and application - Google Patents

A kind of compound micron bouquet of artificial gold-bismuth tungstate and its preparation method and application Download PDF

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CN108355678A
CN108355678A CN201810193853.XA CN201810193853A CN108355678A CN 108355678 A CN108355678 A CN 108355678A CN 201810193853 A CN201810193853 A CN 201810193853A CN 108355678 A CN108355678 A CN 108355678A
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sns
present
compound micron
bouquet
micron bouquet
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代威力
王腾瑶
罗胜联
熊悟琬
罗旭彪
涂新满
邹建平
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Nanchang Hangkong University
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Nanchang Hangkong University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04Sulfides
    • B01J27/047Sulfides with chromium, molybdenum, tungsten or polonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/40Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The present invention provides a kind of SnS2‑Bi2WO6Compound micron bouquet and preparation method thereof, this kind of catalyst include the spherical SnS of petal2And Bi2WO6Particle;The spherical SnS of the petal2By SnS2Piece self assembly forms, the Bi2WO6Distribution of particles is in the SnS2Piece surface.In the present invention, Bi2WO6Distribution of particles is in the SnS2Surface, form hetero-junctions, promote efficiently separating for electron hole pair so that the photocatalytic activity of composite material significantly improves.The present invention generates organic-fuel, petal chondritic SnS using the compound micron bouquet as catalyst for photocatalysis carbon dioxide2Presence help to improve the specific surface area of composite material, and then improve the absorption to visible light, the contact area of bigger and more active sites provided for light-catalyzed reaction system, to improve the photocatalysis efficiency of composite material.

Description

A kind of compound micron bouquet of artificial gold-bismuth tungstate and its preparation method and application
Technical field
The invention belongs to catalysis material technical field more particularly to a kind of SnS2-Bi2WO6Compound micron bouquet and its system Preparation Method and application.
Background technology
With industrialized development, great amount of carbon dioxide greenhouse gas has been discharged in a large amount of uses of fossil fuel.2015 The data in March show that the carbon dioxide gas in air has reached 400.83ppm, have been the tops since 600,000 years, result in Serious greenhouse effects and global warming more bring the problems such as sea level rise, solve what carbon dioxide was brought Greenhouse effects problem is extremely urgent.Researcher trial now cures carbon dioxide, and being translated into the mankind can profit The energy.
The method of fixed carbon dioxide relates generally to these two issues:(1) how the required energy is cleanly obtained; (2) how the carbon dioxide molecule of activation stable.Since Inoue etc. reported in 1979 carbon dioxide photocatalysis generate it is organic The precedent of object, the catalysis material of photocatalytic reduction of carbon oxide become a focus of researcher research.
Traditional wide band gap semiconducter photochemical catalyst, such as:TiO2, the forbidden bands broadband such as ZnO it is larger, to the utilization rate of solar energy It is relatively low, in solar energy 4% ultraviolet light can only be absorbed, photocatalysis efficiency is relatively low.In order to more effectively solar energy be utilized to realize Solidification to carbon dioxide, researcher are dedicated to developing novel visible responsive photocatalyst.Bi2WO6It is one kind to have The semiconductor multivariant oxide of layer structure has certain response, (Bi being alternately present with it under visible light2O2)2+Layer With octahedral (WO4)2-Structure feature made of accumulation, have higher photocatalytic activity, carbon dioxide solidification field by To extensive concern.
But Bi2WO6It is a kind of direct band-gap semicondictor, and energy gap is only 2.75eV or so, when illumination generates Light induced electron and hole direct combination probability it is higher, it is seen that photoresponse is weaker, and photo-quantum efficiency is relatively low, and Bi2WO6Material Specific surface area it is small, photogenerated charge migration distance is longer, and then that there are still photocatalysis efficiencies is relatively low, and photocatalysis effect is still undesirable The problem of.
Invention content
In view of this, the purpose of the present invention is to provide a kind of SnS2-Bi2WO6Compound micron bouquet and preparation method thereof and Using SnS provided by the invention2-Bi2WO6Compound micron bouquet has higher photocatalysis efficiency.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme:
A kind of SnS2-Bi2WO6Compound micron bouquet, including Bi2WO6With the SnS of flower ball-shaped2;The SnS of the flower ball-shaped2By SnS2Piece self assembly forms, the Bi2WO6It is distributed in the SnS2Piece surface.
Preferably, the SnS2-Bi2WO6The grain size of compound micron bouquet is 5~6 μm;
The SnS2-Bi2WO6SnS in compound micron bouquet2And Bi2WO6Substance amount ratio be (0.025~0.15):1.
The present invention provides the SnS described in above-mentioned technical proposal2-Bi2WO6The preparation method of compound micron bouquet, including with Lower step:
(1) butter of tin, thiocarbamide and ethylene glycol are mixed, carries out heating reaction, obtains flower ball-shaped SnS2
(2) sodium tungstate and bismuth nitrate are added to the flower ball-shaped SnS2Ethylene glycol dispersion liquid in, carry out solvent heat seal At reaction, SnS is obtained2-Bi2WO6Compound micron bouquet.
Preferably, the amount of the substance of butter of tin in the step (1), thiocarbamide substance amount and ethylene glycol volume ratio For 1.5~2mmol:8~10mmol:80mL.
Preferably, the temperature of heating reaction is 180~200 DEG C in the step (1), the time for heating reaction is 18~ 20h。
Preferably, SnS in the step (2)2Ethylene glycol dispersion liquid in SnS2Substance amount and organic solvent volume Than for (0.0125~0.075) mmol:80mL.
Preferably, the amount ratio of the substance of the amount and bismuth nitrate of the substance of sodium tungstate is 0.5~0.6 in the step (2):1;
Sodium tungstate and SnS in the step (2)2Substance amount ratio be 1:(0.025~0.15).
Preferably, the temperature that solvent-thermal process reacts in the step (2) is 160~180 DEG C, solvent-thermal process reaction Time be 20~for 24 hours.
The present invention also provides the SnS described in above-mentioned technical proposal2-Bi2WO6Compound micron bouquet or above-mentioned preparation method Obtained SnS2-Bi2WO6Application of the compound micron bouquet as photochemical catalyst in carbon dioxide light-catalyzed reaction.
Preferably, the application includes the following steps:By the SnS2-Bi2WO6Compound micron bouquet is mixed with water, is obtained SnS2-Bi2WO6The aqueous dispersions of compound micron bouquet;Remove the SnS2-Bi2WO6In the aqueous dispersions of compound micron bouquet After gas, it is passed through CO2Gas is stood under non-illuminated conditions, and catalysis reaction is then carried out under illumination condition.
The present invention provides a kind of SnS2-Bi2WO6Compound micron bouquet, includes the SnS of flower ball-shaped2And Bi2WO6Particle;Institute State the SnS of flower ball-shaped2By SnS2Piece self assembly forms, the Bi2WO6Distribution of particles is in the SnS2Piece surface.In the present invention, Bi2WO6Distribution of particles is in the SnS2The surface of piece, forms hetero-junctions, promotes efficiently separating for electron-hole pair, simultaneously The formation of hetero-junctions can make SnS2Hole in valence band and Bi2WO6Electronics on conduction band combines, and effectively prevents electron hole pair Combination, and then can effectively prevent the compound of Pair production so that the photocatalytic activity of composite material significantly improves;And Petal chondritic SnS2Presence help to improve the specific surface area of composite material, increase the absorption area of visible light and anti- Active site is answered, to improve the photocatalysis efficiency of composite material.In the present invention, the sheet knot of the compound micron bouquet Structure, is conducive to light and is constantly reflected among, fully allows incident light and composite material to interact, light is avoided only to limit to In the position directly struck by light, and then improve photocatalysis efficiency.Embodiment the result shows that, by the present invention be prepared it is compound When material is used for carbon dioxide light-catalyzed reaction, methanol and ethyl alcohol are generated, by 4h light-catalyzed reactions, the yield of methanol reaches 50.20 μm of ol/g-Cat, the yield of ethyl alcohol is up to 19.70 μm of ol/g-Cat.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the spherical SnS of the petal that is prepared of embodiment 12Field emission scanning electron microscope figure;
Fig. 2 is the SnS that embodiment 1 is prepared2-Bi2WO6The field emission scanning electron microscope figure of compound micron bouquet;
Fig. 3 is the SnS that Examples 1 to 4 is prepared2-Bi2WO6Bi in compound micron bouquet and embodiment 12WO6With SnS2XRD diagram.
Specific implementation mode
The present invention provides a kind of SnS2-Bi2WO6Compound micron bouquet, including Bi2WO6With the SnS of flower ball-shaped2;The flower Spherical SnS2By SnS2Piece self assembly forms, the Bi2WO6It is distributed in the SnS2Piece surface.
In the present invention, the SnS of the flower ball-shaped2By SnS2Piece self assembly forms;In the present invention, the SnS2Piece Self-assembling method is preferably SnS2Piece cluster is at radial.In the present invention, the SnS2The thickness of piece preferably stands alone as 50~ 60nm, further preferably 52~55nm;In the present invention, the SnS2Bouquet diameter is preferably 5~6 μm.In the present invention, The SnS2The laminated structure of piece, is conducive to light and is constantly reflected among, fully allows incident light and composite material phase interaction With avoiding light from being only confined in certain part, and then improve photocatalysis efficiency.
In the present invention, the Bi2WO6For nano-grade structure;The Bi2WO6It is preferably dimensioned to be 25~30nm. In the present invention, the Bi2WO6It is distributed in the SnS2The surface of piece, the Bi under intermolecular force2WO6With the flower Petaloid SnS2It is stably connected with, forms hetero-junctions, promote efficiently separating for electron-hole pair so that the light of composite material is urged Change activity to significantly improve.
In the present invention, the SnS2-Bi2WO6The grain size of compound micron bouquet is preferably 5~6 μm, further preferably 5.2~5.5 μm.In the present invention, Bi2WO6It is distributed in the SnS2The surface of piece forms compound micron bouquet, keeps flower ball-shaped SnS2Bouquet diameter.
In the present invention, the SnS2-Bi2WO6SnS in compound micron bouquet2And Bi2WO6The amount ratio of substance be preferably (0.025~0.15):1, further preferably (0.05~0.10):1.
In the present invention, the SnS2-Bi2WO6The presence of the petal chondritic of compound micron bouquet helps to improve multiple The specific surface area of condensation material, and then the absorption to visible light is improved, the contact area of bigger is provided for light-catalyzed reaction system With more active sites, to improve the photocatalysis efficiency of composite material.
The present invention provides the SnS described in above-mentioned technical proposal2-Bi2WO6The preparation method of compound micron bouquet, including with Lower step:
(1) butter of tin, thiocarbamide and ethylene glycol are mixed, carries out heating reaction, obtains flower ball-shaped SnS2
(2) sodium tungstate and bismuth nitrate are added to the flower ball-shaped SnS2Ethylene glycol dispersion liquid in, carry out solvent heat seal At reaction, SnS is obtained2-Bi2WO6Compound micron bouquet.
The present invention mixes butter of tin, thiocarbamide and ethylene glycol, carries out heating reaction, obtains the SnS of flower ball-shaped2.At this In invention, the volume ratio of the amount of the substance of butter of tin, the amount of the substance of thiocarbamide and ethylene glycol is preferably 1.5~2mmol:8~ 10mmol:80mL, further preferably 1.8mmol:9mmol:80mL.The present invention is to the butter of tin, thiocarbamide and ethylene glycol Source there is no particular/special requirement, using well-known to those skilled in the art;In an embodiment of the present invention, the tetrachloro It is specially stannic chloride pentahydrate to change tin.
The present invention mixes butter of tin and thiocarbamide with ethylene glycol, makes full use of the viscosity advantage of ethylene glycol, hinders particle Mass transport process, and then reduce crystal growth rate, avoid agglomeration traits caused by too fast growth, and ethylene glycol can rise To the effect of surfactant;The present invention is using ethylene glycol as directed agents, to SnS2Crystal growth when nucleation process controlled System plays the role of structure directing during Crystallization, and then forms laminated structure, and effectively finishing is in self assembly Pattern finally obtains the spherical SnS of petal2
The present invention does not have particular/special requirement to the hybrid mode of the butter of tin, thiocarbamide and ethylene glycol, using this field skill Material hybrid mode known to art personnel.
After the mixing, the mixture of the butter of tin, thiocarbamide and ethylene glycol is carried out heating reaction by the present invention, is obtained The SnS of flower ball-shaped2.In the present invention, the temperature of the heating reaction is preferably 180~200 DEG C, further preferably 185~ 190℃.In the present invention, the time of the heating reaction is preferably 18~20h, further preferably 19~19.5h.The present invention There is no particular/special requirement to the specific implementation mode of the heating, using the embodiment of heating well-known to those skilled in the art .In the present invention, the heating reaction preferably carries out in a kettle.
After the heating reaction, the present invention preferably post-processes the heating reaction product, obtains flower ball-shaped SnS2。 In the present invention, the post-processing preferably includes:The heating reaction product is cooling successively, washing, centrifugation and drying.At this In invention, the temperature after cooling is preferably room temperature, further preferably 25~30 DEG C.The present invention is to the crystallisation by cooling Mode does not have particular/special requirement, uses crystallisation by cooling mode well-known to those skilled in the art can realize the abundant analysis of solute Go out.
In the present invention, the washing preferably use successively ethyl alcohol and distilled water to the heating reaction product of the precipitation into Row washing.The present invention does not have particular/special requirement to the mode of the washing, using mode of washing well-known to those skilled in the art .In an embodiment of the present invention, the washing is specially to be washed 3 times using ethyl alcohol, adopt and be washed with distilled water 3 times.
After completing the washing, the present invention preferably centrifuges the washed product, obtains SnS2Bouquet.The present invention couple The specific implementation mode of the centrifugation does not have particular/special requirement, uses centrifugation well-known to those skilled in the art can realize The separation of feed liquid.In the present invention, the centrifugation carries out preferably in centrifuge, and the present invention does not have the model of the centrifuge Particular/special requirement.
After completing the centrifugation, the present invention is preferably dried solid product after the centrifugation, and it is spherical to obtain petal SnS2.In the present invention, the temperature of the drying is preferably 60~80 DEG C, further preferably 65~70 DEG C;In the present invention, The time of the drying is preferably 10~12h, further preferably 11~11.5h.The present invention does not have the mode of the drying Particular/special requirement, using drying mode well-known to those skilled in the art;In an embodiment of the present invention, the dry tool Body carries out in an oven.
In the present invention, the SnS2For flower ball-shaped structure, by SnS2Piece self assembly forms;The SnS2The thickness of piece is excellent It is selected as 50~60nm.In the present invention, the SnS2The diameter of bouquet is preferably 5~6 μm.
Obtain the SnS of bouquet structure2Afterwards, sodium tungstate and bismuth nitrate are added to the SnS by the present invention2Ethylene glycol dispersion In liquid, solvent-thermal process reaction is carried out, SnS is obtained2-Bi2WO6Compound micron bouquet.
In the present invention, the SnS2Ethylene glycol dispersion liquid in SnS2Substance amount and ethylene glycol volume ratio it is preferred For (0.0125~0.075) mmol:80mL, further preferably (0.025~0.055) mmol:80mL.In the present invention, institute The use of ethylene glycol is stated, can not only be realized to SnS2Dispersion, moreover it is possible to contribute to the dispersion of sodium tungstate and bismuth nitrate, Jin Erbian In sodium tungstate and bismuth nitrate and SnS2Come into full contact with, it is ensured that Bi2WO6Synthesis.The present invention is to the SnS2Ethylene glycol point The manner of formulation of dispersion liquid does not have particular/special requirement, using the manner of formulation of organic solution well-known to those skilled in the art; In an embodiment of the present invention, the SnS2Ethylene glycol dispersion liquid specifically using by SnS2It is scattered in ethylene glycol.
Obtain SnS2Ethylene glycol dispersion liquid after, sodium tungstate and bismuth nitrate are added to the SnS by the present invention2Ethylene glycol In dispersion liquid, solvent-thermal process reaction is carried out, SnS is obtained2-Bi2WO6Compound micron bouquet.In the present invention, the sodium tungstate Amount ratio with the substance of bismuth nitrate is preferably 0.5~0.6:1, further preferably 0.55:1;The sodium tungstate and SnS2Object The amount of matter is than preferably 1:(0.025~0.15), further preferably 1:(0.05~0.10).In the present invention, the wolframic acid Sodium and bismuth nitrate are added to the SnS2The process of ethylene glycol dispersion liquid preferably carry out under agitation, help to disperse It is even;The present invention does not have particular/special requirement to the specific implementation mode of the stirring, using stirring well-known to those skilled in the art Mode.
Sodium tungstate and bismuth nitrate are added to and are dispersed with SnS by the present invention2Ethylene glycol dispersion liquid in, contribute to solvent heat seal Bi is obtained at reaction process2WO6When, it is dispersed in SnS in granular form2Petal surface.
The present invention carries out solvent-thermal process reaction to obtained mixed solution, obtains SnS2-Bi2WO6Compound micron bouquet. In the present invention, the temperature of the solvent-thermal process reaction is preferably 160~180 DEG C, further preferably 165~170 DEG C;Institute The time for stating solvent-thermal process reaction is preferably 20~for 24 hours, further preferably 22~23h.In the present invention, the solvent heat Synthetic reaction preferably carries out in a kettle;The present invention does not have particular/special requirement to the model of reaction kettle, using people in the art Known to member.
The present invention realizes that the synthetic reaction of bismuth nitrate and sodium tungstate obtains wolframic acid in the solvent-thermal process reaction process Bismuth, and synthesized bismuth tungstate can it is fully dispersed in a solvent, synthesized bismuth tungstate and SnS2Between because intermolecular Graininess Bi is realized in the effect of interaction force2WO6In SnS2The attachment of petal surface.
After the solvent-thermal process reaction, the present invention preferably post-processes the solvent-thermal process reaction product, obtains To SnS2-Bi2WO6Compound micron bouquet.In the present invention, the post-processing preferably includes:The solvent-thermal process is reacted and is produced Object cooling, washing, centrifugation and drying successively.In the present invention, the temperature after cooling is preferably room temperature, further preferably 25~30 DEG C.The present invention does not have particular/special requirement to the mode of the crystallisation by cooling, using well-known to those skilled in the art cold But crystallization mode is can realize the abundant precipitation of solute.
In the present invention, the washing preferably use successively ethyl alcohol and distilled water to the heating reaction product of the precipitation into Row washing.The present invention does not have particular/special requirement to the mode of the washing, using mode of washing well-known to those skilled in the art .In an embodiment of the present invention, the washing is specially to be washed 3 times using ethyl alcohol, adopt and be washed with distilled water 3 times.
After completing the washing, the present invention preferably centrifuges the washed product, obtains SnS2-Bi2WO6It is compound micro- Popped rice ball.The present invention does not have particular/special requirement, use well-known to those skilled in the art the specific implementation mode of the centrifugation Centrifugation is can realize the separation of feed liquid.In the present invention, the centrifugation carries out preferably in centrifuge, and the present invention is to described The model of centrifuge does not have particular/special requirement.
After completing the centrifugation, the present invention is preferably dried solid product after the centrifugation, obtains SnS2-Bi2WO6 Compound micron bouquet.In the present invention, the temperature of the drying is preferably 60~80 DEG C, further preferably 65~70 DEG C; In the present invention, the time of the drying is preferably 10~12h, further preferably 10.5~11h.The present invention is to the drying Mode does not have particular/special requirement, using drying mode well-known to those skilled in the art.
The present invention also provides the SnS described in above-mentioned technical proposal2-Bi2WO6Compound micron bouquet exists as photochemical catalyst Application in carbon dioxide light-catalyzed reaction.In the present invention, the application is preferred is specially:By the SnS2-Bi2WO6It is compound Micron bouquet is used for carbon dioxide light-catalyzed reaction as catalyst, obtains methanol and ethyl alcohol.The present invention is by the SnS2- Bi2WO6Compound micron bouquet is used for photo catalytic reduction CO as catalyst2Organic-fuel is generated, hypercapnia can be solved Caused environmental hazard, moreover it is possible to provide effective way to generate more cleaning organic-fuels.
In the present invention, described apply further preferably includes:By the SnS2-Bi2WO6Compound micron bouquet is mixed with water It closes, obtains SnS2-Bi2WO6The aqueous dispersions of compound micron bouquet;Remove the SnS2-Bi2WO6The moisture of compound micron bouquet After gas in dispersion liquid, it is passed through CO2Gas is stood under non-illuminated conditions, and catalysis reaction is then carried out under illumination condition. In the present invention, the SnS2-Bi2WO6SnS in the aqueous solution of compound micron bouquet2-Bi2WO6The quality and water of compound micron bouquet Volume ratio be preferably 20~50mg:50~100mL;The removing method of the gas is preferably vacuum degassing, and the present invention is to institute Stating vacuum degassed mode does not have particular/special requirement, using vacuum degassing mode well-known to those skilled in the art.At this In invention, the CO2Gas is from the SnS2-Bi2WO6It is risen after gas removal in the aqueous dispersions of compound micron bouquet to carrying For being continually fed into before illumination condition.In the present invention, the CO2The rate that is passed through of gas is preferably 50~100mL/min.
In the present invention, the time of the standing under the non-illuminated conditions is preferably 0.5~1h;Under the non-illuminated conditions Standing make CO2It is fully adsorbed on catalyst surface, reaches adsorption equilibrium, while CO2Solubility in water also reaches full With.In the present invention, the illumination condition is preferably the illumination condition within the scope of wavelength >=420nm;The wave of the illumination condition Long is more preferably 450~720nm;The catalysis reaction time under the illumination condition is preferably 4~6h.
In an embodiment of the present invention, the temperature of the light-catalyzed reaction is preferably 4 DEG C;The light-catalyzed reaction preferably exists It is carried out in closed quartz reactor.The light-catalyzed reaction is specially:(1) by 50mL ultra-pure waters and 50mg SnS2-Bi2WO6 Compound micron bouquet mixing;(2) after removing the gas in water removal by the way of vacuumizing under the conditions of magnetic agitation, with 50mL/ The rate of min is passed through high-purity CO2After light reaction 4h being carried out after gas half an hour under the 300W Xenon light shinings of wavelength >=420nm, Qualitative and quantitative analysis is carried out to the product in solution, determines the content of methanol and ethyl alcohol in product.
With reference to embodiment to a kind of SnS provided by the invention2-Bi2WO6Compound micron bouquet and preparation method thereof and Using being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) flower-shaped SnS2Synthesis:Weigh the SnCl of 0.525g4·5H2O is dissolved in 80mL ethylene glycol, will after dissolving The thiocarbamide of 0.61g is added thereto, and stirring is to dissolving, and ultrasonic disperse moves in the reaction kettle of 100mL, hydro-thermal under the conditions of 180 DEG C 18h, after reaction cooled to room temperature.Product is washed repeatedly with ethyl alcohol and deionized water respectively, is centrifuged, at 60 DEG C Oven drying 12h to get petal-shaped SnS2
(2)SnS2/Bi2WO6Synthesis:Bi (the NO of 0.485g are weighed respectively3)3·5H2The Na of O and 0.16g2WO4·2H2O It is separately added into and is dispersed with 0.0125mmol SnS280mL ethylene glycol solutions in, stir and ultrasonic disperse it is uniform, it is molten to obtain yellow Liquid is transferred in 100mL reaction kettles, is heated at 160 DEG C for 24 hours, after reaction cooled to room temperature.
Product is washed repeatedly with ethyl alcohol and deionized water respectively, is realized and is separated by solid-liquid separation, and reaction solid product is obtained, at 60 DEG C Oven drying 12h, obtain SnS2-Bi2WO6Compound micron bouquet.
To the flower ball-shaped SnS being prepared2And SnS2-Bi2WO6Compound micron bouquet carries out field emission scanning electron microscope point Analysis, it is as a result as depicted in figs. 1 and 2 respectively.By Fig. 1 and Fig. 2 it is found that the SnS being prepared2With petal chondritic, and Composites are bouquet structure;It is also known by Fig. 2, Bi2WO6Particle is scattered in sheet SnS2Surface.
Obtained SnS2-Bi2WO6SnS in compound micron bouquet2And Bi2WO6Substance amount ratio be 0.025:1, it uses SnS2- BW-2.5 is indicated.The SnS that the present invention will obtain2-Bi2WO6Compound micron bouquet and pure Bi2WO6And SnS2It carries out XRD analysis, from the figure 3, it may be seen that single Bi2WO6XRD diffracting spectrums, all characteristic peaks can be proved that material belongs to orthorhombic system Bi2WO6, and match with standard card PDF#39-0256, (131), (200), (260), (133) corresponding angle of diffraction difference For 2 θ=28.3 °, 32.8 °, 47.0 °, 55.9 °;Single SnS2With (001) of standard card PDF#23-0677, (100), (101), (102), (110), (111), (103), (202), (113) crystal face are consistent, illustrate to successfully synthesize the flower-shaped knot of pure phase Structure SnS2, the position " ■ " corresponds to SnS in composite material in the diagram of composite material in figure2The position of characteristic peak, it is seen that composite material In existing Bi2WO6Characteristic peak have SnS again2Characteristic peak, illustrate the composite material being prepared be SnS2-Bi2WO6
Embodiment 2
Compound micron bouquet is prepared in the way of embodiment 1, difference lies in the present embodiment is according to SnS2And Bi2WO6's The amount ratio of substance is 0.05:1, control Bi (NO3)3·5H2O and Na2WO4·2H2O and SnS2Dosage, obtained SnS2- Bi2WO6SnS in compound micron bouquet2And Bi2WO6Substance amount ratio be 0.05:1, use SnS2- BW-5 is indicated.
Embodiment 3
Compound micron bouquet is prepared in the way of embodiment 1, difference lies in the present embodiment is according to SnS2And Bi2WO6's The amount ratio of substance is 0.1:1, control Bi (NO3)35H2O and Na2WO4·2H2O and SnS2Dosage, obtained SnS2-Bi2WO6 SnS in compound micron bouquet2And Bi2WO6Substance amount ratio be 0.1:1, use SnS2- BW-10 is indicated.
Embodiment 4
Compound micron bouquet is prepared in the way of embodiment 1, difference lies in the present embodiment is according to SnS2And Bi2WO6's The amount ratio of substance is 0.15:1, control Bi (NO3)3·5H2O and Na2WO4·2H2O and SnS2Dosage, obtained SnS2- Bi2WO6SnS in compound micron bouquet2And Bi2WO6Substance amount ratio be 0.15:1, use SnS2- BW-15 is indicated.
SnS is prepared to Examples 1 to 42-Bi2WO6The petal that compound micron bouquet and embodiment are prepared is spherical SnS2And the SnS of petal ball surface2XRD analysis is carried out, the results are shown in Figure 3.From the figure 3, it may be seen that being made under the conditions of different mol ratio Standby obtained composite material is SnS2-Bi2WO6, the ingredient for forming the laminated structure part of microballoon main body is SnS2
The flower ball-shaped SnS that embodiment 2~4 is prepared respectively2And SnS2-Bi2WO6Compound micron bouquet carries out field Emit scanning electron microscope analysis, the SnS that can be clearly prepared2With petal chondritic, and composites are flower Spherical structure;Bi2WO6Particle is scattered in sheet SnS2Surface.
Embodiment 5:
The SnS that Examples 1 to 4 is prepared2-Bi2WO6Compound micron bouquet, pure Bi2WO6, pure SnS2And SnS2With Bi2WO6Substance amount ratio be 0.1:1 physical mixture is used for carbon dioxide light-catalyzed reaction respectively as photochemical catalyst.
Light-catalyzed reaction carries out in closed quartz reactor, and temperature control is at 4 DEG C with maintaining reaction temperature.It is reacting 50mL ultra-pure waters and 50mg photochemical catalysts are added in device, it is continuous logical after the gas removed in water is vacuumized under the conditions of magnetic agitation Enter high-purity CO2Gas (flow 50mL/min) continues after dark reaction half an hour under the 300W Xenon light shinings of wavelength >=420nm After carrying out light reaction 4h, the content of methanol and ethyl alcohol in product, methanol and alcohol yied such as 1 institute of table of different catalysts are measured Show:
Under the conditions of the different photochemical catalysts of table 1, the methanol of carbon dioxide light-catalyzed reaction and the yield of ethyl alcohol
As shown in Table 1, the SnS that the present invention is prepared2-Bi2WO6Compound micron bouquet is anti-for carbon dioxide photocatalysis It answers, methanol yield is above 20 μm of ol/g-Cat, and alcohol yied is above 10 μm of ol/g-Cat;Far above pure SnS2, pure Bi2WO6 And Bi2WO6And SnS2Physical mixture as in carbon dioxide light-catalyzed reaction when catalyst methanol and ethyl alcohol yield. Wherein, the mensuration mode of the yield of methanol and ethyl alcohol is:The content for measuring methanol and ethyl alcohol in water after light reaction first, further according to The dosage of catalyst calculates the content of methanol and ethyl alcohol that the catalysis of every gram of catalyst theory generates.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of SnS2-Bi2WO6Compound micron bouquet, including Bi2WO6With the SnS of flower ball-shaped2;The SnS of the flower ball-shaped2By SnS2Piece self assembly forms, the Bi2WO6It is distributed in the SnS2Piece surface.
2. SnS according to claim 12-Bi2WO6Compound micron bouquet, which is characterized in that the SnS2-Bi2WO6It is compound The grain size of micron bouquet is 5~6 μm;
The SnS2-Bi2WO6SnS in compound micron bouquet2And Bi2WO6Substance amount ratio be (0.025~0.15):1.
3. SnS as claimed in claim 1 or 22-Bi2WO6The preparation method of compound micron bouquet, includes the following steps:
(1) butter of tin, thiocarbamide and ethylene glycol are mixed, carries out heating reaction, obtains flower ball-shaped SnS2
(2) sodium tungstate and bismuth nitrate are added to the flower ball-shaped SnS2Ethylene glycol dispersion liquid in, carry out solvent-thermal process it is anti- It answers, obtains SnS2-Bi2WO6Compound micron bouquet.
4. preparation method according to claim 3, which is characterized in that the amount of the substance of butter of tin in the step (1), The amount of the substance of thiocarbamide and the volume ratio of ethylene glycol are 1.5~2mmol:8~10mmol:80mL.
5. preparation method according to claim 3 or 4, which is characterized in that the temperature of heating reaction is in the step (1) 180~200 DEG C, the time for heating reaction is 18~20h.
6. preparation method according to claim 3, which is characterized in that SnS in the step (2)2Ethylene glycol dispersion liquid in SnS2Substance amount and ethylene glycol volume ratio be (0.0125~0.075) mmol:80mL.
7. preparation method according to claim 6, which is characterized in that the amount and nitre of the substance of sodium tungstate in the step (2) The amount ratio of the substance of sour bismuth is 0.5~0.6:1;
Sodium tungstate and SnS in the step (2)2Substance amount ratio be 1:(0.025~0.15).
8. the preparation method according to claim 3 or 7, which is characterized in that solvent-thermal process reacts in the step (2) Temperature be 160~180 DEG C, solvent-thermal process reaction time be 20~for 24 hours.
9. SnS as claimed in claim 1 or 22-Bi2WO6It is prepared described in compound micron bouquet or claim 3~8 any one SnS made from method2-Bi2WO6Application of the compound micron bouquet as photochemical catalyst in carbon dioxide light-catalyzed reaction.
10. application according to claim 9, which is characterized in that the application includes the following steps:By the SnS2- Bi2WO6Compound micron bouquet is mixed with water, obtains SnS2-Bi2WO6The aqueous dispersions of compound micron bouquet;Remove the SnS2- Bi2WO6After gas in the aqueous dispersions of compound micron bouquet, it is passed through CO2Gas is stood under non-illuminated conditions, then in light Catalysis reaction is carried out according under the conditions of.
CN201810193853.XA 2018-03-09 2018-03-09 A kind of compound micron bouquet of artificial gold-bismuth tungstate and its preparation method and application Pending CN108355678A (en)

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