CN102080262A - Visible light catalytic material, and preparation method and application thereof - Google Patents
Visible light catalytic material, and preparation method and application thereof Download PDFInfo
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- CN102080262A CN102080262A CN 201010600382 CN201010600382A CN102080262A CN 102080262 A CN102080262 A CN 102080262A CN 201010600382 CN201010600382 CN 201010600382 CN 201010600382 A CN201010600382 A CN 201010600382A CN 102080262 A CN102080262 A CN 102080262A
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Abstract
The invention discloses a visible light catalytic material used for environmental purification and a preparation method thereof. The visible light catalytic material is an indirect gas semiconductor with a dispersed energy band structure, is a crystalline nano material, comprises the chemical formula of Bi2Sn2O7, has the corresponding optical band gap width of 2.68 to 2.78eV and exhibits high visible light catalytic performance. In the preparation method provided by the invention, Bi2Sn2O7 nanoparticles can be prepared from readily-available raw materials with low cost under moderate conditions only by one-step hydrothermal reaction so as to avoid the coarsening and aggregation of the high-temperature sintered crystal particles; the preparation method is simple to operate; parameters are adjustable in a reaction process, and the crystallinity and material phase compositions of the product are easy to control; in addition, the sample provided by the invention exhibits high stability in photocatalysis cycle tests of dye degradation and harmful gas purification, and is favorable for industrial application.
Description
Technical field
The present invention relates to a kind of visible light catalytic material and preparation method thereof and application, especially relate to a kind of visible light catalytic material that is used for environment purification and preparation method thereof and application, belong to technical field of function materials.
Background technology
Find at TiO from Fujishima in 1972 and Honda
2Since the electrode material surface photoresponse product hydrogen phenomenon (Fujishima, A.Honda, K., Nature 238, and 37-38), photochemical catalysis causes global concern as solving environmental pollution and a kind of potential technology of energy dilemma.In the conductor photocatalysis process, rayed excites transition of electron in the valence band to conduction band, is forming photohole forming on light induced electron and the valence band on the conduction band; Carrier mobility is behind powder particle surface, and complicated oxidation, reduction reaction take place abundant and environmental activity on every side.TiO
2Powder has excellent photocatalysis activity, particularly is a series of commercialization TiO of representative with P25
2Nano-powder has shown excellent photocatalysis performance especially, yet powder reclaims difficulty, and can cause secondary pollution to former system, can't under the recycle system, reuse, and the TiO of intrinsic
2Only have a ultraviolet light response, thereby limited its application at numerous areas.
Seek new and effective visible light catalyst and be always the long-term and difficult task in one in photocatalysis technology field, it is the core place that photocatalysis technology can be able to large-scale promotion application.Based on the viewpoint of band theory, can be with the hydridization or the disperse state of electronic orbit in (conduction band and valence band), can reduce the virtual mass in current carrier (electronics and hole), improve the transmissibility of current carrier, separate in accelerated electron-hole.In 30 years of past, people's broad research based on d
0And d
10The oxide compound photocatalyst material of electronic configuration.d
0The oxidation photocatalyst of type, valence band generally all is made up of O2p, and conduction band is by the d of transition metal
0(Md
0) the track composition.Because the O2p in the valence band is localized relatively deep energy level, the Md in the conduction band
0Not disperse of track, d
0The photocatalyst of type usually is difficult to have visible light-responded, and performance is inferior to d usually
10The photocatalyst of type.For d
10The photocatalyst of type, though valence band also normally is made up of O2p, its conduction band makes light induced electron have higher mobility and transmittability because there is the sp hydridization of comparison disperse to form.Yet, this class d
10The transition metal oxide of type normally adopts the method for solid state sintering to make, and reunites, is unfavorable for the absorption of objectionable impuritiess such as dyestuff easily, has seriously limited the lifting of its catalytic performance.In addition, if can valence band can also be regulated and control to the state of a suitable disperse on the conduction band basis of relative hydridization, the separation of electron-hole pair and transmittability will improve greatly so, thereby demonstrate more excellent catalytic performance.
In sum, use the simple and cost low-cost preparation method of a kind of technology, the efficient visible light catalyzer that exploitation has the disperse energy band structure just seems particularly important.
Summary of the invention
The object of the present invention is to provide a kind of visible light catalytic material that can be used for environmental purification and preparation method thereof, to improve visible light catalytic material in the performance aspect dyestuff degraded and the toxic gas purification.
Of the present invention being contemplated that: can be with the hydridization or the disperse state of electronic orbit in (conduction band and valence band), can reduce the virtual mass in current carrier (electronics and hole), improve the transmissibility of current carrier, separate in accelerated electron-hole.Electronic configuration is d
10Compound, as In
3+, Sn
4+, Sb
5+, Bi
5+, Ga
3+, Ge
4+Deng, owing to the hydridization that the sp track is arranged in the conduction band disperse that seems, reduced the virtual mass of light induced electron, make that the transmission of electronics is more unobstructed.And if can be in the conduction band disperse, the regulation and control valence band be the disperse structure of hydridization, and the mobility of photohole also will strengthen greatly so, more helps the separation in light induced electron-hole in the photocatalytic process, improves photocatalysis efficiency.Bi
3+(6s
26p
0) because the 6s track that fills up, makes the valence band disperseization and the migration of raising photohole in the effective hydridization of valence band and O2p.Bi base stannate can be lively explaination mental model as above; And have the good advantage of chemically stable, be expected to become novel efficient visible light catalytic material.Therefore, we have selected Bi
2Sn
2O
7As research object.
For achieving the above object, the present invention is by the following technical solutions:
A kind of visible light catalytic material that is used for environment purification is characterized in that, described visible light catalytic material is a kind of indirect band-gap semiconductor with disperse energy band structure, is the crystalline state nano material, and its chemical constitution is Bi
2Sn
2O
7
Preferable, the optical energy gap of described indirect band-gap semiconductor (band gap) is 2.68-2.78eV.
Preferable, the particle diameter of described visible light catalytic material is 5-10nm.
Preferable, the specific surface area of described visible light catalytic material is 50-70m
2/ g.
Above-mentioned Bi provided by the present invention
2Sn
2O
7Visible light catalytic material belongs to pyrochlore-type (A
2B
2O
7, Fd-3m) structure, utilization VASP-GGA carries out Bi
2Sn
2O
7Can calculate by band, the result shows, its conduction band consists of Bi6p+Sn 5s+O2p, valence band consists of O2p+Bi 6s, be a kind of indirect transition material (being the indirect band-gap semiconductor material), the comparatively disperse of conduction band and valence band, this highly dispersed energy band structure, help of the transmission of electronics-hole, improve light induced electron-hole separating power at material internal.Uv-visible absorption spectroscopy shows that ABSORPTION EDGE is about 446-463nm, and its optical energy gap should be 2.68-2.78eV mutually, has high visible light response.
The present invention also further discloses the preparation method of above-mentioned visible light catalytic material, may further comprise the steps: by stoichiometric ratio, Bi source and Sn source are joined in the alkaline solution, under 120-300 ℃, carry out hydro-thermal reaction, collecting reaction product obtains visible light catalytic material Bi
2Sn
2O
7
Described Bi can select in the source metal-salt of stable Bi for use, as BiCl
3, BiBr
3, BiI
3, Bi (NO
3)
3, Bi
2(SO
4)
3, BiPO
4, Bi
2O
2CO
3, Bi (IO
3)
3, and their crystalline hydrate.
Described Sn can select in the source metal-salt of stable Sn for use, as simple substance Sn, SnCl
4, SnBr
4, SnI
4, and their crystalline hydrate, perhaps be selected from base metal stannate or alkali metal stannate (as lithium stannate, sodium stannate, potassium stannate, magnesium stannate, calcium stannate, stronitum stannate etc.).
Described alkaline solution is selected from aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, the cesium hydroxide aqueous solution and the ammoniacal liquor one or more mixing.
Preferable, total concn hydroxy is 10 in the described alkaline solution
-3～10mol/L; Be preferably 1-10mol/L.
Preferable, the time of described hydro-thermal reaction is 2-96h, is preferably 6-96h.
Among the above-mentioned preparation method, parameters such as temperature that can be by regulating hydro-thermal reaction and reaction times, the degree of crystallinity and the phase composite of regulation and control product.
The present invention also further discloses the purposes of above-mentioned visible light catalytic material, promptly in dyestuff degraded be harmful to the application of gas in purifying.
Described dyestuff is selected from tropeolin-D, rhodamine B or methylene blue.
Described obnoxious flavour is selected from acetaldehyde or formaldehyde.
Efficient visible light catalyst B i disclosed by the invention
2Sn
2O
7Beneficial effect be:
1.Bi
2Sn
2O
7Conduction band and valence band with disperse simultaneously, the quick transmission that has guaranteed light induced electron and hole with separate, avoided traditional d
10The localized defective of type photocatalyst material valence band, and demonstrate higher visible light catalytic performance;
2. the precursor solution in the building-up process only needs can obtain nano particle through a step hydro-thermal reaction, avoided the grain coarsening and the reunion of high temperature sintering, and the raw material that adopts is cheap and easy to get, simple to operate, the mild condition of preparation technology; Parameter in the reaction process is adjustable, is easy to realize controlling the degree of crystallinity and the thing phase composite of product;
3. existing Bi
2Sn
2O
7Compare the Bi that the present invention adopts one step hydro thermal method to make
2Sn
2O
7Band gap little, specific surface area is big, particle diameter little (5-10nm); This Bi
2Sn
2O
7Material can absorb and make full use of visible light wave range, and its high specific surface area can be quickened the absorption to target degraded molecule, improves photocatalysis performance.
4. the sample of gained of the present invention shows satisfactory stability in the photochemical catalysis loop test, is beneficial to industrial application.
Description of drawings
Fig. 1 is 240 ℃ of Bi that hydro-thermal reaction 24h obtains
2Sn
2O
7UV-vis collection of illustrative plates and optical photograph.
Fig. 2 is for hydro-thermal reaction 24h under the differing temps obtains the XRD spectrum of sample, and that show that temperature of reaction obtains in the time of 120 ℃ is SnO
2And Bi
2Sn
2O
7Mixed phase form, can obtain pure phase Bi when being higher than 120 ℃
2Sn
2O
7, and along with the increase of temperature of reaction, the degree of crystallinity of sample improves, thus reach the purpose of regulation and control sample degree of crystallinity.
Fig. 3 is the XRD spectrum that 240 ℃ of following hydro-thermal reaction different times obtain sample, shows that obtain when the reaction times is for 2h is Bi
2O
3And Bi
2Sn
2O
7Mixed phase form, can obtain pure phase Bi when being higher than 2h
2Sn
2O
7, along with the prolongation in reaction times, the degree of crystallinity of sample improves, thereby reaches the purpose of regulation and control sample degree of crystallinity.
Fig. 4 is Bi
2Sn
2O
7Energy band structure figure, show that it is an indirect band-gap semiconductor, the theoretical optics band gap is 2.68eV.
Fig. 5 is Bi
2Sn
2O
7Partial density of states and total density of states(DOS), show that conduction band consists of Bi6p+Sn 5s+O2p, valence band consists of O2p+Bi 6s, the comparatively disperse of conduction band and valence band helps the transmission of electronics-hole at material internal, improves light induced electron-hole separating power.
Fig. 6 is 160 ℃ of Bi that hydro-thermal reaction 24h obtains
2Sn
2O
7Bi
2Sn
2O
7SEM (shown in Fig. 6 a), TEM (shown in Fig. 6 b, 6c) and EDS (shown in Fig. 6 d) collection of illustrative plates, the pattern that shows gained is for spherical, this sphere is that the fine particle of 5-10nm is formed by particle diameter, has confirmed that further the stoichiometric ratio of Bi and Sn approached 1: 1 in the gained sample.
Fig. 7 is under the UV-irradiation, 240 ℃ of Bi that hydro-thermal reaction 6h obtains
2Sn
2O
7The activity of photocatalytic degradation tropeolin-D shows that its ultraviolet catalytic activity is better than Bi
2O
3, solid phase preparation Bi
2Sn
2O
7, and the commercial TiO that can match in excellence or beauty
2
Fig. 8 is under the radiation of visible light, 240 ℃ of Bi that hydro-thermal reaction 24h obtains
2Sn
2O
7The activity of photocatalytic degradation tropeolin-D shows that it has best visible light catalysis activity.
Fig. 9 is under the radiation of visible light, 240 ℃ of Bi that hydro-thermal reaction 24h obtains
2Sn
2O
7The stable circulation property testing of photocatalytic degradation tropeolin-D shows that it can be used as a kind of stable photocatalyst material and repeatedly recycles.
Figure 10 is under the radiation of visible light, 240 ℃ of Bi that hydro-thermal reaction 96h obtains
2Sn
2O
7The activity of photocatalytic degradation acetaldehyde shows that it has the photocatalysis performance of superpower purification toxic gas.
Embodiment
Further set forth the present invention below in conjunction with embodiment.Should be understood that these embodiment only are used to illustrate the present invention, but not limit the scope of the invention.
A) material characterizes:
Gained particulate samples of the present invention is passed through scanning electron microscope sem (JSM-6510) and transmission electron microscope TEM (JEM 2100F) and electronic spectrum EDS observation sample pattern and elementary composition; By x-ray powder diffraction instrument (Rigaku D/Max-2550V) analyte phase; Characterize optical band gap by uv-visible absorption spectroscopy UV-vis (Hitachi U3010).
B) performance test:
1. dyestuff degraded
Gained sample powder of the present invention is carried out the research of photocatalytically degradating organic dye in homemade reactor.In the experiment, the concentration of dyestuff is 10mg/L, and the amount of powder in dye solution or in the pure water is 1g/L.In the ultraviolet experiment, the irradiation light source is the high voltage mercury lamp of 500W.Another set of device is adopted in the visible light experiment, and by 300W Xe lamp, filter plate and radiator fan are formed.And, carry out the test of cycle performance, to characterize its stability with the powder recovery.Choose commercial anatase octahedrite TiO
2, commercial Bi
2O
3, and the Bi of high temperature solid-state preparation
2Sn
2O
7As reference, come the nanometer Bi of a step hydrothermal preparation among qualitative judge the present invention
2Sn
2O
7Photocatalytic activity.
2. cleaning harmful gas
Gained sample powder of the present invention is carried out the research of the representative obnoxious flavour of photocatalytic degradation in homemade reactor.Light-catalyzed reaction is carried out in the airtight stainless steel reactor of homemade cylinder shape.Light source is a 300W Xe lamp.Characterize the degradation rate of photochemical catalytic oxidation resolving harmful gas by the carbon dioxide content in the test chamber.
Embodiment 1:
Get 0.9701g Bi (NO
3)
35H
2O and 0.7012g SnCl
45H
2O joins in the 1mol/L aqueous solution of 40mL NaOH, obtains unformed precursor solution after fully stirring.This precursor solution is changed in the hydrothermal reaction kettle, react 24h down at 240 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 446nm, and the respective optical band gap is 2.78eV, have visible light-responded, as shown in Figure 1.Through the XRD test, obtain pure phase pyrochlore-type Bi
2Sn
2O
7, as shown in Figures 2 and 3.Utilization VASP-GGA carries out being with calculating, and the result shows that conduction band consists of Bi6p+Sn 5s+O2p, and valence band consists of O2p+Bi 6s, is a kind of indirect transition material, as shown in Figure 4 and Figure 5.
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 5-10nm, and specific surface area is 58.5m
2/ g.
With the Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degraded tropeolin-D, and the result shows: its photocatalytic activity is better than Bi
2O
3, solid phase preparation Bi
2Sn
2O
7, be much better than commercial TiO
2And have good cyclical stability, as shown in Figure 9.
Embodiment 2:
Get 0.9701g Bi (NO
3)
35H
2O and 0.7012g SnCl
45H
2O joins in the 10M aqueous solution of 40mL KOH, obtains unformed precursor solution after fully stirring.This precursor solution is changed in the hydrothermal reaction kettle, react 6h down at 240 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 452nm, and the respective optical band gap is 2.75eV, have visible light-responded.Through the XRD test, obtain pure phase pyrochlore-type Bi equally
2Sn
2O
7, as shown in Figure 3.
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 5-10nm, and specific surface area is 62.6m
2/ g.
With the Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of ultraviolet degradation tropeolin-D, and the result shows: its photocatalytic activity obviously is better than the Bi of solid phase preparation
2Sn
2O
7, commercial TiO
2And Bi
2O
3, as shown in Figure 7.
Embodiment 3:
Get 0.9701g Bi (NO
3)
35H
2O and 0.7012g SnCl
45H
2O joins in the 40mL ammonia soln, and the pH value of regulator solution obtains unformed precursor solution after fully stirring about 11.This precursor solution is changed in the hydrothermal reaction kettle, react 96h down at 240 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 460nm, and the respective optical band gap is 2.70eV, have visible light-responded.Through the XRD test, obtain pure phase pyrochlore-type Bi equally
2Sn
2O
7
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 5-10nm, and specific surface area is 50.8m
2/ g.
With the Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degrade acetaldehyde, through the radiation of visible light of 5h, the CO of generation
2Nearly 150ppm demonstrates good photocatalytic degradation performance, as shown in figure 10.
Embodiment 4:
Get 0.9701g Bi (NO
3)
35H
2O and 0.2374g Sn powder join in the 10M aqueous solution of 40mL NaOH, obtain unformed precursor solution after fully stirring.This precursor solution is changed in the hydrothermal reaction kettle, react 24h down at 240 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 463nm, and the respective optical band gap is 2.75eV, have visible light-responded.Through the XRD test, obtain pure phase pyrochlore-type Bi equally
2Sn
2O
7
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 5-8nm, and specific surface area is 69.3m
2/ g.
The Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degraded tropeolin-D, and the result shows: its photocatalytic activity obviously is better than the Bi of solid phase preparation
2Sn
2O
7, commercial TiO
2And Bi
2O
3, as shown in Figure 8.Slightly be better than embodiment 2.
Embodiment 5:
Get 0.9701g Bi (NO
3)
35H
2O and 0.7012g SnCl
45H
2O joins in the 1M aqueous solution of 40mL NaOH, obtains unformed precursor solution after fully stirring.This precursor solution is changed in the hydrothermal reaction kettle, react 24h down at 240 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 446nm, and the respective optical band gap is 2.78eV, have visible light-responded.Through the XRD test, obtain pure phase pyrochlore-type Bi
2Sn
2O
7
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 5-10nm, and specific surface area is 58.5m
2/ g.
The Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degrade acetaldehyde, and through the radiation of visible light of 5h, the result is substantially the same manner as Example 3, demonstrates good photocatalytic degradation performance equally.
Embodiment 6:
Get 0.7422g Bi
2(SO
4)
32H
2O and 0.7012g SnCl
45H
2O joins in the 10M aqueous solution of 40mL KOH, obtains unformed precursor solution after fully stirring.This precursor solution is changed in the hydrothermal reaction kettle, react 48h down at 120 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 461nm, and the respective optical band gap is 2.69eV, have visible light-responded.Through the XRD test, obtain pure phase pyrochlore-type Bi
2Sn
2O
7
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 5-8nm, and specific surface area is 70.5m
2/ g.
The Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degraded tropeolin-D, and the result shows: its photocatalytic activity still is better than the Bi of solid phase preparation
2Sn
2O
7, commercial TiO
2And Bi
2O
3, but slightly be inferior to embodiment 2.
Embodiment 7:
Get 0.9701g Bi (NO
3)
35H
2O and 0.8767g SnBr
4Join in the 40mL ammonia soln, the pH value of regulator solution obtains unformed precursor solution after fully stirring about 11.This precursor solution is changed in the hydrothermal reaction kettle, react 96h down at 240 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 446nm, and the respective optical band gap is 2.78eV, have visible light-responded.Through the XRD test, obtain pure phase pyrochlore-type Bi
2Sn
2O
7
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 7-10nm, and specific surface area is 56.2m
2/ g.
The Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degraded tropeolin-D, and the result is substantially the same manner as Example 1, and its photocatalytic activity obviously is better than the Bi of solid phase preparation
2Sn
2O
7, commercial TiO
2And Bi
2O
3And has a good cyclical stability.
Embodiment 8:
Get 0.7422g Bi
2(SO
4)
32H
2O and 0.8767g SnBr
4Join in the mixing solutions of 40mL KOH and NaOH (the alkali lye total concn is 1M), obtain unformed precursor solution after fully stirring.This precursor solution is changed in the hydrothermal reaction kettle, react 24h down at 160 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 450nm, and the respective optical band gap is 2.76eV, have visible light-responded.Through the XRD test, obtain pure phase pyrochlore-type Bi
2Sn
2O
7, as shown in Figure 2.Pattern is spherical, and this sphere is that the fine particle of 5-10nm is formed by particle diameter, has confirmed that further the stoichiometric ratio of Bi and Sn approached 1: 1 in the gained sample, as shown in Figure 6.
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 5-10nm, and specific surface area is 66.4m
2/ g.
The Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degraded rhodamine B, and the result is substantially the same manner as Example 1, and its photocatalytic activity still is better than the Bi of solid phase preparation
2Sn
2O
7, commercial TiO
2And Bi
2O
3And has a good cyclical stability.
Embodiment 9:
Get 0.9701g Bi (NO
3)
35H
2O and 0.7012g SnCl
45H
2O joins in the 1mol/L aqueous solution of 40mL NaOH, obtains unformed precursor solution after fully stirring.This precursor solution is changed in the hydrothermal reaction kettle, react 12h down at 240 ℃, room temperature to be naturally cooled to, filtration drying is collected the gained pale yellow powder.UV-vis test shows, its ABSORPTION EDGE are about 453nm, and the respective optical band gap is 2.74eV, have visible light-responded.Through the XRD test, obtain pure phase pyrochlore-type Bi
2Sn
2O
7
The Bi that present embodiment obtains
2Sn
2O
7The particle diameter of nano particle is 5-10nm, and specific surface area is 64.5m
2/ g.
With the Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degradation of methylene blue, and the result shows: its photocatalytic activity obviously is better than Bi
2O
3, solid phase preparation Bi
2Sn
2O
7And commercial TiO
2And has a good cyclical stability.With the Bi that obtains
2Sn
2O
7Nano particle is used for the experiment of visible light degradation of formaldehyde, through the radiation of visible light of 8h, the CO of generation
2Nearly 180ppm demonstrates good photocatalytic degradation performance equally.
Claims (10)
1. a visible light catalytic material that is used for environment purification is characterized in that, described visible light catalytic material is a kind of indirect band-gap semiconductor with disperse energy band structure, is the crystalline state nano material, and its chemical constitution is Bi
2Sn
2O
7
2. the visible light catalytic material that is used for environment purification as claimed in claim 1 is characterized in that, the optical energy gap of described indirect band-gap semiconductor is 2.68-2.78eV.
3. the visible light catalytic material that is used for environment purification as claimed in claim 1 or 2 is characterized in that, the particle diameter of described visible light catalytic material is 5-10nm; The specific surface area of described visible light catalytic material is 50～70m
2/ g.
4. as arbitrary described preparation method who is used for the visible light catalytic material of environment purification among the claim 1-3, may further comprise the steps: by stoichiometric ratio, Bi source and Sn source are joined in the alkaline solution, under 120-300 ℃, carry out hydro-thermal reaction, collecting reaction product obtains visible light catalytic material Bi
2Sn
2O
7
5. the preparation method who is used for the visible light catalytic material of environment purification as claimed in claim 4 is characterized in that, described Bi source is selected from BiCl
3, BiBr
3, BiI
3, Bi (NO
3)
3, Bi
2(SO
4)
3, BiPO
4, Bi
2O
2CO
3, Bi (IO
3)
3, and their crystalline hydrate; Described Sn source is selected from simple substance Sn, SnCl
4, SnBr
4, SnI
4, and their crystalline hydrate, perhaps be selected from base metal stannate or alkali metal stannate.
6. the preparation method who is used for the visible light catalytic material of environment purification as claimed in claim 4, it is characterized in that described alkaline solution is selected from aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, the cesium hydroxide aqueous solution and the ammoniacal liquor one or more mixing.
7. the preparation method who is used for the visible light catalytic material of environment purification as claimed in claim 4 is characterized in that, total concn hydroxy is 10 in the described alkaline solution
-3～10mol/L.
8. as arbitrary described preparation method who is used for the visible light catalytic material of environment purification among the claim 4-7, it is characterized in that the time of described hydro-thermal reaction is 2-96h.
9. as arbitrary described application that is used for the visible light catalytic material of environment purification at dyestuff degraded or cleaning harmful gas among the claim 1-3.
10. purposes as claimed in claim 9 is characterized in that described dyestuff is selected from tropeolin-D, rhodamine B or methylene blue; Described obnoxious flavour is selected from formaldehyde or acetaldehyde.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055862A (en) * | 2011-11-03 | 2013-04-24 | 合肥美菱股份有限公司 | Photocatalytic nano material |
| CN103332739A (en) * | 2013-07-03 | 2013-10-02 | 南京理工大学 | Bi2Sn2O7 composite oxide with unique morphology and preparation method thereof |
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| CN104941627A (en) * | 2015-06-09 | 2015-09-30 | 江苏大学 | Preparation method and use of yttrium-doped bismuth stannate nanocrystallines |
| CN105297135A (en) * | 2015-10-21 | 2016-02-03 | 中国科学院地球环境研究所 | Bi2Sn2O7 nanocrystals having visible light response capacity and preparation method thereof |
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| CN107185568A (en) * | 2017-07-10 | 2017-09-22 | 河南师范大学 | The method that ion-exchange synthesizes flower ball-shaped BiPO4 catalysis materials |
| CN107185569A (en) * | 2017-07-10 | 2017-09-22 | 河南师范大学 | In situ conversion process synthesis flower ball-shaped Bi2O2CO3/BiPO4The method of heterojunction photocatalysis material |
| CN108927183A (en) * | 2018-07-09 | 2018-12-04 | 福建师范大学 | A kind of heterojunction photocatalyst, preparation method and its usage |
| CN109292895A (en) * | 2018-11-05 | 2019-02-01 | 重庆第二师范学院 | A kind of photocatalyst Li2SnO3Preparation method and utilization |
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| CN114515590A (en) * | 2022-03-11 | 2022-05-20 | 西安建筑科技大学 | Heterogeneous photocatalytic material and preparation and application thereof |
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| CN103055862B (en) * | 2011-11-03 | 2014-06-11 | 合肥美菱股份有限公司 | Photocatalytic nano material |
| CN103055862A (en) * | 2011-11-03 | 2013-04-24 | 合肥美菱股份有限公司 | Photocatalytic nano material |
| CN103332739A (en) * | 2013-07-03 | 2013-10-02 | 南京理工大学 | Bi2Sn2O7 composite oxide with unique morphology and preparation method thereof |
| CN103977785A (en) * | 2014-02-27 | 2014-08-13 | 上海大学 | Bi2Sn2O7-graphene composite visible-light-driven photocatalyst and preparation method thereof |
| CN104941627A (en) * | 2015-06-09 | 2015-09-30 | 江苏大学 | Preparation method and use of yttrium-doped bismuth stannate nanocrystallines |
| CN105297135A (en) * | 2015-10-21 | 2016-02-03 | 中国科学院地球环境研究所 | Bi2Sn2O7 nanocrystals having visible light response capacity and preparation method thereof |
| CN105297135B (en) * | 2015-10-21 | 2018-09-14 | 中国科学院地球环境研究所 | A kind of Bi with visible light-responded ability2Sn2O7Nanocrystal and preparation method thereof |
| CN106111114B (en) * | 2016-06-14 | 2018-07-20 | 西安交通大学 | A kind of In2O3/Bi2Sn2O7Composite visible light catalyst and preparation method thereof |
| CN106111114A (en) * | 2016-06-14 | 2016-11-16 | 西安交通大学 | A kind of In2o3/ Bi2sn2o7composite visible light catalyst and preparation method thereof |
| CN107185569A (en) * | 2017-07-10 | 2017-09-22 | 河南师范大学 | In situ conversion process synthesis flower ball-shaped Bi2O2CO3/BiPO4The method of heterojunction photocatalysis material |
| CN107185568A (en) * | 2017-07-10 | 2017-09-22 | 河南师范大学 | The method that ion-exchange synthesizes flower ball-shaped BiPO4 catalysis materials |
| CN107185568B (en) * | 2017-07-10 | 2020-03-31 | 河南师范大学 | Method for synthesizing flower-ball-shaped BiPO4 photocatalytic material by ion exchange method |
| CN107185569B (en) * | 2017-07-10 | 2020-03-31 | 河南师范大学 | In-situ conversion method for synthesizing flower ball Bi2O2CO3/BiPO4Method for heterojunction photocatalytic material |
| CN108927183A (en) * | 2018-07-09 | 2018-12-04 | 福建师范大学 | A kind of heterojunction photocatalyst, preparation method and its usage |
| CN109292895A (en) * | 2018-11-05 | 2019-02-01 | 重庆第二师范学院 | A kind of photocatalyst Li2SnO3Preparation method and utilization |
| CN109292895B (en) * | 2018-11-05 | 2021-07-13 | 重庆第二师范学院 | Photocatalyst Li2SnO3Preparation method and application of |
| CN114160118A (en) * | 2021-11-03 | 2022-03-11 | 易鹤翔 | Water-resistant nano tin oxide wide-spectral-response photocatalyst porous material and preparation method thereof |
| CN114515590A (en) * | 2022-03-11 | 2022-05-20 | 西安建筑科技大学 | Heterogeneous photocatalytic material and preparation and application thereof |
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