CN103657639B - Preparation method and silicon modification method of visible light catalysis material for graphene/bismuth tungstate flake nanostructure - Google Patents
Preparation method and silicon modification method of visible light catalysis material for graphene/bismuth tungstate flake nanostructure Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 60
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 58
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 57
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 241000446313 Lamella Species 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 16
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- 238000003756 stirring Methods 0.000 claims description 6
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- 241001502050 Acis Species 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
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Abstract
The invention relates to a preparation method and silicon modification method of a visible light catalysis material for a graphene/bismuth tungstate flake nanostructure. According to the preparation method and the silicon modification method, with bismuth nitrate, tungstate, ethyl orthosilicate and graphene as raw materials, the solar catalysis material for the graphene/bismuth tungstate flake nanostructure is prepared by the steps including an organic electrolyte assisted hydrothermal method, low temperature freezing, ageing, washing, drying and the like, and the catalysis performance of the material is further enhanced by silicon modification. The preparation method and the silicon modification method disclosed by the invention have the greatest characteristics that the strong-adsorption and high-activity visible light catalysis material for a graphene/bismuth nitrate flake is obtained by using the low-temperature freezing organic electrolyte assisted hydrothermal method, and the performance of the graphene/bismuth tungstate flake structure is further improved by silicon modification. The catalysis material can be applied to the fields of sewage treatment, light degradation of water, air purification, solar batteries and the like.
Description
Technical field
The invention belongs to field of photocatalytic material, relate to preparation method and the Si modification method thereof of a kind of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material.
Background technology
Bismuth tungstate (Bi
2wO
6) be by octahedral WO
6and Bi
2o
2the one typical case n type semiconductor that lamination is tired out, having the character such as fabulous chemical property, unique ferroelectric properties, catalytic performance and nonlinear dielectric susceptibility, is a kind of well visible light catalyst material.Since Kudo and Hijii reported first bismuth tungstate in 1999 has the activity of photochemical catalyzing, cause the extensive concern of countries in the world scientific worker.Bi
2wO
6valence band be made up of Bi6s and O2p hybridized orbit, and conduction band is made up of W5d track, makes energy gap narrower (being about 2.69 eV), has good absorbing properties to the wavelength of 460 below nm.In addition, Bi6s and O2p orbital hybridization makes valence band more disperse, and is conducive to the movement of photohole in valence band, hinders the compound of itself and light induced electron, improves the photocatalysis oxidation reaction to organic pollution.Research shows, no matter is in water or in air, Bi
2wO
6can catalysis mineralising organic dyestuff, as pollutants such as phenol, acetaldehyde, benzene, ammonia, there is in the field such as water treatment and environmental protection very large commercial value and application prospect.But because the quantum yield of bismuth tungstate material is low, the photo-generate electron-hole commute compound of generation, demonstrates lower photocatalysis efficiency.In addition, tungsten and bismuth are rare metals, and price is more expensive, thus limit bismuth tungstate extensive use industrially.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide and a kind of there is under sunshine strong absorption, the preparation method of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material of high catalytic activity and Si modification method thereof.The present invention is carrier with Graphene, utilize bismuth tungstate and Si modification bismuth tungstate lamellar structure grapheme modified, thus form a kind of novel nano derived material under sunshine with strong absorption, highlight catalytic active.
Technical conceive of the present invention is: grapheme modified by organic bath, utilizes the special nature of organic bath to obtain Bismuth tungstate nano-sheet layer, and strengthens the combination between Graphene and bismuth tungstate lamella.On this basis, utilize Si modification bismuth tungstate lamella improve photocatalysis performance further and reduce costs, promote that it is applied.Graphene is by individual layer or the tightly packed bi-dimensional cellular shape lattice structure carbonaceous material of which floor carbon atom, has huge specific area (calculated value 2630 m
2g
-1); In test material, the intensity of Graphene is the highest, reaches 130 Gpa, is more than 100 times of steel; Its carrier mobility reaches 15000 cm
2v
-1s
-1, be the twice with the indium antimonide materials of most high mobility known at present, exceeding more than 10 times of commercial silicon chip mobility, is the ideal carrier of nanocatalyst.Particularly paired not can move freely electronics containing a large amount of in Graphene, have larger Electronic saving energy, can catch and light conducting excitation electron, the compound hindering or stop photo-excited electron and hole in semiconductor catalyst right, improves photocatalysis performance.In addition, Graphene specific area is large, nanocatalyst effectively can be stoped to reunite and increase its surface area, improve the adsorption capacity of material.Therefore, strengthen bismuth tungstate with Graphene, be expected to obtain strong absorption, efficient visible light catalysis material, be with a wide range of applications in fields such as sewage disposal, environmental protection and solar cells.
For realizing the present invention, technical scheme of the present invention is:
A preparation method for Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material, concrete steps are:
(1) graphene solution being 0.1g/L ~ 1.2 g/L by 1 mL ~ 15 mL concentration joins 40mL ~ 100mL deionized water for ultrasonic and disperses 20 min ~ 40 min, obtains graphene dispersing solution;
(2) described graphene dispersing solution ultrasonic disperse 15 min ~ 30 min at 0 DEG C-40 DEG C, obtains finely dispersed solution;
(3) organic bath add 0.1g ~ 4 g tungstates in described finely dispersed solution, being made up of 0.5g ~ 3g polyacrylic acid and 0.1g ~ 1 g softex kw, after stirring and dissolving, ultrasonic agitation 15 min ~ 60 min is continued at the temperature of 35 DEG C ~ 50 DEG C, then freezing 1h ~ 24 h at the temperature of-20 DEG C ~ 0 DEG C, add 0.485g ~ 1.94 g bismuth salt again, ultrasonic agitation 20 min ~ 30 min, obtains finely dispersed colloidal liquid;
(4) by described colloidal liquid ageing 0.5 h ~ 5 h at 20 DEG C ~ 40 DEG C, then proceed to reaction kettle for reaction 6 h ~ 18 h, reaction temperature is 90 DEG C ~ 180 DEG C, obtains reactant;
(5) described reactant is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 5 ~ 6 times, obtaining washings; Washings is toasted 12 hours ~ 24 hours at 60 DEG C ~ 80 DEG C, then obtains product after grinding.
Step (1) described Graphene is preferably graphene oxide and redox graphene.
Step (3) described tungstates is preferably sodium tungstate or ammonium tungstate, and described bismuth salt is bismuth nitrate.
A Si modification method for Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material, identical with the step of above-mentioned preparation method, in step (2) described graphene dispersing solution, only add the esters of silicon acis of 1 mL-5 mL.
Described esters of silicon acis is preferably ethyl orthosilicate.
Principle of the present invention is: with bismuth nitrate, tungstates, Graphene and ethyl orthosilicate for raw material, polyacrylic acid and softex kw are organic bath, use organic bath assisting alcohol-hydrothermal method to prepare Graphene/bismuth tungstate lamella visible light catalytic material.Modified the dispersion and surface-active that improve Graphene by organic bath, strengthen the interaction between Graphene and bismuth tungstate; Rely on the character of organic bath simultaneously, realize bismuth tungstate nano material uniform deposition on graphene film, being formed with Graphene is the lamella visible light catalytic material of template.The special construction of Graphene and excellent properties, add the quantum yield of bismuth tungstate and reduce the right compound of its photo-generate electron-hole, improving its photocatalysis performance.In addition, use Si modification Graphene/bismuth tungstate lamella, make silicon and bismuth tungstate form effective combination, improve the photocatalysis performance of Graphene/bismuth tungstate lamellar structure further, and reduce preparation cost, thus promote that it is applied.
The softex kw that the present invention is used and polyacrylic acid belong to cation and anion surfactant respectively, be easy to form condensate by electrostatic interaction, these organic polymers are known from experience formation wire and are attached on Graphene at low temperatures, realize function of surface functionalized graphene, add the surface-active of Graphene.Organic bath on graphene film is easy to attract the metal Bi ion in solution, and these Bi ions and the tungstate ion added generate bismuth tungstate and precipitate (Bi
3++ WO
4 2-→ Bi
2wO
6), the further nucleation and growth process of these bismuth tungstates, grows into nano-lamellar structure and is attached on graphene film.Graphene has larger specific area and high electric conductivity, is easy to catch the light induced electron in bismuth tungstate lamella, reduce light induced electron and hole between compound, improve photocatalysis efficiency; The specific area that Graphene is huge simultaneously can increase the specific area of bismuth tungstate lamella, strengthens adsorption capacity.Therefore, absorption, high activity Graphene/bismuth tungstate lamella visible light catalytic material is by force obtained.In addition, silica is a kind of porous material, is commonly used to make the specific area that catalyst carrier improves nanocatalyst.The present invention utilizes teos hydrolysis to generate silica (as Si (C
2h
5o)
4+ 2H
2o=4C
2h
5oH+SiO
2), improve surface area; Simultaneously ethyl orthosilicate easily and Bi ion generation chemical reaction form intermediateness (as Bi
3++ Si (OC
2h
5)
4→ Bi
2siO
22), its photocatalysis performance will be improved further.
Compared with prior art, advantage of the present invention is:
1, modify by the organic bath of softex kw and polyacrylic acid composition the dispersion and surface-active that improve Graphene, strengthen the interaction between Graphene and bismuth tungstate; Rely on the character of organic bath simultaneously, realize bismuth tungstate nano material uniform deposition on graphene film, being formed with Graphene is the lamella visible light catalytic material of template.
2, the present invention uses Si modification Graphene/Bismuth tungstate nano-sheet; by forming intermediate product between Si and Bi; improve the photocatalysis efficiency of Graphene/Bismuth tungstate nano-sheet; to greatly reduce its use cost, thus promote its application in the fields such as sewage disposal, environmental protection and solar cell.
Accompanying drawing explanation
Fig. 1 is the SEM image of embodiment 1 Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material;
Fig. 2 is the TEM image of embodiment 1 Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material;
Fig. 3 is the SEM image of embodiment 2 Graphenes/bismuth tungstate lamella nano-structure visible-light catalysis material;
Fig. 4 is the TEM image of embodiment 2 Graphenes/bismuth tungstate lamella nano-structure visible-light catalysis material;
Fig. 5 is the XRD figure of embodiment 1 and example 2 Graphenes/bismuth tungstate lamella nano-structure visible-light catalysis material; Wherein a is the XRD curve representing the Graphene/bismuth tungstate material (embodiment 1) not carrying out Si modification, and b is the XRD curve of the Graphene/bismuth tungstate material (embodiment 2) of Si modification of the present invention.
Fig. 6 is that embodiment 1 and example 2 Graphenes/bismuth tungstate lamella nano-structure visible-light catalysis material are to the absorption of rhodamine and the degraded situation under simulated solar irradiation; Wherein a be represent do not carry out Si modification Graphene/bismuth tungstate material (embodiment 1) to organic degradation curve, b is that the Graphene/bismuth tungstate material (embodiment 2) of the present invention's Si modification is to organic degradation curve.Within 0 minute, represent the absorption situation being positioned at dark state in the past, within 0 minute, represent and regulate organic concentration in solution to initial concentration, within 0 minute, to represent the degraded situation after turning on light later.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention will be further explained
embodiment 1(does not carry out Si modification)
(1) graphene oxide solution being 0.6 g/L by 3 mL concentration joins 70mL deionized water for ultrasonic and disperses 30 min, obtains stable graphene dispersing solution;
(2) above-mentioned solution is stirred ultrasonic disperse 15 ~ 30 min at the temperature of 0 ~ 40 DEG C, obtain finely dispersed solution;
(3) organic bath add 0.3 g sodium tungstate in above-mentioned solution, being made up of 2 g polyacrylic acid (degree of polymerization is 800-1000) and 0.8 g softex kw, after stirring and dissolving, continues ultrasonic agitation 15 min at the temperature of 35 DEG C; At the temperature of 0 DEG C, add 0.45 g bismuth nitrate again after freezing 14 h under ultrasonic agitation, ultrasonic agitation 30 min, obtains colloidal fluid;
(4) by room temperature (25 DEG C) ageing 2 h of the colloidal solution described in step (3), proceed to reaction kettle for reaction 10 h that volume is 100 mL afterwards, reaction temperature is 120 DEG C;
(5) reactant described in step (4) is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 5 times; Toasted 12 hours at 65 DEG C by washings, obtain Graphene/bismuth tungstate lamella nanostructured after grinding, its electronic features as depicted in figs. 1 and 2.The electron micrograph image display of the sample that Fig. 1 and Fig. 2 obtains, the composite obtained presents flaky nanometer structure.X-ray diffractometer is analyzed (Fig. 5 a curve) and can be drawn, obtains composite main manifestations and goes out Bi
2wO
6the crystal face of crystal.Fig. 6 curve a shows the degraded situation under the absorption to rhodamine B of composite and visible ray.As can be seen from Figure, in 0.25g sample energy adsorbent solution about 50% rhodamine B (300 mL concentration are 1.0 × 10
-5mol/L), when increase solution concentration is to 1.0 × 10
-5after mol/L, the xenon lamp (500 W) opened with recirculated cooling water irradiates, the rhodamine B that 40 min substantially can be whole in degraded solutions.These results show, obtain Graphene/bismuth tungstate composite that product is lamellar structure, and have well absorption and photocatalysis performance to rhodamine B organic matter.
embodiment 2:(carries out Si modification)
(1) the redox graphene solution being 0.8 g/L by 12 mL concentration joins 60 mL deionized water for ultrasonic and disperses 40 min, obtains stable graphene dispersing solution;
(2) in above-mentioned solution, add 3 mL ethyl orthosilicates, then at the temperature of 30 DEG C, stir ultrasonic disperse 30 min, obtain finely dispersed solution, and leave standstill 18 h;
(3) organic bath add 3.042 g ammonium tungstates in above-mentioned solution, being made up of 2 g polyacrylic acid and 0.8 g softex kw, after stirring and dissolving, continues ultrasonic agitation 30 min at the temperature of 40 DEG C; At the temperature of-10 DEG C, add 0.8 g bismuth nitrate after freezing 12 h under ultrasonic agitation, ultrasonic agitation 30 min, obtains colloidal fluid;
(4) by room temperature (25 DEG C) ageing 1 h of the colloidal solution described in step (3), proceed to reaction kettle for reaction 16 h that volume is 100 mL afterwards, reaction temperature is 160 DEG C;
(5) reactant described in step (4) is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 6 times; Washings is toasted 20 hours at 70 DEG C, obtains the Graphene/bismuth tungstate lamella nanostructured of Si modification after grinding, as shown in Figure 3 and Figure 4.
The electron micrograph image of sample is shown, the composite obtained presents flaky nanometer structure, as shown in Figure 3 and Figure 4.X-ray diffractometer analysis result (Fig. 5 curve b) draws, obtains composite except there is Bi
2wO
6outside the crystallographic plane diffraction peak of crystal, also find Bi
12siO
22the diffraction maximum of crystal, the silicon that this explanation adds and bismuth define interaction.Fig. 6 curve b (the degraded situation under the absorption to rhodamine B of composite and visible ray) display, in 0.25g sample energy adsorbent solution about 80% rhodamine B (300 mL concentration are 1.0 × 10
-5mol/L), when increase solution concentration is to 1.0 × 10
-5after mol/L, the xenon lamp (500 W) opened with recirculated cooling water irradiates, whole rhodamine B in 40 min energy degraded solutions.These results show, Graphene/bismuth tungstate the composite of Si modification still shows as lamellar structure, well absorption and photocatalysis performance are also shown to rhodamine B organic matter, and is better than not by the absorption of Si modification Graphene/bismuth tungstate composite and photocatalysis effect.
Claims (7)
1. a preparation method for Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material, it is characterized in that, concrete steps are:
(1) graphene solution being 0.1g/L ~ 1.2 g/L by 1 mL ~ 15 mL concentration joins 40mL ~ 100mL deionized water for ultrasonic and disperses 20 min ~ 40 min, obtains graphene dispersing solution;
(2) described graphene dispersing solution ultrasonic disperse 15 min ~ 30 min at 0 DEG C-40 DEG C, obtains finely dispersed solution;
(3) organic bath add 0.1g ~ 4.0 g tungstates in described finely dispersed solution, being made up of 0.5g ~ 3g polyacrylic acid and 0.1g ~ 1 g softex kw, after stirring and dissolving, ultrasonic agitation 15 min ~ 60 min is continued at the temperature of 35 DEG C ~ 50 DEG C, then freezing 1h ~ 24 h at the temperature of-20 DEG C ~ 0 DEG C, add 0.485g ~ 1.94 g bismuth salt again, ultrasonic agitation 20 min ~ 30 min, obtains finely dispersed colloidal liquid;
(4) by described colloidal liquid ageing 0.5 h ~ 5 h at 20 DEG C ~ 40 DEG C, then proceed to reaction kettle for reaction 6 h ~ 18 h, reaction temperature is 90 DEG C ~ 180 DEG C, obtains reactant;
(5) described reactant is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 5 ~ 6 times, obtaining washings; Washings is toasted 12 hours ~ 24 hours at 60 DEG C ~ 80 DEG C, then obtains product after grinding.
2. the preparation method of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material according to claim 1, it is characterized in that, step (1) described Graphene is graphene oxide and redox graphene.
3. the preparation method of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material according to claim 1 or 2, it is characterized in that, step (3) described tungstates is sodium tungstate or ammonium tungstate, and described bismuth salt is bismuth nitrate.
4. a Si modification method for Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material, it is characterized in that, concrete steps are:
(1) graphene solution being 0.1g/L ~ 1.2 g/L by 1 mL ~ 15 mL concentration joins 40mL ~ 100mL deionized water for ultrasonic and disperses 20 min ~ 40 min, obtains graphene dispersing solution;
(2) add the esters of silicon acis of 1 mL-5 mL in described graphene dispersing solution, at 0 DEG C-40 DEG C, ultrasonic disperse 15 min ~ 30 min, obtains finely dispersed solution;
(3) organic bath add 0.1g ~ 4.0 g tungstates in described finely dispersed solution, being made up of 0.5g ~ 3g polyacrylic acid and 0.1g ~ 1 g softex kw, after stirring and dissolving, ultrasonic agitation 15 min ~ 60 min is continued at the temperature of 35 DEG C ~ 50 DEG C, then freezing 1h ~ 24 h at the temperature of-20 DEG C ~ 0 DEG C, add 0.485g ~ 1.94 g bismuth salt again, ultrasonic agitation 20 min ~ 30 min, obtains finely dispersed colloidal liquid;
(4) by described colloidal liquid ageing 0.5 h ~ 5 h at 20 DEG C ~ 40 DEG C, then proceed to reaction kettle for reaction 6 h ~ 18 h, reaction temperature is 90 DEG C ~ 180 DEG C, obtains reactant;
(5) described reactant is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 5 ~ 6 times, obtaining washings; Washings is toasted 12 hours ~ 24 hours at 60 DEG C ~ 80 DEG C, then obtains product after grinding.
5. the Si modification method of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material according to claim 4, it is characterized in that, described esters of silicon acis is ethyl orthosilicate.
6. the Si modification method of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material according to claim 4, it is characterized in that, step (1) described Graphene is graphene oxide and redox graphene.
7. the Si modification method of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material according to claim 4 or 6, it is characterized in that, step (3) described tungstates is sodium tungstate or ammonium tungstate, and described bismuth salt is bismuth nitrate.
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