CN103657639A - 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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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 a kind of preparation method and silicon method of modifying thereof 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
2lamination is tired out a kind of typical n type semiconductor forming, and has the character such as ferroelectric properties, catalytic performance and nonlinear dielectric susceptibility of fabulous chemical property, uniqueness, is a kind of good visible light catalytic agent material.Since Kudo in 1999 and Hijii reported first bismuth tungstate have the activity of photochemical catalyzing, caused countries in the world scientific workers' extensive concern.Bi
2wO
6valence band by Bi6s and O2p hybridized orbit, formed, and conduction band is comprised of W5d track, makes energy gap narrower (being about 2.69 eV), and the wavelength below 460 nm is had to good absorbing properties.In addition, Bi6s and O2p orbital hybridization are more disperseed valence band, are conducive to the movement of photohole in valence band, hinder the compound of itself and light induced electron, improve 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, in the fields such as water treatment and environmental protection, there is very large commercial value and application prospect.Yet because the quantum yield of bismuth tungstate material is low, light induced electron-hole commute of generation is compound, demonstrates lower photocatalysis efficiency.In addition, tungsten and bismuth are rare metals, and price is more expensive, thereby are limiting bismuth tungstate in industrial extensive use.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of preparation method and silicon method of modifying thereof under sunshine with Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material of strong absorption, high catalytic activity.The present invention be take Graphene as carrier, utilizes bismuth tungstate and silicon modification bismuth tungstate lamellar structure grapheme modified, thereby forms 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, and utilize the special nature of organic bath to obtain bismuth tungstate nanoscale twins, and strengthen the combination between Graphene and bismuth tungstate lamella.On this basis, utilize silicon modification bismuth tungstate lamella further improve photocatalysis performance and reduce costs, promote its application.Graphene is by individual layer or the tightly packed bi-dimensional cellular shape lattice structure carbonaceous material forming 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 current known twice with the indium antimonide material of high mobility, surpass the more than 10 times of commercial silicon chip mobility, be the ideal carrier of nanocatalyst.Particularly in Graphene, contain a large amount of not paired electronics that can move freely, have larger Electronic saving energy, can catch and light conducting excitation electron, hinder or stop right compound of optical excitation electronics and hole in semiconductor catalyst, improve photocatalysis performance.In addition, Graphene specific area is large, can effectively stop nanocatalyst to be reunited and increase its surface area, improves the adsorption capacity of material.Therefore, with Graphene, strengthen bismuth tungstate, be expected to obtain strong absorption, efficient visible light catalysis material, in fields such as sewage disposal, environmental protection and solar cells, be with a wide range of applications.
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 that is 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 dispersion 15 min ~ 30 min at 0 ℃-40 ℃, obtain finely dispersed solution;
(3) organic bath that add 0.1g ~ 4 g tungstates in described finely dispersed solution, is formed by 0.5g ~ 3g polyacrylic acid and 0.1g ~ 1 g softex kw, after stirring and dissolving, at the temperature of 35 ℃ ~ 50 ℃, continue ultrasonic agitation 15 min ~ 60 min, then freezing 1h ~ 24 h at the temperature of-20 ℃ ~ 0 ℃, add again 0.485g ~ 1.94 g bismuth salt, ultrasonic agitation 20 min ~ 30 min, obtain finely dispersed colloidal liquid;
(4) by described colloidal liquid ageing 0.5 h ~ 5 h at 20 ℃ ~ 40 ℃, then proceed to reaction kettle for reaction 6 h ~ 18 h, reaction temperature is 90 ℃ ~ 180 ℃, obtains reactant;
(5) described reactant is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 5 ~ 6 times, obtain washings; Washings is toasted 12 hours ~ 24 hours at 60 ℃ ~ 80 ℃, after then grinding, obtain product.
The described Graphene of step (1) is preferably graphene oxide and redox graphene.
The described tungstates of step (3) is preferably sodium tungstate or ammonium tungstate, and described bismuth salt is bismuth nitrate.
A silicon method of modifying for Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material, identical with above-mentioned preparation method's step, only in the described graphene dispersing solution of step (2), 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: take bismuth nitrate, tungstates, Graphene and ethyl orthosilicate as 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.By organic bath, modify dispersion and the surface-active that improves 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, form and take the lamella visible light catalytic material that Graphene is template.The special construction of Graphene and excellent properties, increased the quantum yield of bismuth tungstate and reduced right compound in its light induced electron-hole, improves its photocatalysis performance.In addition, use silicon modified graphene/bismuth tungstate lamella, make silicon and bismuth tungstate form effective combination, further improve the photocatalysis performance of Graphene/bismuth tungstate lamellar structure, and reduce preparation cost, thereby promote its application.
The softex kw that the present invention is used and polyacrylic acid belong to respectively cation and anion surfactant, by electrostatic interaction, be easy to form condensate, these organic polymers are known from experience formation wire and are attached on Graphene at low temperatures, realize function of surface functionalized graphene, increased the surface-active of Graphene.Organic bath on graphene film is easy to attract the metal Bi ion in solution, and these Bi ions generate bismuth tungstate precipitation (Bi with the tungstate ion adding
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 huge specific area of Graphene can increase the specific area of bismuth tungstate lamella simultaneously, strengthens adsorption capacity.Therefore, obtain absorption, high activity Graphene/bismuth tungstate lamella visible light catalytic material by force.In addition, silica is a kind of porous material, is commonly used to do 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 with Bi ion generation chemical reaction formation intermediateness (as Bi
3++ Si (OC
2h
5)
4→ Bi
2siO
22), will further improve its photocatalysis performance.
Compared with prior art, advantage of the present invention is:
1, the organic bath consisting of softex kw and polyacrylic acid is modified dispersion and the surface-active that improves Graphene, strengthens 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, form and take the lamella visible light catalytic material that Graphene is template.
2, the present invention uses silicon modified graphene/bismuth tungstate nanometer sheet; by forming intermediate product between Si and Bi; improve the photocatalysis efficiency of Graphene/bismuth tungstate nanometer sheet; to greatly reduce its use cost, thereby 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 that represents the Graphene/bismuth tungstate material (embodiment 1) that does not carry out silicon modification, and b is the XRD curve of Graphene/bismuth tungstate material (embodiment 2) of silicon 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 represents that the Graphene/bismuth tungstate material (embodiment 1) that does not carry out silicon modification is to organic degradation curve, and b is that the present invention uses Graphene/bismuth tungstate material (embodiment 2) of silicon modification to organic degradation curve.Within 0 minute, represent to be positioned in the past the absorption situation of dark state, within 0 minute, represent that in regulator solution, organic concentration, to initial concentration, represents the degraded situation after turning on light for 0 minute later.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further explained
embodiment 1(does not carry out silicon modification)
(1) the graphene oxide solution that is 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 at the temperature of 0 ~ 40 ℃ to ultrasonic dispersion 15 ~ 30 min, obtain finely dispersed solution;
(3) organic bath that add 0.3 g sodium tungstate in above-mentioned solution, is comprised 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 ℃; At the temperature of 0 ℃, after freezing 14 h, add under ultrasonic agitation 0.45 g bismuth nitrate, ultrasonic agitation 30 min, obtain colloidal fluid again;
(4) by (25 ℃) ageing 2 h at room temperature of colloidal solution step (3) Suo Shu, proceeding to afterwards volume is reaction kettle for reaction 10 h of 100 mL, and reaction temperature is 120 ℃;
(5) reactant step (4) Suo Shu is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 5 times; Washings is toasted 12 hours at 65 ℃, obtain Graphene/bismuth tungstate lamella nanostructured after grinding, its electronics pattern as depicted in figs. 1 and 2.The electron micrograph image demonstration of the sample that Fig. 1 and Fig. 2 obtain, the composite obtaining presents nano-sheet 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 shown composite to the degraded situation under the absorption of rhodamine B and visible ray.As can be seen from Figure, in 0.25g sample energy adsorbent solution the rhodamine B of 50% left and right (300 mL concentration are 1.0 * 10
-5mol/L), when increasing solution concentration to 1.0 * 10
-5after mol/L, the xenon lamp (500 W) of opening with recirculated cooling water irradiates, 40 min substantially can degraded solutions in whole rhodamine Bs.These results show, obtaining product is Graphene/bismuth tungstate composite of lamellar structure, and rhodamine B organic matter is had to good absorption and photocatalysis performance.
embodiment 2:(carries out silicon modification)
(1) the redox graphene solution that is 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 ℃, stir ultrasonic dispersion 30 min, obtain finely dispersed solution, and standing 18 h;
(3) organic bath that add 3.042 g ammonium tungstates in above-mentioned solution, is comprised 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 ℃; At the temperature of-10 ℃, after freezing 12 h, under ultrasonic agitation, add 0.8 g bismuth nitrate, ultrasonic agitation 30 min, obtain colloidal fluid;
(4) by (25 ℃) ageing 1 h at room temperature of colloidal solution step (3) Suo Shu, proceeding to afterwards volume is reaction kettle for reaction 16 h of 100 mL, and reaction temperature is 160 ℃;
(5) reactant step (4) Suo Shu is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 6 times; Washings is toasted 20 hours at 70 ℃, after grinding, obtain Graphene/bismuth tungstate lamella nanostructured of silicon modification, as shown in Figure 3 and Figure 4.
The electron micrograph image displaying of sample, the composite obtaining presents nano-sheet 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 crystal face diffraction maximum of crystal, also find Bi
12siO
22the diffraction maximum of crystal, silicon and bismuth that this explanation adds have formed interaction.Fig. 6 curve b (composite to the degraded situation under the absorption of rhodamine B and visible ray) shows, in 0.25g sample energy adsorbent solution the rhodamine B of 80% left and right (300 mL concentration are 1.0 * 10
-5mol/L), when increasing solution concentration to 1.0 * 10
-5after mol/L, the xenon lamp (500 W) of opening with recirculated cooling water irradiates, whole rhodamine Bs in 40 min energy degraded solutions.These results show, Graphene/bismuth tungstate composite of silicon modification still shows as lamellar structure, rhodamine B organic matter is also shown to good absorption and photocatalysis performance, and be better than not by absorption and the photocatalysis effect of silicon modified graphene/bismuth tungstate composite.
Claims (5)
1. a preparation method for Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material, is characterized in that, concrete steps are:
(1) graphene solution that is 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 dispersion 15 min ~ 30 min at 0 ℃-40 ℃, obtain finely dispersed solution;
(3) organic bath that add 0.1g ~ 4.0 g tungstates in described finely dispersed solution, is formed by 0.5g ~ 3g polyacrylic acid and 0.1g ~ 1 g softex kw, after stirring and dissolving, at the temperature of 35 ℃ ~ 50 ℃, continue ultrasonic agitation 15 min ~ 60 min, then freezing 1h ~ 24 h at the temperature of-20 ℃ ~ 0 ℃, add again 0.485g ~ 1.94 g bismuth salt, ultrasonic agitation 20 min ~ 30 min, obtain finely dispersed colloidal liquid;
(4) by described colloidal liquid ageing 0.5 h ~ 5 h at 20 ℃ ~ 40 ℃, then proceed to reaction kettle for reaction 6 h ~ 18 h, reaction temperature is 90 ℃ ~ 180 ℃, obtains reactant;
(5) described reactant is naturally cooled to room temperature, filter and use distilled water and absolute ethanol washing 5 ~ 6 times, obtain washings; Washings is toasted 12 hours ~ 24 hours at 60 ℃ ~ 80 ℃, after then grinding, obtain product.
2. the preparation method of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material according to claim 1, is characterized in that, the described Graphene of step (1) is graphene oxide and redox graphene.
3. according to the preparation method of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material described in claim 1 or 2, it is characterized in that, the described tungstates of step (3) is sodium tungstate or ammonium tungstate, and described bismuth salt is bismuth nitrate.
4. the silicon method of modifying of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material, it is characterized in that, identical with one of claim 1-3 described preparation method's step, only in the described graphene dispersing solution of step (2), add the esters of silicon acis of 1 mL-5 mL.
5. the method for modifying of Graphene/bismuth tungstate lamella nano-structure visible-light catalysis material according to claim 4, is characterized in that, described esters of silicon acis is ethyl orthosilicate.
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