CN108855202A - For photocatalytic water and the composite photo-catalyst of contaminant degradation and preparation method thereof - Google Patents
For photocatalytic water and the composite photo-catalyst of contaminant degradation and preparation method thereof Download PDFInfo
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- CN108855202A CN108855202A CN201810582412.9A CN201810582412A CN108855202A CN 108855202 A CN108855202 A CN 108855202A CN 201810582412 A CN201810582412 A CN 201810582412A CN 108855202 A CN108855202 A CN 108855202A
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- catalyst
- composite photo
- mesoporous
- photocatalytic activity
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 89
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 81
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of for photocatalytic water and the composite photo-catalyst of contaminant degradation and preparation method thereof, which can realize solar energy to chemical energy Efficient Conversion；It is mainly combined by mesoporous template and photocatalytic activity ingredient in nanoscale, the photocatalytic activity ingredient is the nano particle of composite metal salt, and the photocatalytic activity ingredient that is complex as is dispersed in the duct skeleton of the mesoporous template；It is described compound through the following steps that realize：Soluble metallic salt presoma and complexing agent are complexed, and diffused into the duct of mesoporous template, the then high-temperature calcination under confinement environment.Catalyst of the present invention is mainly used under sunlight in photocatalysis Decomposition aquatic products hydrogen or photocatalytic degradation water or organic pollutant such as VOC, s-VOC etc. in air.Gained catalyst stability of the invention is good, and good dispersion decomposes the photocatalysis of water completely and the photocatalytic degradation of organic matter is highly active by Supported Pt Nanoparticles or other co-catalysts.
Description
Technical field
The present invention relates to photocatalyst technology fields, and in particular, to a kind of for photocatalytic water and contaminant degradation
Composite photo-catalyst and preparation method thereof.The present invention provides a kind of and compound composite photocatalyst of porous material preparation,
Especially there is the photocatalytic compound of certain mesoporous pattern, be used for inorganic semiconductor photocatalysis technology field.
Background technique
Photocatalysis is one kind by suitable catalyst, to use the energy of luminous energy (solar energy) realization solar energy to Hydrogen Energy
The new technique of amount conversion and Organic Pollutants in Wastewater removal.Since it can be the energy problem nowadays got worse
One ideal solution is all provided with environmental problem, and has at low cost, reaction condition is mild, and it is easy to operate, without two
The advantages that secondary pollution is a kind of new energy and Environmental Technology for having great potential.The inorganic semiconductor studied extensively now
The basic principle of type photochemical catalyst is under illumination condition, and photochemical catalyst generates light induced electron and hole, they are migrated to catalysis
On the active site on agent surface, redox reaction occurs with water or organic pollutants respectively and realizes production hydrogen and degradation.Mesh
The preceding main problem for limiting its technical application is that the efficiency of existing photochemical catalyst is generally lower, main reason is that one side light
Catalyst is weaker to the absorbability of sunlight, and another aspect photo-generate electron-hole is easy compound, these factors make photocatalysis
The quantum efficiency of agent is generally lower.Current main research direction focuses primarily upon the exploration to novel photocatalyst, including right
Existing photochemical catalyst carries out certain doping vario-property etc., and to the composite photocatalyst with specific morphology and synergistic effect
Exploration.
Porous material, especially mesoporous material specific surface area with higher, extremely strong adsorption capacity and high-sequential
Meso-hole structure, the attention by many researchers.Many has the photochemical catalyst of certain mesoporous pattern all successfully to be prepared, and by
Proof is all significantly increased on photocatalysis effect.And mesic hole compound is due to the coupling of multi phase interface, quantum confinement effect
It answers and the influence of environment, makes it have a series of special performances, therefore cause the great interest of people.Compared to common zeolite
Molecular sieve, mesoporous material has bigger aperture and porosity, and has better adjustability and expansion, is more advantageous to catalyst
Active reaction is carried out in duct.By the retrieval discovery to existing technical literature, Chinese invention patent application number is
201510290917.4 entitled：Compound colloidal sol preparation method with high efficiency photocatalysis performance, that application discloses one kind
Using mesoporous carbon template CMK-3 as substratess, using butyl titanate as titanium source, CMK-3/TiO is prepared by sol-gel method2It is situated between
The method of hole composite photo-catalyst.The catalyst can effectively degrade methyl blue, and efficiency with higher.But it is above-mentioned
Catalyst synthesis processes are complicated, long preparation period, while obtaining material is simple metal oxide, and can not complete solution water, have
Lower application prospect.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide a kind of for photocatalytic water and contaminant degradation
Composite photo-catalyst and preparation method thereof.
The prepared catalyst of present invention work can obtain the complex light of the complex composite metal salt with mesoporous pattern
Catalyst, and the close contact between photochemical catalyst and carrier in nanoscale is realized, high knot is being obtained by high-temperature calcination
Guarantee catalyst good dispersion while crystalline substance and be unlikely to reunite, keeps the crystallite dimension of Nano grade, height may be implemented
Decompose the removal of aquatic products hydrogen and organic pollutant in effect ground；Preparation method has good expansibility and facilitates progress simultaneously
Other modifications, can successfully prepare the composite catalyst of different types of complex composite metal salt and porous carrier, have to research
The exploration and design for having the composite photocatalyst of specific morphology and synergistic effect have positive meaning.
The purpose of the present invention is achieved through the following technical solutions：
In a first aspect, the present invention provides a kind of composite photo-catalyst, including mesoporous template and photocatalytic activity ingredient；It is described
Photocatalytic activity ingredient is dispersed in the duct skeleton of mesoporous template；In the composite photo-catalyst, photocatalytic activity at
The mass fraction divided is 10%-90%；The photocatalytic activity ingredient is the nano particle of composite metal salt.
Preferably, the composite metal salt includes BixM2-xA2O8Type compound, D-SrTiO3Type compound, SrTiO3Type
Close the mixing of one or more of object；The BixM2-xA2O8In type compound, in M=Y, La, Ce, Pr, Nd, Sm, In one
Kind or several mixing, one or more of A=V, W, Mo mixing, 0<x<2；The D-SrTiO3In type compound, D=
The mass fraction of the mixing of one or more of Ga, La, Na, Ta, Rh, Mn, Ru, Pd, Ir, Pt, Sb, Al, D element is
0.1%~10%.The Bi that the present invention selectsxM2-xA2O8Type compound, D-ETiO3Type compound, ETiO3Type compound compared to
Other compounds have better effect.
Preferably, the mesoporous template includes mesoporous silicon oxide, meso-porous alumina, at least one in fumed silica
Kind.The better heat stability of silica and alumina material, translucency are also more preferable；Active carbon or porous Nano carbon balls are due to carbon
Template thermal stability is poor, is unsuitable for the present invention.
It is highly preferred that the mesoporous silicon oxide is the mesoporous silicon oxide of hydro-thermal process, specifically, including rare earth element
Y, the mesoporous silicon oxide of Yb, Er, Tm, Pr doping or Ti, Al doping；The meso-porous alumina is the mesoporous oxygen of hydro-thermal process
Change aluminium, specifically, the meso-porous alumina including Y, Yb, Er, Tm, Pr doping or Ti doping.
Preferably, the composite photo-catalyst it is mainly compound in nanoscale by mesoporous template and photocatalytic activity ingredient and
At；It is described compound to include the following steps：Soluble metallic salt presoma and complexing agent are complexed, obtained complex compound diffuses into
In the duct of mesoporous template, the then high-temperature calcination under confinement environment.Core of the invention is to be existed by template and photochemical catalyst
The composite construction with mesoporous pattern that nanoscale is constituted；The synthesis of composite photo-catalyst needs preferable calcination temperature, and
It is acted on by mesoporous confinement and stablizes photochemical catalyst partial size.
Preferably, the complexing agent include citric acid, ethylene glycol, glycine, in ethylenediamine tetra-acetic acid (EDTA) at least
It is a kind of；The solvent for dissolving the complexing agent includes at least one of deionized water, acetic acid, dehydrated alcohol, anhydrous methanol.Selection
The reason of above-mentioned complexing agent is that the complexing effect based on these complexing agents is more preferable, and this is a kind of carbon containing small molecule, contains hydroxyl
The complexing agent of base and carboxylic group can also provide acidic environment.
Preferably, the high-temperature calcination condition is：400~1000 DEG C are risen to the heating rate of 1 DEG C/min, calcination time
It is 6~24 hours.Too low temperature or too short calcination time are unfavorable for the formation of solid solution, and crystallinity is not high, influence to live
Property；Excessively high temperature will lead to composite construction collapsing sintering, cause active decline.Moreover, too fast heating rate is unfavorable for living
Diffusion of the property catalyst component in duct；It crosses slow heating rate then to take more time, influences efficiency.
Preferably, it is 30%~85% that the photocatalytic activity ingredient, which accounts for the mass fraction of the composite photo-catalyst,.When
Template can make that active constituent is very few in composite catalyst when excessive, influence overall activity；When template is very few, can light be urged
It is excessive to change active constituent, overflows duct and reunites in duct outgrowth, influence activity.
It is highly preferred that the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 50%~70%.
There is best catalytic activity when photocatalytic activity ingredient is the range.
It preferably, further include co-catalyst, the co-catalyst is supported on photocatalytic activity ingredient；The co-catalyst
Including Pt, Au, Ag, RuO2、NiOx、RhCrO3、Co3O4、MoO3、IrO2At least one of, wherein 0<x<1.
Second aspect, the present invention provide a kind of preparation method of composite photo-catalyst, including the mesoporous template with it is described
The compound method of photocatalytic activity ingredient, specifically comprises the following steps：
B1, enveloping agent solution is prepared, metal salt presoma is added in the enveloping agent solution, stir simultaneously ultrasonic disperse,
Obtain forerunner's liquid suspension；
B2, mesoporous template is mixed with forerunner's liquid suspension, stirs simultaneously ultrasonic disperse, obtains mixing suspension；
B3, the mixing suspension heating stirring is evaporated, then drying, calcining are lived to get mesoporous template and photocatalysis
The compound of property ingredient.
The present invention is by selecting specific condition：Such as complexing agent, the ratio of complexing agent additive amount and precursor salt, presoma
The selection of metal salt, the selection of templating species, presoma metal salt and template additive amount ratio, solution ph, calcination temperature
And calcination time etc., final obtain have order mesoporous pattern, the higher composite photo-catalyst of activity.
Preferably, in step B1, the complexing agent includes citric acid, ethylene glycol, glycine, ethylenediamine tetra-acetic acid (EDTA)
At least one of；Prepare the enveloping agent solution solvent include deionized water, acetic acid, dehydrated alcohol, in anhydrous methanol
It is at least one.
Preferably, the pH value of the enveloping agent solution is 1.0-6.0.PH selects the reason of environment of slant acidity to be to inhibit
The hydrolysis of presoma metal salt promotes complexing.If the too low destruction that will lead to template, too high to will affect solid solution.
Preferably, total dosage of the metal salt presoma and the molar ratio of amount of complex are 4:1~1:4.Excessive
Complexing agent can make cellular structure be destroyed, and very few complexing agent will affect complexing effect.
Preferably, in step B2, the mesoporous template mixed with forerunner's liquid suspension the specific steps are：It will be mesoporous
Template adds in forerunner's liquid suspension, and stirring is sufficiently submerged in the duct of mesoporous template for 0.5~10 hour to presoma, institute
The molar ratio for giving an account of the dosage of hole template and total dosage of the metal salt presoma is 1:1~10:1.Too low mixing time
It will lead to forerunner's liquid suspension to be unable to fully in the duct for immersing mesoporous template, excessively high mixing time influences combined coefficient.
Preferably, in step B3, the method for the calcining is：Collected powder will be dried to be placed in crucible, with 1 DEG C/
The heating rate of min rises to 400~1000 DEG C, and calcination time is 6~24 hours.
The third aspect, the present invention provide a kind of composite photo-catalyst in photochemical catalyzing, photocatalysis Decomposition organic contamination
Application in object.Catalyst of the present invention be mainly used under sunlight in photocatalysis Decomposition aquatic products hydrogen or photocatalytic degradation water or
Organic pollutant such as VOC, s-VOC etc. in air.
The invention discloses it is a kind of may be implemented solar energy to chemical energy Efficient Conversion composite photocatalyst material and its system
Preparation Method；The photochemical catalyst be by with porous, the template and photocatalytic activity ingredient of especially mesoporous pattern at high temperature,
It is combined in the case of nano-pore confinement, the photocatalytic activity ingredient is BixM2-xA2O8Or other metal composite oxides or
One or more of composite metal salt；The catalyst carrier is mesoporous silicon oxide or other porous high-ratio surface product modules
Plate；The invention further relates to aforementioned catalytic agent and the preparation methods of catalyst carrier.Catalyst of the present invention is mainly used in sunlight
Organic pollutant such as VOC, s-VOC etc. in lower photocatalysis Decomposition aquatic products hydrogen or photocatalytic degradation water or in air.System of the present invention
Standby process is simple, easily modified and expand, and gained catalyst stability is good, good dispersion, by Supported Pt Nanoparticles or other help and urge
Agent decomposes the photocatalysis of water completely and the photocatalytic degradation of organic matter is highly active.
Compared with prior art, the present invention has following beneficial effect：
1, nano-photocatalyst and the compound preparation method of mesoporous material are realized the present invention provides a kind of, it is more by having
Photocatalytic activity ingredient in the template and entrance duct of the hard template of pore structure, especially ordered mesopore structure is in nanoscale
Be combined, may be implemented under illumination condition to water it is complete decompose or sewage in or the light of Atmospheric Organic Pollutants urge
Change and decomposes.Orderly porous pattern improves the specific surface area of composite catalyst, is obtaining high crystalline by high-temperature calcination
Guarantee the good dispersion of catalyst simultaneously and be unlikely to reunite, keeps the crystallite dimension of Nano grade, and facilitate the suction to light
It receives, the transmission of reactant and product in the migration and reaction process in light induced electron and hole；Evenly dispersed light in duct
Catalytic active component is by the way that with the contact of the sufficient nanoscale of hole wall, the coupling and quantum for generating multi phase interface are limited
Domain effect and electron delocalization effect, have effectively facilitated the separation of photo-generate electron-hole, to improve photocatalytic activity.
2, composite mesoporous catalyst process prepared by the present invention is simple, easily controllable, easy to operate；Used catalyst template
Large specific surface area, stability is good, has the mesoporous pattern of high-sequential, and easily modified, facilitates and carries out element doping or use
Similar approach synthesizes the composite oxides template of other mesoporous patterns；The mesic hole compound formed after compound with photochemical catalyst is in water
Middle good dispersion, stability is high, not easy in inactivation, shows high activity in the test of complete solution water and contaminant degradation.Invention
The preparation method expansibility being related to is good, and a series of composite mesoporous catalyst systems synthesized based on this show higher
Activity.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is that the mesoporous silicon oxide template TEM prepared in the embodiment of the present invention 1 characterizes schematic diagram；
Fig. 2 is that the TEM of the mesoporous nano composite photocatalyst material prepared in the embodiment of the present invention 1 characterizes schematic diagram.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Embodiment 1
This example is related to the preparation method and its photocatalytic water activity of a kind of composite photo-catalyst with order mesoporous pattern
Test：
Step 1, weighs 0.5464g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 15ml deionized water；Complexing
Solution ph is 2.0；
Step 2 weighs five nitric hydrate bismuth Bi (NO of 0.4851g3)3·5H2O is as bismuth source, six nitric hydrate of 0.3830g
Yttrium Y (NO3)3·6H2O is as yttrium source, 0.2340g ammonium metavanadate NH4VO3As vanadium source, sequentially add in step 1 acquired solution,
Magnetic agitation 30min and ultrasonic disperse 30min are to forming unit for uniform suspension；Weigh the 0.334g silica template of preparation
(SBA-15) (TEM figure is shown in Fig. 1), it can be seen from figure 1 that prepared SBA-15 has mesopore orbit structure well, aperture
About 6nm, wall thickness are about 5nm.SBA-15 is added in aforementioned suspension, stirs ultrasound uniformly；
Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, dries 12 hours in 80 DEG C of baking ovens by step 3
It after grinding is collected afterwards, is put into the porcelain crucible that volume is 50ml, 800 DEG C of guarantors is risen with the heating rate of 1 DEG C/min in Muffle furnace
Temperature calcining 12 hours takes out grinding after cooling, obtains dry powder solid sample, sample TEM figure is shown in Fig. 2；It can from Fig. 2
Out, photocatalytic activity ingredient is homogeneously dispersed in mesopore orbit, and cellular structure is preferably retained, and forms good receive
The compound mesic hole compound structure catalyst of meter ruler cun.In the present embodiment, the photocatalytic activity ingredient accounts for the complex light and urges
The mass fraction of agent is 61.2%.
Step 4 weighs 0.1g step 3 obtained solid powder infusion in 1.35ml chloroplatinic acid aqueous solution, passes through 300W
Xenon light shining 3 hours, form the BiYV of Pt load2O8- SBA composite photo-catalyst, the mass fraction of institute's supporting Pt are 2wt%.
Implementation result：By the above-mentioned BiYV loaded through Pt of 0.1g2O8- SBA mesoporous nano complex material is scattered in 100ml
It in water, is placed in the photo catalysis reactor that material is Pyrex glass, the test of illumination complete solution water is carried out under 300W xenon lamp, light is urged
Change the gas that reaction generates and makees quantitative analysis with the gas chromatograph with thermal-conductivity detector.It tests obtained production hydrogen and produces oxygen speed
Rate is respectively averagely 180.5 μm of ol/h and 83.7 μm of ol/h.
In the present embodiment, the catalyst carrier of high adsorption, bigger serface, mesoporous silicon oxide template (SBA-15)
Preparation, includes the following steps：
Step 1.1, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) is dissolved in hydrochloric acid
The P123 solution of clear homogeneous is formed in solution；
Step 1.2, it stirs, on one side instills tetraethyl orthosilicate (TEOS) in the clear solution dropwise on one side；
Step 1.3, which is stirred evenly under water bath；
Step 1.4, which is put into heating and thermal insulation in reaction kettle；
Step 1.5, after being cooled to room temperature, reaction kettle is taken out, washing and drying obtains white powder；
Step 1.6, remaining polymer in white powder is removed, mesoporous SiO can be obtained2Template；
Further, in the step 1.1, the P123 solution preparation method is：
3~6g P123 is dissolved in 97.5~195ml water, and 15~30ml concentrated hydrochloric acid is added, it is molten P123 can be obtained
Liquid.
Further, in the step 1.2, the clear solution preparation method is：
It stirs, on one side slowly instills 6.7~13.4ml TEOS in step 1.1 acquired solution dropwise on one side.
Further, in the step 1.3, the stirring environment is：
It is slowly stirred under 35~40 DEG C of water baths 12~24 hours.
Further, in the step 1.4, the heating heat preserving method is：
Step 1.3 acquired solution is placed in 160~200ml water heating kettle, 100~110 DEG C of hydro-thermals 12~24 in baking oven
Hour.
Further, in the step 1.6, it is by the method that residual polyalcohol removes：
White powder after drying is risen to 500~550 DEG C with the heating rate of 1 DEG C/min to calcine 180~300 minutes；Or
Polymer is removed using concentrated hydrochloric acid and mixed solution of hydrogen peroxide extracting process；Or use concentrated nitric acid and mixed solution of hydrogen peroxide
Microwave heating method removes polymer.
Embodiment 1-1
The present embodiment is the change case of embodiment 1, only relates to change calcination temperature and time：Specially in embodiment 1
In step 3：Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, is ground after being dried 12 hours in 80 DEG C of baking ovens
It after collection, is put into the porcelain crucible that volume is 50ml, 600 DEG C of heat preservation calcinings is risen with the heating rate of 1 DEG C/min in Muffle furnace
12 hours, grinding is taken out after cooling, obtains dry powder solid sample；Other steps and test condition are constant.What test obtained
Producing hydrogen and producing oxygen rate is respectively averagely 128.3 μm of ol/h and 59.4 μm of ol/h.
Embodiment 1-2
The present embodiment is the change case of embodiment 1, only relates to change calcination temperature and time：Specially in embodiment 1
In step 3：Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, is ground after being dried 12 hours in 80 DEG C of baking ovens
It after collection, is put into the porcelain crucible that volume is 50ml, 400 DEG C of heat preservation calcinings 6 is risen with the heating rate of 1 DEG C/min in Muffle furnace
Hour, grinding is taken out after cooling, obtains dry powder solid sample；Other steps and test condition are constant.Test obtained production
Hydrogen and production oxygen rate are respectively averagely 5.4 μm of ol/h and 8.7 μm of ol/h.
Pass through Experimental Characterization, the results showed that be that can form composite construction and solid solution, but activity is lower to be at 400 DEG C
Since temperature and time is lower, crystallinity reason high not enough.
Embodiment 1-3
The present embodiment is the change case of embodiment 1, only relates to change calcination temperature and time：Specially in embodiment 1
In step 3：Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, is ground after being dried 12 hours in 80 DEG C of baking ovens
It after collection, is put into the porcelain crucible that volume is 50ml, 1000 DEG C of heat preservation calcinings is risen with the heating rate of 1 DEG C/min in Muffle furnace
24 hours, grinding is taken out after cooling, obtains dry powder solid sample；Other steps and test condition are constant.What test obtained
Producing hydrogen and producing oxygen rate is respectively averagely 45.3 μm of ol/h and 20.1 μm of ol/h.
Embodiment 2
This example is related to the preparation method and its photocatalytic water activity of a kind of composite photo-catalyst with order mesoporous pattern
Test：
Step 1, weighs 0.5464g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 15ml deionized water；
Step 2 weighs five nitric hydrate bismuth Bi (NO of 0.4851g3)3·5H2O is as bismuth source, six nitric hydrate of 0.4330g
Lanthanum La (NO3)3·6H2O is as lanthanum source, 0.2340g ammonium metavanadate NH4VO3As vanadium source, step 1 acquired solution is sequentially added
In, magnetic agitation 30min and ultrasonic disperse 30min are to forming unit for uniform suspension；Weigh 0.334g silica template (SBA-
15) it is added in aforementioned suspension, stirs ultrasound uniformly；
Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, dries 12 hours in 80 DEG C of baking ovens by step 3
It after grinding is collected afterwards, is put into the porcelain crucible that volume is 50ml, 800 DEG C of guarantors is risen with the heating rate of 1 DEG C/min in Muffle furnace
Temperature calcining 12 hours takes out grinding after cooling, obtains dry powder solid sample；In the present embodiment, the photocatalytic activity at
Dividing the mass fraction for accounting for the composite photo-catalyst is 63.4%.
Step 4 weighs 0.1g step 3 obtained solid powder infusion in 1.35ml chloroplatinic acid aqueous solution, passes through 300W
Xenon light shining 3 hours, form the BiLaV of Pt load2O8- SBA composite photo-catalyst, the mass fraction of institute's supporting Pt are 2wt%.
Implementation result：By the above-mentioned BiLaV loaded through Pt of 0.1g2O8- SBA mesoporous nano complex material is scattered in 100ml
It in water, is placed in the photo catalysis reactor that material is Pyrex glass, the test of illumination complete solution water is carried out under 300W xenon lamp, light is urged
Change the gas that reaction generates and makees quantitative analysis with the gas chromatograph with thermal-conductivity detector.It tests obtained production hydrogen and produces oxygen speed
Rate is respectively averagely 157.9 μm of ol/h and 67.3 μm of ol/h.
Embodiment 2-1
The present embodiment is the change case of embodiment 2, only relates to change doped chemical：Specially two embodiment 2 the step of
In：Weigh six nitric hydrate cerium Ce (NO of 0.4342g3)3·6H2O is as cerium source, and instead of lanthanum source, other steps are constant and test-strips
Part is constant.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 63.4%.Gained
The BiCeV of Pt load2O8The production hydrogen and produce oxygen rate respectively averagely 134.6 μm of ol/h that-SBA composite photo-catalyst is tested
With 56.3 μm of ol/h.
Embodiment 2-2
The present embodiment is the change case of embodiment 2, only relates to change doped chemical：Specially two embodiment 2 the step of
In：Weigh six nitric hydrate praseodymium Pr (NO of 0.4350g3)3·6H2O is as praseodymium source, and instead of lanthanum source, other steps are constant and test-strips
Part is constant.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 63.4%.Gained
The BiPrV of Pt load2O8The production hydrogen and produce oxygen rate respectively averagely 125.4 μm of ol/h that-SBA composite photo-catalyst is tested
With 49.7 μm of ol/h.
Embodiment 2-3
The present embodiment is the change case of embodiment 2, only relates to change doped chemical：Specially two embodiment 2 the step of
In：Weigh six nitric hydrate neodymium Nd (NO of 0.4383g3)3·6H2O is as neodymium source, and instead of lanthanum source, other steps are constant and test-strips
Part is constant.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 63.6%.Gained
The BiNdV of Pt load2O8The production hydrogen and produce oxygen rate respectively averagely 108.5 μm of ol/h that-SBA composite photo-catalyst is tested
With 41.3 μm of ol/h.
Embodiment 2-4
The present embodiment is the change case of embodiment 2, only relates to change doped chemical：Specially two embodiment 2 the step of
In：Weigh six nitric hydrate samarium Sm (NO of 0.4445g3)3·6H2O is as samarium source, and instead of lanthanum source, other steps are constant and test-strips
Part is constant.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 63.8%.Gained
The BiSmV of Pt load2O8Production hydrogen that-SBA composite photo-catalyst is tested and produce oxygen rate be respectively averagely 97.3 μm of ol/h and
38.4μmol/h。
Embodiment 3
The present embodiment is related to a kind of preparation method its photocatalytic water activity of composite photo-catalyst with order mesoporous pattern
Test：
Step 1, weighs 0.5464g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 15ml deionized water；
Step 2 weighs five nitric hydrate bismuth Bi (NO of 0.4851g3)3·5H2O is as bismuth source, six nitric hydrate of 0.3830g
Yttrium Y (NO3)3·6H2O is sequentially added in step 1 acquired solution, magnetic force as yttrium source, 0.2479g ammonium metatungstate as tungsten source
Stirring 30min and ultrasonic disperse 30min is to forming unit for uniform suspension；Before weighing 0.334g silica template (SBA-15) addition
It states in suspension, stirs ultrasound uniformly；
Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, dries 12 hours in 80 DEG C of baking ovens by step 3
It after grinding is collected afterwards, is put into the porcelain crucible that volume is 50ml, 800 DEG C of guarantors is risen with the heating rate of 1 DEG C/min in Muffle furnace
Temperature calcining 12 hours takes out grinding after cooling, obtains dry powder solid sample；In the present embodiment, the photocatalytic activity at
Dividing the mass fraction for accounting for the composite photo-catalyst is 63.4%.
Step 4 weighs 0.1g step 3 obtained solid powder infusion in 1.35ml chloroplatinic acid aqueous solution, passes through 300W
Xenon light shining 3 hours, form the BiYWO of Pt load6- SBA composite photo-catalyst, the mass fraction of institute's supporting Pt are 2wt%.
Implementation result：By the above-mentioned BiYWO loaded through Pt of 0.1g6- SBA mesoporous nano complex material is scattered in 100ml
It in water, is placed in the photo catalysis reactor that material is Pyrex glass, the test of illumination complete solution water is carried out under 300W xenon lamp, light is urged
Change the gas that reaction generates and makees quantitative analysis with the gas chromatograph with thermal-conductivity detector.It tests obtained production hydrogen and produces oxygen speed
Rate is respectively averagely 156.3 μm of ol/h and 67.3 μm of ol/h.
Embodiment 3-1
The present embodiment is the change case of embodiment 3, only relates to change doped chemical：Specially two embodiment 3 the step of
In：Weigh 0.1960g ammonium molybdate (NH4)2MoO4As molybdenum source, instead of tungsten source, other steps are constant and test condition is constant.This
In embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 59.5%.Gained Pt load
BiYMoO6The production hydrogen and produce oxygen rate respectively averagely 145.2 μm of ol/h and 64.9 μ that-SBA composite photo-catalyst is tested
mol/h。
Embodiment 4
This example is related to the preparation method and its photocatalytic water activity of a kind of composite photo-catalyst with order mesoporous pattern
Test：
Step 1, weighs 0.5464g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 15ml deionized water；
Step 2 weighs five nitric hydrate bismuth Bi (NO of 0.4851g3)3·5H2O is as bismuth source, six nitric hydrate of 0.3830g
Yttrium Y (NO3)3·6H2O is as yttrium source, 0.2340g ammonium metavanadate NH4VO3As vanadium source, sequentially add in step 1 acquired solution,
Magnetic agitation 30min and ultrasonic disperse 30min are to forming unit for uniform suspension；0.334g silica template (KIT-6) is weighed to add
Enter in aforementioned suspension, stirs ultrasound uniformly；
Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, dries 12 hours in 80 DEG C of baking ovens by step 3
It after grinding is collected afterwards, is put into the porcelain crucible that volume is 50ml, 800 DEG C of guarantors is risen with the heating rate of 1 DEG C/min in Muffle furnace
Temperature calcining 12 hours takes out grinding after cooling, obtains dry powder solid sample；In the present embodiment, the photocatalytic activity at
Dividing the mass fraction for accounting for the composite photo-catalyst is 61.2%.
Step 4 weighs 0.1g step 3 obtained solid powder infusion in 1.35ml chloroplatinic acid aqueous solution, passes through 300W
Xenon light shining 3 hours, form the BiYV of Pt load2O8- KIT composite photo-catalyst, the mass fraction of institute's supporting Pt are 2wt%.
Implementation result：By the above-mentioned BiYV loaded through Pt of 0.1g2O8- KIT mesoporous nano complex material is scattered in 100ml
It in water, is placed in the photo catalysis reactor that material is Pyrex glass, the test of illumination complete solution water is carried out under 300W xenon lamp, light is urged
Change the gas that reaction generates and makees quantitative analysis with the gas chromatograph with thermal-conductivity detector.It tests obtained production hydrogen and produces oxygen speed
Rate is respectively averagely 43.5 μm of ol/h and 19.2 μm of ol/h.
In the present embodiment, the bibliography for preparing of silica template KIT-6 is：Kim T W,Kleitz F,Paul B,
et al.MCM-48-like large mesoporous silicas with tailored pore structure:
facile synthesis domain in a ternary triblock copolymer-butanol-water system
[J].Journal of the American Chemical Society,2005,127(20):7601-7610.
Embodiment 4-1
The present embodiment is the change case of embodiment 4, only relates to change addition templating species and quality：Specially in embodiment
In 4 the step of two：0.1g silica template (SBA-15) is weighed as template, is added in aforementioned suspension, other steps are not
Become and test condition is constant.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is
84.1%.The BiYV of gained Pt load2O8The production hydrogen and produce oxygen rate respectively averagely that-SBA composite photo-catalyst is tested
127.5 μm of ol/h and 54.8 μm of ol/h.
Embodiment 4-2
The present embodiment is the change case of embodiment 4, only relates to change addition templating species and quality：Specially in embodiment
In 4 the step of two：Weigh 1.0g fumed silica (gSiO2) as template, (fumed silica purchase is certainly：Aladdin,
No. CAS is：112945-52-5), it is added in aforementioned suspension, other steps are constant and test condition is constant.In the present embodiment,
The mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 34.5%.The BiYV of gained Pt load2O8-
gSiO2The production hydrogen and produce oxygen rate respectively averagely 45.7 μm of ol/h and 23.2 μm of ol/h that composite photo-catalyst is tested.
Embodiment 4-3
The present embodiment is the change case of embodiment 4, only relates to change addition templating species and quality：Specially in embodiment
In 4 the step of two：Weigh 0.334g meso-porous alumina (Al2O3) it is used as template, it is added in aforementioned suspension, other steps are constant
It is constant with test condition.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is
61.2%.The BiYV of gained Pt load2O8-Al2O3The production hydrogen and produce oxygen rate respectively averagely that composite photo-catalyst is tested
125.7 μm of ol/h and 65.9 μm of ol/h.
In the present embodiment, meso-porous alumina prepares bibliography and is：Vaudry F,Khodabandeh S,Davis M
E.Synthesis of pure alumina mesoporous materials[J].Chemistry of Materials,
1996,8(7):1451-1464.
Embodiment 5
This example is related to the preparation method and its photocatalytic water activity of a kind of composite photo-catalyst with order mesoporous pattern
Test：
Step 1, weighs 0.5464g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 15ml deionized water；Gradually
It instills 2mol/L dust technology or ammonium hydroxide adjusts solution ph to 1.0；
Step 2 weighs five nitric hydrate bismuth Bi (NO of 0.4851g3)3·5H2O is as bismuth source, six nitric hydrate of 0.3830g
Yttrium Y (NO3)3·6H2O is as yttrium source, 0.2340g ammonium metavanadate NH4VO3As vanadium source, sequentially add in step 1 acquired solution,
Magnetic agitation 30min and ultrasonic disperse 30min are to forming unit for uniform suspension；0.334g silica template (SBA-15) is weighed to add
Enter in aforementioned suspension, stirs ultrasound uniformly；
Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, dries 12 hours in 80 DEG C of baking ovens by step 3
It after grinding is collected afterwards, is put into the porcelain crucible that volume is 50ml, 800 DEG C of guarantors is risen with the heating rate of 1 DEG C/min in Muffle furnace
Temperature calcining 12 hours takes out grinding after cooling, obtains dry powder solid sample；In the present embodiment, the photocatalytic activity at
Dividing the mass fraction for accounting for the composite photo-catalyst is 61.2%.
Step 4 weighs 0.1g step 3 obtained solid powder infusion in 1.35ml chloroplatinic acid aqueous solution, passes through 300W
Xenon light shining 3 hours, form the BiYV of Pt load2O8- SBA composite photo-catalyst, the mass fraction of institute's supporting Pt are 2wt%.
Implementation result：By the above-mentioned BiYV loaded through Pt of 0.1g2O8- SBA mesoporous nano complex material is scattered in 100ml
It in water, is placed in the photo catalysis reactor that material is Pyrex glass, the test of illumination complete solution water is carried out under 300W xenon lamp, light is urged
Change the gas that reaction generates and makees quantitative analysis with the gas chromatograph with thermal-conductivity detector.It tests obtained production hydrogen and produces oxygen speed
Rate is respectively averagely 127.5 μm of ol/h and 55.2 μm of ol/h.
Embodiment 5-1
The present embodiment is the change case of embodiment 5, only relates to change complexing environment acid-base property (pH value)：Specially implementing
In the step of example 5 one：It is gradually dropped 2mol/L dust technology or ammonium hydroxide adjusts solution ph to 3.0, other steps are constant and survey
Strip part is constant.The BiYV of gained Pt load2O8The production hydrogen and production oxygen rate that-SBA composite photo-catalyst is tested are respectively flat
Equal 234.9 μm of ol/h and 109.3 μm of ol/h.
Embodiment 5-2
The present embodiment is the change case of embodiment 5, only relates to change complexing environment acid-base property (pH value)：Specially implementing
In the step of example 5 one：It is gradually dropped 2mol/L dust technology or ammonium hydroxide adjusts solution ph to 5.0, other steps are constant and survey
Strip part is constant.The BiYV of gained Pt load2O8The production hydrogen and production oxygen rate that-SBA composite photo-catalyst is tested are respectively flat
Equal 93.3 μm of ol/h and 40.1 μm of ol/h.
Embodiment 6
This example is related to the preparation method and its photocatalytic water activity of a kind of composite photo-catalyst with order mesoporous pattern
Test：
Step 1, weighs 0.4204g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 10ml deionized water and 10ml vinegar
In acid and 10ml dehydrated alcohol mixed solution；Complex solution pH value is 3.0；
Step 2 weighs 0.4232g strontium nitrate Sr (NO3)2As barium source, 0.6807g butyl titanate C16H36O4Ti makees
It for titanium source, sequentially adds in step 1 acquired solution, magnetic agitation 30min and ultrasonic disperse 30min are to forming unit for uniform suspension；
It weighs 0.2g silica template (SBA-15) to be added in aforementioned suspension, stirs ultrasound uniformly；
Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, dries 12 hours in 80 DEG C of baking ovens by step 3
It after grinding is collected afterwards, is put into the porcelain crucible that volume is 50ml, 650 DEG C of guarantors is risen with the heating rate of 1 DEG C/min in Muffle furnace
Temperature calcining 6 hours takes out grinding after cooling, obtains dry powder solid sample；In the present embodiment, the photocatalytic activity ingredient
The mass fraction for accounting for the composite photo-catalyst is 64.7%.
Step 4 weighs 0.1g step 3 obtained solid powder infusion in 1.35ml chloroplatinic acid aqueous solution, passes through 300W
Xenon light shining 3 hours, form the SrTiO of Pt load3- SBA composite photo-catalyst, the mass fraction of institute's supporting Pt are 2wt%.
Implementation result：By the above-mentioned SrTiO loaded through Pt of 0.1g3- SBA mesoporous nano complex material is scattered in 100ml
It in water, is placed in the photo catalysis reactor that material is Pyrex glass, the test of illumination complete solution water is carried out under 300W xenon lamp, light is urged
Change the gas that reaction generates and makees quantitative analysis with the gas chromatograph with thermal-conductivity detector.It tests obtained production hydrogen and produces oxygen speed
Rate is respectively averagely 135.7 μm of ol/h and 65.4 μm of ol/h.
Embodiment 6-1
The present embodiment is the change case of embodiment 6, only relates to change complexing agent additive amount：Specially in the step of embodiment 6
In rapid one：It weighs 0.2102g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 10ml deionized water and 10ml acetic acid and 10ml
In dehydrated alcohol mixed solution；Other steps are constant and test condition is constant.The SrTiO of gained Pt load3- SBA complex light is urged
The production hydrogen and produce oxygen rate respectively averagely 187.5 μm of ol/h and 86.3 μm of ol/h that agent is tested.
Embodiment 6-2
The present embodiment is the change case of embodiment 6, only relates to change complexing agent additive amount：Specially in the step of embodiment 6
In rapid one：It weighs 0.4204g monohydrate potassium and 0.2482g ethylene glycol is dissolved in 10ml deionized water and 10ml acetic acid and 10ml
In dehydrated alcohol mixed solution；Other steps are constant and test condition is constant.The SrTiO of gained Pt load3- SBA complex light is urged
The production hydrogen and produce oxygen rate respectively averagely 126.4 μm of ol/h and 54.8 μm of ol/h that agent is tested.
Embodiment 6-3
The present embodiment is the change case of embodiment 6, only relates to change complexing agent addition type：Specially in embodiment 6
In step 1：Weigh 0.3003g glycine (C2H5NO2) to be dissolved in 10ml deionized water and 10ml acetic acid and 10ml dehydrated alcohol mixed
It closes in solution；Other steps are constant and test condition is constant.The SrTiO of gained Pt load3- SBA composite photo-catalyst is tested
The production hydrogen and production oxygen rate arrived is respectively averagely 144.8 μm of ol/h and 69.2 μm of ol/h.
Embodiment 7
This example is related to the preparation method and its photocatalytic water activity of a kind of composite photo-catalyst with order mesoporous pattern
Test：
Step 1, weighs 0.4204g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 10ml deionized water and 10ml vinegar
In acid and 10ml dehydrated alcohol mixed solution；Complex solution pH value is 3.0；
Step 2 weighs 0.4232g strontium nitrate Sr (NO3)2As barium source, 0.6807g butyl titanate C16H36O4Ti makees
It for titanium source, sequentially adds in step 1 acquired solution, instills 5.89ml rhodium nitrate Rh (NO3)3Aqueous solution (0.49mg/ml) conduct
Rhodium source, magnetic agitation 30min and ultrasonic disperse 30min are to forming unit for uniform suspension；Weigh 0.2g silica template (SBA-
15) it is added in aforementioned suspension, stirs ultrasound uniformly；
Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, dries 12 hours in 80 DEG C of baking ovens by step 3
It after grinding is collected afterwards, is put into the porcelain crucible that volume is 50ml, 650 DEG C of guarantors is risen with the heating rate of 1 DEG C/min in Muffle furnace
Temperature calcining 6 hours takes out grinding after cooling, obtains dry powder solid sample；In the present embodiment, the photocatalytic activity ingredient
The mass fraction for accounting for the composite photo-catalyst is 64.8%.
Step 4 weighs 0.1g step 3 obtained solid powder infusion in 1.35ml chloroplatinic acid aqueous solution, passes through 300W
Xenon light shining 3 hours, form the 0.5%Rh-SrTiO of Pt load3The mass fraction of-SBA composite photo-catalyst, institute's supporting Pt is
2wt%.
Implementation result：By the above-mentioned 0.5%Rh-SrTiO loaded through Pt of 0.1g3The dispersion of-SBA mesoporous nano complex material
It in 100ml water, is placed in the photo catalysis reactor that material is Pyrex glass, illumination complete solution water is carried out under 300W xenon lamp and is surveyed
Examination, the gas that light-catalyzed reaction generates make quantitative analysis with the gas chromatograph with thermal-conductivity detector.Test obtained production hydrogen
It is respectively averagely 165.2 μm of ol/h and 78.4 μm of ol/h with oxygen rate is produced.
Embodiment 7-1
The present embodiment is the change case of embodiment 7, only relates to change doping ratio：Specially two embodiment 7 the step of
In：Instill 2.95ml rhodium nitrate Rh (NO3)3Aqueous solution (0.49mg/ml) is used as rhodium source；Other steps are constant and test condition not
Become.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 64.8%.Gained Pt is negative
The 0.25%Rh-SrTiO of load3The production hydrogen and produce oxygen rate respectively averagely 143.2 μ that-SBA composite photo-catalyst is tested
Mol/h and 63.1 μm of ol/h.
Embodiment 7-2
The present embodiment is the change case of embodiment 7, only relates to change doping ratio：Specially two embodiment 7 the step of
In：Instill 11.79ml rhodium nitrate Rh (NO3)3Aqueous solution (0.49mg/ml) is used as rhodium source；Other steps are constant and test condition not
Become.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 65.0%.Gained Pt is negative
The 1%Rh-SrTiO of load3The production hydrogen and produce oxygen rate respectively averagely 103.1 μm of ol/h that-SBA composite photo-catalyst is tested
With 43.5 μm of ol/h.
Embodiment 7-3
The present embodiment is the change case of embodiment 7, only relates to change doped chemical：Specially two embodiment 7 the step of
In：0.0150g ANN aluminium nitrate nonahydrate Al (NO is added3)3·9H2O is as silicon source, instead of rhodium source；Other steps are constant and test-strips
Part is constant.In the present embodiment, the mass fraction that the photocatalytic activity ingredient accounts for the composite photo-catalyst is 65.2%.Gained
The 2%Al-SrTiO of Pt load3The production hydrogen and produce oxygen rate respectively averagely 173.1 μ that-SBA composite photo-catalyst is tested
Mol/h and 79.5 μm of ol/h.
Embodiment 8
This example is related to the preparation method and its light degradation atmosphere of a kind of composite photo-catalyst with order mesoporous pattern
Pollutant active testing：
Step 1, weighs 0.5464g monohydrate potassium and 0.1241g ethylene glycol is dissolved in 15ml deionized water；
Step 2 weighs five nitric hydrate bismuth Bi (NO of 0.4851g3)3·5H2O is as bismuth source, six nitric hydrate of 0.3830g
Yttrium Y (NO3)3·6H2O is as yttrium source, 0.2340g ammonium metavanadate NH4VO3As vanadium source, sequentially add in step 1 acquired solution,
Magnetic agitation 30min and ultrasonic disperse 30min are to forming unit for uniform suspension；0.334g silica template (SBA-15) is weighed to add
Enter in aforementioned suspension, stirs ultrasound uniformly；
Suspension obtained by step 2 is evaporated under 80 DEG C of water baths, dries 12 hours in 80 DEG C of baking ovens by step 3
It after grinding is collected afterwards, is put into the porcelain crucible that volume is 50ml, 800 DEG C of guarantors is risen with the heating rate of 1 DEG C/min in Muffle furnace
Temperature calcining 12 hours takes out grinding after cooling, obtains dry powder solid sample；In the present embodiment, the photocatalytic activity at
Dividing the mass fraction for accounting for the composite photo-catalyst is 61.2%.
Step 4 weighs 0.1g step 3 obtained solid powder infusion in 1.35ml chloroplatinic acid aqueous solution, passes through 300W
Xenon light shining 3 hours, form the BiYV of Pt load2O8- SBA composite photo-catalyst, the mass fraction of institute's supporting Pt are 2wt%.
Implementation result：By the above-mentioned BiYV loaded through Pt of 0.1g2O8The grinding of-SBA mesoporous nano complex material is placed on U
In type pipe, the test of illumination degrading atmosphere pollution is carried out under 300W xenon lamp, test condition is：Initial ozone concentration is 60ppm,
Concentration of formaldehyde is 60ppm, and benzene concentration 60ppm, diethyl phthalate concentration is 60ppm, volume space velocity 50,000h-1,
Test result is：The removal efficiency of ozone is 100%, and the removal efficiency of formaldehyde is 34.4%, and the removal efficiency of benzene is 15.4%,
The removal efficiency of diethyl phthalate is 12.1%.
Embodiment 8-1
The present embodiment is the change case of embodiment 8, only relates to change test ozone concentration：Specially in the survey of embodiment 8
During try is rapid：By the above-mentioned BiYV loaded through Pt of 0.1g2O8The grinding of-SBA mesoporous nano complex material is placed in U-tube,
The test of illumination degrading atmosphere pollution is carried out under 300W xenon lamp, test condition is：Initial ozone concentration is 180ppm, concentration of formaldehyde
For 60ppm, benzene concentration 60ppm, diethyl phthalate concentration is 60ppm, volume space velocity 50,000h-1, test result
For：The removal efficiency of ozone is 100%, and the removal efficiency of formaldehyde is 78.4%, and the removal efficiency of benzene is 60.2%, O-phthalic
The removal efficiency of diethyl phthalate is 45.3%.
Comparative example 1
This comparative example is related to the preparation method and its photocatalytic water active testing, preparation method and reality of a kind of composite photo-catalyst
It is almost the same to apply example 1, the difference is that only：Silica template (SBA-15) is not added in this comparative example, in step 2.
The test condition of this comparative example is constant.The 2%BiYV of gained Pt load2O8The production that composite photo-catalyst is tested
Hydrogen and production oxygen rate are respectively averagely 40.1 μm of ol/h and 11.2 μm of ol/h.
It should be noted that without adding template to make activity compared to declining to a great extent in the comparative example, but if being forged with 400 DEG C
The sample (embodiment 1-2) of burning is compared, and higher temperature makes comparative example can have relatively high activity.
Comparative example 2
This comparative example is related to the preparation method and its photocatalytic water active testing, preparation method and reality of a kind of composite photo-catalyst
It is almost the same to apply example 1, the difference is that only：In this comparative example, the calcination condition of step 3 is：In Muffle furnace with 1 DEG C/
The heating rate of min rises 1100 DEG C of heat preservations and calcines 12 hours.
The test condition of this comparative example is constant.The 2%BiYV of gained Pt load2O8- SBA mesoporous nano composite photo-catalyst
Testing obtained production hydrogen and producing oxygen rate is respectively averagely 5.7 μm of ol/h and 2.5 μm of ol/h.
Comparative example 3
This comparative example is related to the preparation method and its photocatalytic water active testing, preparation method and reality of a kind of composite photo-catalyst
It is almost the same to apply example 1, the difference is that only：In this comparative example, the calcination condition of step 3 is：In Muffle furnace with 1 DEG C/
The heating rate of min rises 300 DEG C of heat preservations and calcines 12 hours.
The test condition of this comparative example is constant.The 2%BiYV of gained Pt load2O8- SBA mesoporous nano composite photo-catalyst
Testing obtained production hydrogen and producing oxygen rate is respectively averagely 0 μm of ol/h and 0 μm of ol/h.Temperature is too low so that can not be formed solid at this time
Solution is without complete solution water activity.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (10)
1. a kind of composite photo-catalyst, which is characterized in that including mesoporous template and photocatalytic activity ingredient；The photocatalytic activity
Ingredient is dispersed in the duct skeleton of mesoporous template；In the composite photo-catalyst, the quality point of photocatalytic activity ingredient
Number is 10%-90%；The photocatalytic activity ingredient is the nano particle of composite metal salt.
2. composite photo-catalyst according to claim 1, which is characterized in that the composite metal salt includes BixM2-xA2O8
Type compound, D-SrTiO3Type compound, SrTiO3The mixing of one or more of type compound；The BixM2-xA2O8Type
It closes in object, the mixing of one or more of M=Y, La, Ce, Pr, Nd, Sm, In, one or more of A=V, W, Mo are mixed
It closes, 0<x<2；The D-SrTiO3In type compound, in D=Ga, La, Na, Ta, Rh, Mn, Ru, Pd, Ir, Pt, Sb, Al one
Kind or several mixing, the mass fraction of D element are 0.1%~10%；
The mesoporous template includes at least one of mesoporous silicon oxide, meso-porous alumina, fumed silica.
3. composite photo-catalyst according to claim 1, which is characterized in that the composite photo-catalyst is mainly by mesoporous mould
Plate and photocatalytic activity ingredient are combined in nanoscale；It is described compound to include the following steps：By soluble metal salt precursor
Body and complexing agent are complexed, and obtained complex compound diffuses into the duct of mesoporous template, the then high-temperature calcination under confinement environment.
4. composite photo-catalyst according to claim 3, which is characterized in that the complexing agent include citric acid, ethylene glycol,
At least one of glycine, ethylenediamine tetra-acetic acid；The solvent for dissolving the complexing agent includes deionized water, acetic acid, anhydrous second
At least one of alcohol, anhydrous methanol；
The high-temperature calcination condition is：400~1000 DEG C are risen to the heating rate of 1 DEG C/min, calcination time is 6~24 small
When.
5. composite photo-catalyst according to claim 1, which is characterized in that it further include co-catalyst, the co-catalyst
It is supported on photocatalytic activity ingredient；The co-catalyst includes Pt, Au, Ag, RuO2、NiOx、RhCrO3、Co3O4、MoO3、
IrO2At least one of, wherein 0<x<1.
6. a kind of preparation method of composite photo-catalyst according to claim 1, which is characterized in that including the mesoporous mould
Plate and the compound method of the photocatalytic activity ingredient, specifically comprise the following steps：
B1, enveloping agent solution is prepared, metal salt presoma is added in the enveloping agent solution, stirred simultaneously ultrasonic disperse, obtain
Forerunner's liquid suspension；
B2, mesoporous template is mixed with forerunner's liquid suspension, stirs simultaneously ultrasonic disperse, obtains mixing suspension；
B3, the mixing suspension heating stirring is evaporated, then drying, calcining to get mesoporous template and photocatalytic activity at
The compound divided.
7. the preparation method of composite photo-catalyst according to claim 6, which is characterized in that in step B1, the complexing
Agent includes at least one of citric acid, ethylene glycol, glycine, ethylenediamine tetra-acetic acid；Prepare the solvent of the enveloping agent solution
Including at least one of deionized water, acetic acid, dehydrated alcohol, anhydrous methanol；
The pH value of the enveloping agent solution is 1.0-6.0；
Total dosage of the metal salt presoma and the molar ratio of amount of complex are 4:1~1:4.
8. the preparation method of composite photo-catalyst according to claim 6, which is characterized in that described mesoporous in step B2
Template mixed with forerunner's liquid suspension the specific steps are：Mesoporous template is added in forerunner's liquid suspension, is stirred
It is sufficiently submerged in presoma in the duct of mesoporous template within 0.5~10 hour, before the dosage of the mesoporous template and the metal salt
The molar ratio for driving total dosage of body is 1:1~10:1.
9. the preparation method of composite photo-catalyst according to claim 6, which is characterized in that in step B3, the calcining
Method be：Collected powder will be dried to be placed in crucible, rise to 400~1000 DEG C with the heating rate of 1 DEG C/min, calcining
Time is 6~24 hours.
10. a kind of composite photo-catalyst according to claim 1 is in photochemical catalyzing, photocatalysis Decomposition organic pollutant
In application.
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| CN112371124A (en) * | 2020-12-01 | 2021-02-19 | 齐鲁工业大学 | Preparation method of catalyst capable of degrading indoor formaldehyde pollutants |
| CN112724763A (en) * | 2021-01-14 | 2021-04-30 | 白山市科学技术研究所 | Water-based diatom coating and preparation method thereof |
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