CN104909579B - The glass bead of plated surface Ag/BiOCl silica membrane and its technique and purposes - Google Patents
The glass bead of plated surface Ag/BiOCl silica membrane and its technique and purposes Download PDFInfo
- Publication number
- CN104909579B CN104909579B CN201510266251.9A CN201510266251A CN104909579B CN 104909579 B CN104909579 B CN 104909579B CN 201510266251 A CN201510266251 A CN 201510266251A CN 104909579 B CN104909579 B CN 104909579B
- Authority
- CN
- China
- Prior art keywords
- glass bead
- biocl
- thin film
- film
- silicon dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
The present invention provides a kind of technique of glass bead plated surface Ag/BiOCl silicon dioxide adsorption photochemical catalysis thin film, including step 1:Clean and dry glass ball；Step 2:Loaded mesoporous silica membrane in glass ball surface, forms the glass bead of area load mesoporous silica film；Step 3:Glass ball surface loaded Ag/BiOCl visible light catalytic thin film again in step 2 gained；Step 4:Repeat 06 steps 3 and obtain the loaded Ag/BiOCl visible light catalytic thin film of different-thickness and the glass bead of mesoporous silica film.The surface of the technique preparation being provided using the present invention be coated with Ag/BiOCl silicon dioxide adsorption photochemical catalysis thin film glass bead be placed in floating type reactor can rhodamine B degradation, methyl orange or methylene blue organic pollution under illumination, there is excellent adsorption photochemical catalysis synergisticing performance.
Description
Technical field
The invention belongs to the preparation technique and application field of conductor photocatalysis reactor is and in particular to a kind of plated surface
The glass bead of Ag/BiOCl- silicon dioxide absorption-photocatalysis film and its preparation technology and purposes.
Background technology
In commercial production, the discharge of garbage destroys ecological balance and pollutes environment, seriously threatens human health.Partly lead
Body catalysis material due to Strong oxdiative ability can degrade multiple hazardous contaminants, environmental friendliness, can be utilized solar energy, instead
The features such as mild condition and low cost is answered to make it have extremely wide application prospect.Wherein TiO2Material is because of photocatalytic activity
Height, stable in properties, nontoxic and material are cheap, become the photocatalyst of current most application potential.But TiO2Due to too
Sunlight utilization is relatively low, limits its range of application.In order to expand the utilization to sunlight, researcher is constantly endeavoured to develop visible
The stratiform BiOCl quasiconductor of photocatalyst, wherein carried noble metal such as Ag etc. is extensively concerned.The research of BiOCl mainly collects at present
Middle hydrolysis or solvent-thermal method preparation BiOX powder body, and there are three major defects in terms of wastewater treatment in powder body catalysis material：
1) due to " screen effect " of the absorption to exciting light for the Organic substance itself and catalyst powder itself, exciting light wearing in the solution
Depth is too shallow thoroughly, so that the degradation efficiency of unit mass catalyst declines；2) light induced electron and hole are in powder body catalyst
Surface is easily voluntarily combined and so that degradation efficiency is declined；3) powder body catalyst is difficult and solution separating after disperseing in aqueous,
It is difficult to the recycling and reuse of catalyst.Compared with powder body catalyst, Ag/BiOCl photocatalysis film is in actual applications
Loss and the energy waste causing because catalyst separates can be avoided with reactant.Meanwhile, setting in photo catalysis reactor
If the irradiation light utilization efficiency of the current generally existing of consideration is low and the low problem of mass-transfer efficiency will more have application valency in meter
Value.Ordered mesoporous material has the ordered arrangement in duct, aperture continuously adjustable, high specific surface area in variable range because of it
And extremely pay attention in adsorption applications field the features such as heat stability.The thing but adsorbing material is simply transferred the pollution and cannot eliminate
Pollutant.Therefore absorption is combined with photocatalysis, while pollutant mass-transfer efficiency can be effectively improved, removes pollutant completely,
Make its thorough mineralising, it is to avoid secondary pollution.
Content of the invention
It is an object of the invention to obtaining the simple and effective coating technique of absorption-photocatalysis film and to solve photocatalysis anti-
Answer and in device design, irradiate that light utilization efficiency is low, the low problem of mass-transfer efficiency, with low cost, easy-operating coating process is provided.This
The technique of bright glass bead plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film, including：
Step 1：Clean and dry glass ball；
Step 2：Loaded mesoporous silica membrane in glass ball surface, forms area load mesoporous silica film
Glass bead；
Step 3：Glass ball surface loaded Ag/BiOCl visible light catalytic thin film again in step 2 gained；
Step 4：0-6 step 3 of repetition obtains the loaded Ag/BiOCl visible light catalytic thin film and mesoporous two of different-thickness
The glass bead of silicon oxide film.
Absorption is combined by the present invention with photocatalysis, is urged by loaded mesoporous silica membrane and Ag/BiOCl visible ray
Change thin film, can effectively improve and remove pollutant completely while pollutant mass-transfer efficiency so as to thorough mineralising, it is to avoid secondary dirt
Dye, improves irradiation light utilization efficiency in light-catalyzed reaction simultaneously.
It is further preferred that step 1 specifically includes：Glass bead is placed in stirring in sulfuric acid solution, removes surface impurity, use
Deionized water cleans up and is dried；Afterwards glass bead is placed in deionized water after stirring in sodium hydroxide solution to clean up
And be dried.
The present invention carries out pretreatment to vial, ensures the accurate of experimental data on the premise of not affecting experimental data
Property.
It is further preferred that glass bead is plain hollow glass bead, density is 2.5～2.6g/cm3, glass bead is a diameter of
10～11mm, wall thickness 0.3～0.4mm.
It is further preferred that step 2 specifically includes：
2.1 cetyl trimethylammonium bromide surfactant is added in deionized water, is stirring evenly and then adding into hydrogen
Sodium oxide, adjusts pH value of solution to 12, is stirring evenly and then adding into 0.5～7.0mL tetraethyl orthosilicate and stirs, obtain mesoporous silicon oxide
The loading solution of adsorbent thin film；Cetyl trimethylammonium bromide surfactant and deionized water amount ratio are 1g：480mL；
2.2 by the loading solution putting into the mesoporous silicon oxide adsorbent thin film that step 2.1 obtains through step 1 glass bead
Rotation makes its surface and the loading solution of mesoporous silicon oxide adsorbent thin film be fully contacted, and is placed in drying 24h at 80 DEG C after stirring,
Roasting 4h at 350-450 DEG C, obtain the glass bead of area load mesoporous silica film.
Silicon dioxide ordered mesoporous material is adopted, it has the ordered arrangement in duct, aperture in variable range in the present invention
The features such as interior continuously adjustable, high specific surface area and heat stability, the adsorptivity of silicon dioxide is combined with photocatalysis, can
Effectively improve and remove pollutant completely while pollutant mass-transfer efficiency so as to thorough mineralising, it is to avoid secondary pollution.
It is further preferred that step 3 specifically includes：
3.1 pluronic P123 surfactant is dissolved in ethanol, is stirring evenly and then adding into five nitric hydrate bismuths, drips
Stir after salt adding acid solution；Adding silver nitrate and adjusting silver with bismuth mol ratio is 2.0～20%, adds 0.3-0.8g afterwards
Glucose simultaneously stirs, and obtains the loading solution of Ag/BiOCl visible light catalytic thin film；Pluronic P123 surfactant
Amount ratio with ethanol is 1g：40mL；
3.2 glass beads obtaining step 3 put into the loading solution of Ag/BiOCl visible light catalytic thin film, are placed in after stirring
At 80 DEG C dry 24h, roasting 4h at 250-300 DEG C, obtain area load Ag/BiOCl visible light catalytic thin film and Jie
The glass bead of hole silica membrane.
The present invention adopts the stratiform BiOCl quasiconductor of carried noble metal Ag as catalysis material, because it is to sunlight profit
With rate compared to traditional TiO2Material is higher.Compared to traditional powder body catalysis material, the Ag/BiOCl visible ray of the present invention
The glass bead of catalytic film and mesoporous silica film can avoid in actual applications because catalyst separates with reactant
The loss causing and energy waste, and coating process is easy, surface thickness of liquid film is little, and light transmittance is high and mass-transfer efficiency is high.
It is further preferred that silver and bismuth mol ratio are 10% in step 3.1.
It is further preferred that number of repetition is 3 times in step 4.
Present invention also offers a kind of glass bead of plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film, by upper
State the technique preparation of any one.
It is further preferred that the glass bead of plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film, for suspending
In type reactor, adsorb and photocatalytic degradation rhodamine B, methyl orange or methylene blue.
The present invention, compared with existing photo catalysis reactor, has advantages below：Irradiate light utilization efficiency high, mass-transfer efficiency is high,
The features such as coating process is simple and convenient to operate, solves the problems, such as the separation and recovery of powder photocatalyst.
Brief description
With reference to the accompanying drawings and detailed description the present invention is described in further detail：
X-ray diffraction spectrum (XRD) figure of the sample that Fig. 1 is prepared for embodiment of the present invention 1-2；
Fig. 2 is scanning electron microscope (SEM) photo of the sample of the embodiment of the present invention 1 preparation；
Fig. 3 is X-ray photoelectron spectroscopic analysis (XPS) collection of illustrative plates of the sample of the embodiment of the present invention 1 preparation；
Fig. 4 is transmission electron microscope (HRTEM) photo of the sample of the embodiment of the present invention 7 preparation；
Fig. 5 is UV-Vis DRS spectrum (UV-Vis DRS) figure of the embodiment of the present invention 1,2,8；
Fig. 6 is the absorption property of the embodiment of the present invention 7；
Fig. 7 is the absorption-photocatalysis performance contrast of embodiment of the present invention 1-6；
Fig. 8 is the absorption-photocatalysis performance contrast of embodiment of the present invention 1-2,9-11；
Fig. 9 is the embodiment of the present invention 1, the absorption of 12-16-photocatalysis performance contrast；
Figure 10 is absorption-photocatalysis performance to different organic pollutions for the embodiment of the present invention 1；
Figure 11 is the schematic diagram of floating type photo catalysis reactor provided by the present invention.
Specific embodiment
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this
Some embodiments of invention, to those skilled in the art, on the premise of not paying creative work, acceptable
Other accompanying drawings are obtained according to these accompanying drawings.
The technique of glass bead plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film includes：
Step 1 is cleaned and dry glass ball；
Step 2 loaded mesoporous silica membrane in glass ball surface, forms area load mesoporous silica film
Glass bead；
Step 3 is in the glass ball surface loaded Ag/BiOCl visible light catalytic thin film again of step 2 gained；
Step 4 repeats 0-6 step 3 and obtains the loaded Ag/BiOCl visible light catalytic thin film of different-thickness and mesoporous dioxy
The glass bead of SiClx thin film.
Specifically, glass bead is simple glass hollow ball, and density is 2.5～2.6g/cm3, glass bead is a diameter of 10～
11mm, wall thickness 0.3～0.4mm.
Step 1 specifically includes：Glass bead is placed in stirring in sulfuric acid solution, removes surface impurity, deionized water is cleaned
Clean and dry；Afterwards glass bead is placed in deionized water after stirring in sodium hydroxide solution to clean up and be dried.This
Bright accuracy pretreatment being carried out to vial, ensureing experimental data on the premise of not affecting experimental data.
Step 2 specifically includes：
2.1 cetyl trimethylammonium bromide surfactant is added in deionized water, is stirring evenly and then adding into hydrogen
Sodium oxide, adjusts pH value of solution to 12, is stirring evenly and then adding into 0.5～7.0mL tetraethyl orthosilicate and stirs, obtain mesoporous silicon oxide
The loading solution of adsorbent thin film；Cetyl trimethylammonium bromide surfactant and deionized water amount ratio are 1g：480mL；
2.2 by the loading solution putting into the mesoporous silicon oxide adsorbent thin film that step 2.1 obtains through step 1 glass bead
Rotation makes its surface and the loading solution of mesoporous silicon oxide adsorbent thin film be fully contacted, and is placed in drying 24h at 80 DEG C after stirring,
Roasting 4h at 350-450 DEG C, obtain the glass bead of area load mesoporous silica film.
Silicon dioxide ordered mesoporous material is adopted, it has the ordered arrangement in duct, aperture in variable range in the present invention
The features such as interior continuously adjustable, high specific surface area and heat stability, the adsorptivity of silicon dioxide is combined with photocatalysis, can
Effectively improve and remove pollutant completely while pollutant mass-transfer efficiency so as to thorough mineralising, it is to avoid secondary pollution.
Step 3 specifically includes：
3.1 pluronic P123 surfactant is dissolved in ethanol, is stirring evenly and then adding into five nitric hydrate bismuths, drips
Stir after salt adding acid solution；Adding silver nitrate and adjusting silver with bismuth mol ratio (being designated as Ag/Bi) is 2.0～20%, afterwards
Add 0.3-0.8g glucose and stir, obtain the loading solution of Ag/BiOCl visible light catalytic thin film；pluronic
P123 surfactant is 1g with the amount ratio of ethanol：40mL；
3.2 glass beads obtaining step 3 put into the loading solution of Ag/BiOCl visible light catalytic thin film, are placed in after stirring
At 80 DEG C dry 24h, roasting 4h at 250-300 DEG C, obtain area load Ag/BiOCl visible light catalytic thin film and Jie
The glass bead of hole silica membrane.
The present invention adopts the stratiform BiOCl quasiconductor of carried noble metal Ag as catalysis material, because it is to sunlight profit
With rate compared to traditional TiO2Material is higher.Compared to traditional powder body catalysis material, the Ag/BiOCl visible ray of the present invention
The glass bead of catalytic film and mesoporous silica film can avoid in actual applications because catalyst separates with reactant
The loss causing and energy waste, and coating process is easy, surface thickness of liquid film is little, and light transmittance is high and mass-transfer efficiency is high.
It is making further detailed, clear and complete description of how realizing to the present invention with reference to specific embodiment, institute
Row embodiment is only further described to the present invention, not thereby limiting the invention：
The product of present invention preparation carries out structural characterization by the following means：Using in Japanese Rigaku D/Max-RB type X
On x ray diffractometer x, the X ray diffracting spectrum of measurement carries out the structural analyses of sample；Using in Japanese JEOL JSM-6380LV type
The scanning electron microscope of scanning electron microscope and the acquisition of JEM-2010 type transmission electron microscope and the appearance structure of transmission electron microscope photo analysis sample.Adopt
The light abstraction width of UV-vis DRS spectrum analysis sample obtaining on Shimadzu UV-2450 type spectrophotometer and light
Absorption intensity.
Embodiment 1
After glass bead surface treatment, weigh 1.0g cetyl trimethylammonium bromide (CTAB) surfactant and be added to
In 480mL deionized water, add 5.0mL 2.0mol/L sodium hydroxide after stirring 30min, regulation pH value of solution to 12, after stirring 1h
Add 5mL tetraethyl orthosilicate and stir 1h.It is placed in after putting into 60 glass bead stirring 180min through pretreatment and dry at 80 DEG C
Dry 24h, roasting 4h at 400 DEG C (heating rate be 4 DEG C/min), you can obtain area load mesoporous silica film
Glass bead.Afterwards 1.0g surfactant pluronic P123 is dissolved in 40mL ethanol and adds 0.278g after stirring 30min
Five nitric hydrate bismuth (Bi (NO3)3.5H2O), stir 30min after Deca 1.5mL hydrochloric acid (HCl) solution.Add certain mass
AgNO3Adjusting silver with bismuth (Ag/Bi) mol ratio is 10%.Add 0.5g glucose afterwards and stir 1h.Put into 60 surfaces to bear
After carrying the glass bead stirring 180min of mesoporous silica film, it is placed in drying 24h at 80 DEG C.Repeating aforesaid operations 3 is plated film
After number of times is 3 times, by glass bead at 280 DEG C roasting 4h (heating rate be 4 DEG C/min), you can obtain area load Ag/
BiOCl visible light catalytic thin film and the glass bead of mesoporous silica film.
X-ray diffraction spectrum (XRD) figure of the sample that Fig. 1 is prepared for embodiment of the present invention 1-2, as shown in figure 1, show this reality
Apply the sample predominantly tetragonal phase BiOCl (JCPDS 06-0249) of example 1 preparation, degree of crystallinity is good, and there is certain Ag and receive
Rice corpuscles.
Fig. 2 is scanning electron microscope (SEM) photo of the sample of the embodiment of the present invention 1 preparation, as shown in Fig. 2 showing this enforcement
It is in lamellar structure after example roasting, and structure is more uniform.
Fig. 3 is X-ray photoelectron spectroscopic analysis (XPS) collection of illustrative plates of the sample of the embodiment of the present invention 1 preparation, as shown in figure 3,
Show Ag element in the present embodiment 1 mainly presented in simple substance.
Fig. 5 is UV-Vis DRS spectrum (UV-Vis DRS) figure of the embodiment of the present invention 1,2,8, as shown in figure 5,
It is followed successively by the UV-Vis DRS spectrogram of embodiment 1,8,2 from top to bottom.Fig. 5 show the present embodiment 1 have optimal can
See absorbing properties.Plasma effect mainly due to simple substance Ag nanoparticle enhances the absorption to visible ray for the catalyst.
Fig. 6 is that the embodiment of the present invention 7 is compared with the absorption property of the silica membrane adding other ratios TEOS, shows
The present embodiment 7 has optimal absorption property.
Fig. 7 is the absorption-photocatalysis performance contrast of embodiment of the present invention 1-6；Fig. 8 is embodiment of the present invention 1-2,9-11
Absorption-photocatalysis performance contrasts；Fig. 9 is the embodiment of the present invention 1, the absorption of 12-16-photocatalysis performance contrast；
By shown in Fig. 7-9, showing that the present embodiment 1 has more preferably photocatalytic activity compared with other embodiments.
Figure 10 is absorption-photocatalysis performance to different organic pollutions for the embodiment of the present invention 1, shows that the present invention can apply
Removal in Some Organic Pollutants.
Embodiment 2
It is added without AgNO in preparation process3, that is, Ag/Bi mol ratio is 0, and remaining content is same as Example 1.The X of Fig. 1 penetrates
Line diffraction spectra (XRD) figure shows that the present embodiment 2 is mainly tetragonal phase BiOCl (JCPDS 06-0249), and degree of crystallinity is good.Fig. 5
In UV-Vis DRS spectrum (UV-vis DRS) collection of illustrative plates show that the present embodiment 2 no substantially absorbs in visible region.Fig. 7
Show the present embodiment 2 no obvious photocatalytic activity under visible light.
Embodiment 3
Ag/Bi mol ratio is controlled to be 2.5% in preparation process, remaining content is same as Example 1.Fig. 7 shows visible
Under light, the present embodiment 3 has obvious photocatalytic activity compared with embodiment 2.
Embodiment 4
Ag/Bi mol ratio is controlled to be 5.0% in preparation process, remaining content is same as Example 1.Fig. 7 shows visible
Under light, the present embodiment 4 has obvious photocatalytic activity compared with embodiment 2.
Embodiment 5
Ag/Bi mol ratio is controlled to be 15.0% in preparation process, remaining content is same as Example 1.Fig. 7 shows visible
Under light, the present embodiment 5 has obvious photocatalytic activity compared with embodiment 2.
Embodiment 6
Ag/Bi mol ratio is controlled to be 20.0% in preparation process, remaining content is same as Example 1.Fig. 7 shows visible
Under light, the present embodiment 6 has obvious photocatalytic activity compared with embodiment 2.
Embodiment 7
Preparation process is added without Bi (NO3)3.5H2O, HCl solution and AgNO3, i.e. only loaded mesoporous silica membrane, its
Remaining content is same as Example 1.Transmission electron microscope (HRTEM) photo of Fig. 4 show silica membrane that the present embodiment 7 obtains by
Elliposoidal microsphere is piled up and is formed, size uniform and have ordered mesoporous pore canals.Specific surface area is 987.5m2/g.This is contrasted in Fig. 6
Embodiment 7 and the absorption property of the silica membrane adding other ratios TEOS, show that the present embodiment 7 has optimal absorption
Performance.
Embodiment 8
It is added without Bi (NO in preparation process3)3.5H2O and HCl solution, i.e. no BiOCl generation, remaining content and embodiment 1
Identical.Fig. 5 UV-Vis DRS spectrum (UV-Vis DRS) bright the present embodiment of chart 8 has certain absorption in visible region.
Embodiment 9
It is added without CTAB, sodium hydroxide, TEOS and AgNO in preparation process3, that is, not loaded mesoporous silica membrane and
No Ag nanoparticle, only generates BiOCl thin film.Remaining content is same as Example 1.Fig. 8 shows that the present embodiment 9 no substantially adsorbs
Performance and visible light catalysis activity.
Embodiment 10
It is added without CTAB, sodium hydroxide, TEOS, Bi (NO in preparation process3)3.5H2O and HCl solution, that is, not loaded mesoporous
Silica membrane and no BiOCl thin film, only generate Ag particle thin film.Remaining content is same as Example 1.Fig. 8 shows this reality
Apply the no obvious absorption property of example 10 and weaker visible light catalysis activity.
Embodiment 11
It is added without CTAB, sodium hydroxide and TEOS, that is, not loaded mesoporous silica membrane, only generates in preparation process
Ag/BiOCl thin film.Remaining content is same as Example 1.Fig. 8 shows the no obvious absorption property of the present embodiment 11, but display is relatively
Good visible light catalysis activity.
Embodiment 12
Coating times are changed to 1 time, remaining content is same as Example 1.Fig. 9 show the present embodiment 12 have certain can
See photocatalytic activity.
Embodiment 13
Coating times are changed to 2 times, remaining content is same as Example 1.Fig. 9 show the present embodiment 13 have certain can
See photocatalytic activity.
Embodiment 14
Coating times are changed to 4 times, remaining content is same as Example 1.Fig. 9 show the present embodiment 14 have certain can
See photocatalytic activity.
Embodiment 15
Coating times are changed to 5 times, remaining content is same as Example 1.Fig. 9 show the present embodiment 15 have certain can
See photocatalytic activity.
Embodiment 16
Coating times are changed to 6 times, remaining content is same as Example 1.Fig. 9 show the present embodiment 16 have certain can
See photocatalytic activity.
The invention also discloses the glass bead of plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film, by above-mentioned work
Skill is prepared from, for the collaborative processes of absorption in floating type reactor and photocatalytic degradation rhodamine B etc..
Specifically, adsorption-photocatalytic degradation system provided by the present invention is placed in for 150ml 10mg/L rhodamine B solution
In floating type reactor, investigate its degradation property.The showing of the floating type photo catalysis reactor that Figure 11 is provided by surface of the present invention
It is intended to, reactor diameter 125mm, the bubbling loop diameter 85mm of bottom, be uniformly distributed 12 pores, each hole diameter 5mm.Logical
Cross and change different gas speed and can obtain different reaction conditions, the gas speed scope in reactor is 0.28-0.60m/s, most preferably
Gas speed is 0.47m/s, and corresponding gas holdup is 0.32-0.43, and wherein optimal gas holdup is 0.39.
Concretely comprise the following steps：The glass bead of 60 plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis films is made before illumination
It is placed in reactor and rotates 30 minutes to reach adsorption equilibrium, open light source afterwards and start reaction.One 300W Xe lamp conduct
Light source is located at reactant ullage 18cm, and reaction temperature is 30 DEG C, and the response time is 30min.Sieve in solution after reaction
Red bright B concentration is calculated according to the absorbance that ultraviolet spectrophotometer (UV 7504/PC) measures at 553nm.
It is shown experimentally that, using the plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis of above-described embodiment 1 preparation
The glass bead of thin film has preferably absorbability and photocatalytic activity, being capable of the effective organic pollution such as rhodamine B degradation.
Obviously, those skilled in the art can carry out various change and deformation, without deviating from the present invention's to the present invention
Spirit and scope.So, if these modifications of the present invention belong within the scope of the claims in the present invention and its equivalent technology,
Then the present invention is also intended to comprise these changes and deforms.
Claims (8)
1. a kind of technique of glass bead plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film is it is characterised in that include：
Step 1:Clean and dry glass ball；
Step 2:Loaded mesoporous silica membrane in described glass ball surface, forms area load mesoporous silica film
Glass bead；
Step 3:Described glass ball surface loaded Ag/BiOCl visible light catalytic thin film again in step 2 gained；
Step 4:0-6 step 3 of repetition obtains loaded Ag/BiOCl visible light catalytic thin film and the meso-porous titanium dioxide of different-thickness
The glass bead of silicon thin film；
Step 2 specifically includes：
2.1 cetyl trimethylammonium bromide is added in deionized water, is stirring evenly and then adding into sodium hydroxide, adjusts solution
PH to 12, is stirring evenly and then adding into 0.5～7.0mL tetraethyl orthosilicate and stirs, and obtains the load of mesoporous silicon oxide adsorbent thin film
Solution；Cetyl trimethylammonium bromide surfactant and deionized water amount ratio are 1g：480mL；
2.2 put into glass bead described in step 1 in the loading solution of the mesoporous silicon oxide adsorbent thin film that step 2.1 obtains
Rotation makes its surface and the loading solution of mesoporous silicon oxide adsorbent thin film be fully contacted, and is placed in drying 24h at 80 DEG C after stirring,
Roasting 4h at 350-450 DEG C, obtain the glass bead of area load mesoporous silica film.
2. the technique of glass bead plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film as claimed in claim 1, its
It is characterised by：
Step 1 specifically includes：Described glass bead is placed in stirring in sulfuric acid solution, removes surface impurity, deionized water is cleaned
Clean and dry；Afterwards described glass bead is placed in deionized water after stirring in sodium hydroxide solution to clean up and be dried.
3. the technique of glass bead plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film as claimed in claim 2, its
It is characterised by：
Described glass bead is plain hollow glass bead, and density is 2.5～2.6g/cm3, a diameter of 10～11mm of glass bead, wall thickness
0.3～0.4mm.
4. the technique of glass bead plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film as claimed in claim 1, its
It is characterised by：
Step 3 specifically includes：
3.1 pluronic P123 surfactant is dissolved in ethanol, is stirring evenly and then adding into five nitric hydrate bismuths, Deca salt
Stir after acid solution；Adding silver nitrate and adjusting silver with bismuth mol ratio is 2.0～20%, adds 0.3-0.8g Fructus Vitis viniferae afterwards
Sugar simultaneously stirs, and obtains the loading solution of Ag/BiOCl visible light catalytic thin film；Described pluronic P123 surfactant
Amount ratio with described ethanol is 1g：40mL；
The 3.2 described glass beads obtaining step 3 put into the loading solution of Ag/BiOCl visible light catalytic thin film, are placed in after stirring
At 80 DEG C dry 24h, roasting 4h at 250-300 DEG C, obtain area load Ag/BiOCl visible light catalytic thin film and Jie
The glass bead of hole silica membrane.
5. the technique of glass bead plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film as claimed in claim 4, its
It is characterised by：
In described step 3.1, silver and bismuth mol ratio are 10%.
6. the technique of glass bead plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film as claimed in claim 1, its
It is characterised by, in described step 4, number of repetition is 3 times.
7. a kind of glass bead of plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film is it is characterised in that wanted by right
The technique described in 1-6 any one is asked to be prepared from.
8. the purposes of the glass bead of plated surface Ag/BiOCl- silicon dioxide absorption-photocatalysis film as claimed in claim 7,
It is characterized in that, in floating type reactor, adsorbing and photocatalytic degradation rhodamine B, methyl orange or methylene blue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510266251.9A CN104909579B (en) | 2015-05-22 | 2015-05-22 | The glass bead of plated surface Ag/BiOCl silica membrane and its technique and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510266251.9A CN104909579B (en) | 2015-05-22 | 2015-05-22 | The glass bead of plated surface Ag/BiOCl silica membrane and its technique and purposes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104909579A CN104909579A (en) | 2015-09-16 |
| CN104909579B true CN104909579B (en) | 2017-03-01 |
Family
ID=54079089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510266251.9A Expired - Fee Related CN104909579B (en) | 2015-05-22 | 2015-05-22 | The glass bead of plated surface Ag/BiOCl silica membrane and its technique and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104909579B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070197A (en) * | 2006-05-09 | 2007-11-14 | 北京化工大学 | Method for preparing porous glass bau with optical catalytic activity |
| CN101724839A (en) * | 2008-10-21 | 2010-06-09 | 国家纳米科学中心 | Micron/nanoscale BiOCl film material and preparation method thereof |
| CN103084163A (en) * | 2012-12-14 | 2013-05-08 | 上海师范大学 | Process for coating Bi2O3/TiO2 photocatalysis film on surface of hollow lightweight glass sphere |
| JP2014133678A (en) * | 2013-01-09 | 2014-07-24 | Toshiharu Kawasaki | Functional hollow glass microspheres and method for manufacturing the same |
-
2015
- 2015-05-22 CN CN201510266251.9A patent/CN104909579B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070197A (en) * | 2006-05-09 | 2007-11-14 | 北京化工大学 | Method for preparing porous glass bau with optical catalytic activity |
| CN101724839A (en) * | 2008-10-21 | 2010-06-09 | 国家纳米科学中心 | Micron/nanoscale BiOCl film material and preparation method thereof |
| CN103084163A (en) * | 2012-12-14 | 2013-05-08 | 上海师范大学 | Process for coating Bi2O3/TiO2 photocatalysis film on surface of hollow lightweight glass sphere |
| JP2014133678A (en) * | 2013-01-09 | 2014-07-24 | Toshiharu Kawasaki | Functional hollow glass microspheres and method for manufacturing the same |
Non-Patent Citations (1)
| Title |
|---|
| 《可见光催化薄膜复合体系应用于悬浮玻璃珠光催化反应器的研究》;李虎;《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》;20140228;20 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104909579A (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Heterostructured TiO2/WO3 nanocomposites for photocatalytic degradation of toluene under visible light | |
| Ji et al. | Fabrication and high photocatalytic performance of noble metal nanoparticles supported on 3DOM InVO4–BiVO4 for the visible-light-driven degradation of rhodamine B and methylene blue | |
| Li et al. | Preparation of visible light-driven SnS2/TiO2 nanocomposite photocatalyst for the reduction of aqueous Cr (VI) | |
| Sun et al. | Photocatalyst of organic pollutants decomposition: TiO2/glass fiber cloth composites | |
| CN106807430B (en) | G-C with special clad structure3N4The preparation method of@diatomite composite photocatalytic agent | |
| Yu et al. | Pd quantum dots loading Ti3+, N co-doped TiO2 nanotube arrays with enhanced photocatalytic hydrogen production and the salt ions effects | |
| CN102380367B (en) | Control synthetic method of high-visible-light-activity mixed crystal type BiVO4 photocatalysts | |
| CN106975503B (en) | A kind of preparation method of the modified phosphotungstic acid/titanium dioxide composite film catalyst of silver | |
| Chen et al. | Fabrication of tunable oxygen vacancies on BiOCl modified by spiral carbon fiber for highly efficient photocatalytic detoxification of typical pollutants | |
| CN108298591B (en) | synthesis method and application of hexagonal iron titanate nanosheet material | |
| Zhu et al. | TiO2 NTAs decorated with thin CuBi2O4 nanosheets for efficient photocatalytic dye degradation and hydrogen generation | |
| CN108864463B (en) | Self-supporting flexible super-hydrophilic titanium oxide film and preparation method thereof | |
| Liu et al. | Modification of ZIF-8 nanocomposite by a Gd atom doped TiO2 for high efficiency photocatalytic degradation of neutral red dye: An experimental and theoretical study | |
| CN106582619A (en) | Application of manganese oxide composite activated carbon material in denitrification | |
| CN106861723A (en) | A kind of visible light-responded bismuth oxygen hydrochlorate photochemical catalyst Bi16Te5O34Preparation method and applications | |
| CN104909579B (en) | The glass bead of plated surface Ag/BiOCl silica membrane and its technique and purposes | |
| Shu et al. | Design of silver-deposited carbon nitride nanotubes by a one-step solvothermal treatment strategy and their efficient visible-light photocatalytic activity toward methyl orange degradation | |
| CN103506104B (en) | Carbon-doped TiO2 visible light-responding catalytic film on glass carrier and preparation method thereof | |
| Zhang et al. | A multifunctional composite membrane with photocatalytic, self-cleaning, oil/water separation and antibacterial properties | |
| CN102786080A (en) | Indium tin oxide compound, its preparation method and its photocatalytic application | |
| Cen et al. | The effect of background irradiation on photocatalytic efficiencies of TiO2 thin films | |
| CN102600819A (en) | Porous titanium dioxide photocatalyst film and preparation method thereof | |
| Yang et al. | One pot microwave-assisted synthesis of Ag decorated yolk@ shell structured TiO 2 microspheres | |
| Meng et al. | Growth of TiO2/Ti-MOF nanorod array with enhanced photoabsorption and photocatalytic properties on carbon cloth for efficient auto-cleaning solar desalination | |
| CN109095546A (en) | A kind of method of photocatalysis treatment of waste water collaboration hydrogen making |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170301 Termination date: 20180522 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |