CN106944155A - A kind of method of photochemical catalyst and photocatalytically degradating organic dye - Google Patents
A kind of method of photochemical catalyst and photocatalytically degradating organic dye Download PDFInfo
- Publication number
- CN106944155A CN106944155A CN201710202218.9A CN201710202218A CN106944155A CN 106944155 A CN106944155 A CN 106944155A CN 201710202218 A CN201710202218 A CN 201710202218A CN 106944155 A CN106944155 A CN 106944155A
- Authority
- CN
- China
- Prior art keywords
- zirconium phosphate
- basic zirconium
- dimensional nano
- nano piece
- present
- 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.)
- Granted
Links
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
- A62D3/176—Ultraviolet radiations, i.e. radiation having a wavelength of about 3nm to 400nm
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of photochemical catalyst, including：Solvent；Scattered zinc oxide and basic zirconium phosphate two-dimensional nano piece in a solvent；The average diameter of the basic zirconium phosphate two-dimensional nano piece is 200~2000nm；The average thickness of the basic zirconium phosphate two-dimensional nano piece is 1~5nm.The addition of basic zirconium phosphate two-dimensional nano piece improves the suspension stability of zinc oxide in the present invention, zinc oxide is spreaded more evenly across in a solvent, and zinc oxide is the key component of catalytic degradation organic dyestuff, so as to improve the degree of photocatalytically degradating organic dye；In addition, basic zirconium phosphate two-dimensional nano piece also has partly shielding effect effect to light, this shielding action can reduce the degree of photocatalytically degradating organic dye.The present invention adjusts degree of the zinc oxide to organic dyestuff photocatalytic degradation using double action of the basic zirconium phosphate two-dimensional nano piece to photocatalytic degradation by controlling the consumption of basic zirconium phosphate two-dimensional nano piece.Present invention also offers a kind of method of photocatalytically degradating organic dye.
Description
Technical field
The present invention relates to catalysis material technical field, more particularly to a kind of photochemical catalyst and photocatalytically degradating organic dye
Method.
Background technology
Zinc oxide is a kind of typical broadband based semiconductor material, with good chemical stability and ultraviolet absorbability
Can, it is a kind of important raw material of industry, it is widely used in the production and processing of the materials such as coating rubber, glass, ceramics.With it is general
Logical zinc oxide is compared, and the zinc oxide of nanoscale is except the feature application such as the Small-scale fading with nano material, skin effect
In outside sensor, stealth material, also with unique piezo-electric effect and photocatalytic effect, photocatalytic degradation field can be applied to.
Prior art is more to the research of organic dyestuff type photocatalytic degradation for catalyst for using zinc oxide, but for how
Research of the zinc oxide to degradation of organic dyes degree is controlled to have not been reported, photocatalytic degradation of the regulation and control zinc oxide to organic dyestuff
Degree has great directive function to commercial Application.
The content of the invention
In view of this, it is an object of the invention to provide a kind of method of photochemical catalyst and photocatalytically degradating organic dye,
The photochemical catalyst that the present invention is provided can regulate and control photocatalytic degradation degree of the zinc oxide to organic dyestuff.
The invention provides a kind of photochemical catalyst, including：
Solvent；
Scattered zinc oxide and basic zirconium phosphate two-dimensional nano piece in a solvent；
The average diameter of the basic zirconium phosphate two-dimensional nano piece is 200~2000nm；
The average thickness of the basic zirconium phosphate two-dimensional nano piece is 1~5nm.
It is preferred that, the average diameter of the basic zirconium phosphate two-dimensional nano piece is 350~1500nm.
It is preferred that, the average thickness of the basic zirconium phosphate two-dimensional nano piece is 2~3nm.
It is preferred that, the granularity of the zinc oxide is 1~100nm.
It is preferred that, the solvent is TBAH.
It is preferred that, the mass fraction of the zinc oxide in a solvent is 20~30mg/mL.
It is preferred that, the mass fraction of the basic zirconium phosphate two-dimensional nano piece in a solvent is 0.01~0.5mg/mL.
It is preferred that, the mass fraction of the basic zirconium phosphate two-dimensional nano piece in a solvent is 0.01~0.15mg/mL.
The invention provides a kind of method of photocatalytically degradating organic dye, what the photocatalytically degradating organic dye was used
Photochemical catalyst is the photochemical catalyst described in above-mentioned technical proposal.
It is preferred that, the light that the photocatalytically degradating organic dye is used is ultraviolet light.
Compared with prior art, on the one hand the addition of basic zirconium phosphate two-dimensional nano piece can improve the outstanding of zinc oxide in the present invention
Floating stability, makes zinc oxide spread more evenly across in a solvent, zinc oxide is the key component of catalytic degradation organic dyestuff, so that
Improve the degree of photocatalytically degradating organic dye；On the other hand, basic zirconium phosphate two-dimensional nano piece also has partly shielding effect effect to light,
This shielding action can reduce the degree of photocatalytically degradating organic dye.The present invention is urged light using basic zirconium phosphate two-dimensional nano piece
Change the double action of degraded, zinc oxide is adjusted to organic dyestuff photocatalytic degradation by controlling the consumption of basic zirconium phosphate two-dimensional nano piece
Degree.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the zirconium phosphate nano powder scanning electron microscope diagram that the embodiment of the present invention 1 is obtained；
Fig. 2 is the TEM figures for the basic zirconium phosphate two-dimensional nano piece that the embodiment of the present invention 1 is prepared；
Fig. 3 is the obtained mixed liquor of embodiment 1~5 color sample picture after 10 minutes ultraviolet lights；
Fig. 4 is the obtained mixed liquor of embodiment 1~5 color sample picture after 15 minutes ultraviolet lights；
Fig. 5 is the obtained mixed liquor of embodiment 1~5 color sample picture after 20 minutes ultraviolet lights；
Fig. 6 is the obtained mixed liquor of embodiment 1~5 color sample picture after 25 minutes ultraviolet lights；
Fig. 7 is absorbance of the obtained sample of the embodiment of the present invention 1~5 after ultraviolet light；
Fig. 8 is the infrared test spectrogram of mixed liquor in the embodiment of the present invention 1~5.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
The invention provides a kind of photochemical catalyst, including：
Solvent；
Scattered zinc oxide and basic zirconium phosphate two-dimensional nano piece in a solvent；
The average diameter of the basic zirconium phosphate two-dimensional nano piece is 200~2000nm；
The average thickness of the basic zirconium phosphate two-dimensional nano piece is 1~5nm.
In the present invention, the solvent is preferably water, makes zinc oxide and basic zirconium phosphate two-dimensional nano piece be dispersed in water to be formed
Soliquid.In the present invention, the zinc oxide is preferably nano zine oxide, and the granularity of the zinc oxide is preferably 1~
100nm, more preferably 5~90nm, more preferably 10~80nm, more preferably 20~70nm, more preferably 30~60nm, it is optimal
Elect 40~50nm as.In the present invention, the basic zirconium phosphate two-dimensional nano piece radius-thickness ratio (ratio of diameter and thickness) is larger, described
The average diameter of basic zirconium phosphate two-dimensional nano piece be 200~2000nm, preferably 350~1500nm, more preferably 500~
1200nm, most preferably 800~1000nm；The average thickness of the basic zirconium phosphate two-dimensional nano piece be 1~5nm, preferably 2~
3nm, more preferably 2.2~2.8nm, most preferably 2.4~2.6nm.
In the present invention, the mass fraction of the zinc oxide in a solvent is preferably 20~30mg/mL, more preferably 22~
28mg/mL, more preferably 24~26mg/mL, most preferably 25mg/mL.The present invention is to the consumption of the basic zirconium phosphate without special
Limitation, the organic dyestuff that those skilled in the art can be according to actual needs palliating degradation degree selection addition suitable dose phosphoric acid
Zirconium two-dimensional nano piece.In the present invention, the mass fraction of the basic zirconium phosphate two-dimensional nano piece in a solvent can for 0.01~
0.5mg/mL, mass fraction is 0.01~0.15mg/mL to preferably phosphoric acid zirconium two-dimensional nano piece in a solvent, and the light now obtained is urged
The efficiency of agent catalytic degradation organic dyestuff is higher.In the present invention, the quality of zinc oxide and the basic zirconium phosphate two-dimensional nano piece
Than being preferably (100~150)：(10~20), more preferably (120~130)：(12~16), most preferably 125：14.
The present invention does not have special limitation to the preparation method of the photochemical catalyst, preferably first prepares basic zirconium phosphate two dimension
Nanometer sheet solution, adds zinc oxide into basic zirconium phosphate two-dimensional nano piece solution, obtains photochemical catalyst.The present invention is to the basic zirconium phosphate
The preparation method of two-dimensional nano piece solution does not have special limitation, using basic zirconium phosphate two-dimensional nano well known to those skilled in the art
The preparation method of piece is prepared, molten described in the solvent and above-mentioned technical proposal in the basic zirconium phosphate two-dimensional nano piece solution
Agent is consistent, will not be repeated here.
In the present invention, the preparation method of the basic zirconium phosphate two-dimensional nano piece solution is preferably：
Zirconium phosphate nano powder is suspended in water ultrasonic disperse；
Shaken after obtained dispersion liquid and solvent are mixed；
Ultrasonically treated rear standing is carried out after solution after concussion is diluted with water；
Solution after standing is centrifuged, bottom solid is removed；
Remaining liquid after solid will be removed to be centrifuged again,
Bottom solid after centrifugation and supernatant liquor are removed, take the suspension in intermediate layer to obtain the wiener of basic zirconium phosphate two
Rice piece solution.
In the present invention, basic zirconium phosphate two-dimensional nano piece described in the particle diameter and above-mentioned technical proposal of the basic zirconium phosphate powder is straight
Footpath is consistent, will not be repeated here.The present invention does not have special limitation to the zirconium phosphate nano raw powder's production technology, using this
Zirconium phosphate nano raw powder's production technology is prepared known to art personnel.In the present invention, the basic zirconium phosphate
The preparation method of nano-powder is preferably：
By zirconium oxychloride and phosphatase reaction；
Obtained reaction product is centrifuged；
It is centrifuged again after the solid being centrifugally separating to obtain is washed；
Obtained solid after centrifugation is dried and ground successively, zirconium phosphate nano powder is obtained.
In the present invention, the zirconium oxychloride is preferably eight water oxygen zirconium chlorides.In the present invention, the phosphoric acid is preferably phosphorus
Acid solution, more preferably phosphate aqueous solution.In the present invention, the concentration of the phosphoric acid solution is preferably 10~20mol/L, more excellent
Elect 12~18mol/L, most preferably 14~16mol/L as.In the present invention, the quality of the zirconium oxychloride and phosphoric acid solution
Volume ratio is preferably 1g:(5~15) mL, more preferably 1g:(8~12) mL, most preferably 1g:10mL.In the present invention, it is described
Reaction is carried out preferably under air-proof condition, can such as be carried out in sealed reactor.In the present invention, the temperature of the reaction is preferred
For 180~220 DEG C, more preferably 190~210 DEG C, most preferably 200 DEG C.In the present invention, the time of the reaction is preferably
10~15 hours, most preferably more preferably 11~14 hours, 12~13 hours.
After reaction terminates, the present invention is centrifuged after preferably obtained reaction product is cooled down, and removes supernatant liquid
It is centrifuged again after obtained solid is washed afterwards.In the present invention, the speed of the centrifugation is preferably 1800
~2200r/min, more preferably 1900~2100r/min, most preferably 2000r/min.In the present invention, it is described to centrifuge
Time be preferably 2~8min, more preferably 3~6min, most preferably 4~5min.In the present invention, the reagent of the washing
Preferably water, more preferably deionized water.The present invention preferably repeats obtained solid product the behaviour of washing-centrifugation
Make, preferably repeatedly 4~6 times.In the present invention, the temperature of the drying is preferably 60~80 DEG C, more preferably 65~75 DEG C, most
Preferably 70 DEG C.
In the present invention, the water is preferably deionized water.In the present invention, the quality of the zirconium phosphate nano powder and
The ratio of the volume of water is preferably 1g:(5~15) mL, more preferably 1g:(8~12) mL, most preferably 1g：10mL.In the present invention
In, the time of the ultrasonic disperse is preferably 25~35min, more preferably 30min.
Solvent is preferably added in dispersion liquid after mixing by the present invention to be shaken, and the solvent is preferably tetrabutylammonium hydroxide
Ammonium, more preferably TBAH solution, most preferably the TBAH aqueous solution.In the present invention, described four
The mass concentration of butyl ammonium hydroxide solution is preferably 30~50%, more preferably 35~45%, most preferably 40% aqueous solution.
In the present invention, the ratio of the quality of the basic zirconium phosphate and the volume of solvent is preferably 1g：(2~3) mL, more preferably 1g：
(2.2~2.8) mL, most preferably 1g：(2.4~2.6) mL.In the present invention, the concussion can enter in test tube oscillator
OK, the time of the concussion is preferably 3~5min.
In the present invention, it is preferred to by the solution after concussion be diluted with water to the mass concentration of wherein basic zirconium phosphate for 0.3~
0.4mg/mL, is more preferably diluted with deionized water.In the present invention, the ultrasonically treated time is preferably 25~35min,
More preferably 30min.In the present invention, the time of the standing is preferably 1~3 day, more preferably 2 days.The present invention is using super
Zirconium phosphate nano powder can be efficiently peeled off into individual layer basic zirconium phosphate two-dimensional nano piece by being stood after sonication.
In the present invention, the speed solution after standing being centrifuged is preferably 3500~4500r/min, more excellent
Elect 3800~4200r/min, most preferably 4000r/min as；The time of the centrifugation is preferably 25~35min, more excellent
Elect 30min as.The present invention removes the solid that bottom is not completely exfoliated by the way that the solution after standing is centrifuged.
The present invention will remove remaining liquid after solid and be centrifuged again, and the speed of the centrifugation is preferably
3500~4500r/min, more preferably 3800~4200r/min, most preferably 4000r/min；The time of the centrifugation
Preferably 1.5~2.5 hours, more preferably 2 hours.The present invention makes liquid by the way that remaining liquid is centrifuged again
Body is layered, and the basic zirconium phosphate solid and supernatant liquor that bottom is not completely exfoliated are removed, and take the suspension in intermediate layer to obtain basic zirconium phosphate
Two-dimensional nano piece solution.In the present invention, the volume fraction of the basic zirconium phosphate two-dimensional nano piece solution is preferably 3~6%, more excellent
Elect 4~5% as.
Zinc oxide powder is preferably added in above-mentioned basic zirconium phosphate two-dimensional nano piece solution and carries out ultrasound by the present invention, obtains light
Catalyst；Zinc oxide powder is first more preferably dispersed in water ultrasound, then dispersion liquid is added to the basic zirconium phosphate two-dimensional nano
It is ultrasonic in piece solution；The ultrasonic time is preferably 25~35min, more preferably 30min.In the present invention, the oxidation
The volume ratio of zinc powder weight and water, preferably deionized water is preferably (2~3) mg:10mL, more preferably 2.5mg：10mL.
The present invention uses hydro-thermal method synthesizing zirconium phosphate crystal, and Zirconium phosphate crystal intercalation, which is peeled off, obtains two-dimentional zirconium phosphate nano sheet
Solution.Obtained two-dimentional zirconium phosphate nano sheet solution and zinc oxide is fully ultrasonic, make two-dimentional zirconium phosphate nano sheet and zinc oxide
It is uniformly dispersed obtaining stable mixing suspension, photocatalytic degradation finally is carried out to organic dyestuff using the suspension.This hair
Bright use two-dimensional nano piece additive, on the one hand can improve the dispersion stabilization of zinc oxide suspension；On the other hand, by adjusting
The amount that whole two-dimensional nano piece is added can effectively adjust degree of the zinc oxide to organic dyestuff photocatalytic degradation.This inorganic two
Dimension nanometer sheet is not chemically reacted with the material in the catalyst system and catalyzing (zinc oxide) of photocatalytic degradation, and its can be kept intrinsic
Chemical property, meets and is required for clean environment is free of contamination, can be widely used in photocatalysis field.
The invention provides a kind of method of photocatalytically degradating organic dye, what the photocatalytically degradating organic dye was used
Photochemical catalyst is the photochemical catalyst described in above-mentioned technical proposal.Specific method of the present invention to the photocatalytically degradating organic dye
There is no special limitation, using the technical scheme of photocatalytically degradating organic dye well known to those skilled in the art.This hair
Bright not have special limitation to the organic dyestuff and light source, those skilled in the art can be according to actual needs using different
Organic dyestuff and suitable light source carry out photocatalytic degradation.In the present invention, the organic dyestuff can be methylene blue, institute
It can be ultraviolet light to state light source.In the present invention, the method for the photocatalytically degradating organic dye is preferably：
Under dark room conditions, ultraviolet light is used after above-mentioned photochemical catalyst is added into methylene blue solution；Specific method
For：
Under dark room conditions, ultrasound after Zinc oxide powder is added into methylene blue solution；Then to obtaining in mixture
The basic zirconium phosphate two-dimensional nano piece solution described in above-mentioned technical proposal is added, mixed liquor is obtained；Using ultraviolet light to the mixed liquor
It is irradiated.
In the present invention, the methylene blue solution is preferably aqueous solution of methylene blue；The matter of the methylene blue solution
It is preferably 15~25mg/L to measure concentration, more preferably 18~22mg/L, most preferably 20mg/L.In the present invention, the methylene
The ratio of base indigo plant liquor capacity, zinc oxide quality and basic zirconium phosphate two-dimensional nano piece liquor capacity is preferably (5~15) mL：(2~3)
mg:(100~500) μ L, more preferably (8~12) mL：(2.3~2.7) mg:(100~300) μ L, most preferably 10mL：
2.5mg:(100~200) μ L.
In the present invention, the ultrasonic time is preferably 25~35min, more preferably 30min.In the present invention, institute
State intensity preferably 20~30mW/cm of ultraviolet light2, more preferably 22~28mW/cm2, most preferably 26.5mW/cm2.In this hair
In bright, the irradiation time of the ultraviolet light is preferably 1~30min, more preferably 5~25min, more preferably 10~20min, most
Preferably 15min.
Regulate and control zinc oxide to the method for the photocatalytic degradation of organic dyestuff, the party the invention provides a kind of two-dimensional nano piece
Method improves zinc oxide suspension dispersion stabilization on the premise of zinc oxide is not influenceed to organic dyestuff light-catalyzed reaction, passes through control
The amount of two-dimensional nano piece processed controls zinc oxide to organic dyestuff photocatalysis degree.
Raw material used in following examples of the present invention is commercial goods.
Embodiment 1
The preparation of nanometer basic zirconium phosphate powder：
6g zirconium oxychlorides crystal powder and 60mL phosphate aqueous solutions (15mol/L) are mixed, then mixed solution is sealed
In 100mL hydrothermal reaction kettle, it is placed in 200 DEG C of constant temperature, reaction is carried out 12 hours.Reaction cooling after, take out product in
50mL centrifuge tubes 2000r/min centrifuges 5min, removes supernatant liquid and adds deionized water to be centrifuged after washing, repetition 4~6 times, finally
70 DEG C of dryings, take out, grind solid product be zirconium phosphate nano crystalline flour end.
Testing electronic microscope, test knot are scanned to the sodium phosphate nano-powder that the embodiment of the present invention 1 is prepared
Fruit is as shown in figure 1, Fig. 1 is the zirconium phosphate nano powder scanning electron microscope diagram that the embodiment of the present invention 1 is obtained, it can be seen that
The particle diameter that the embodiment of the present invention 1 prepares zirconium phosphate nano powder is 1124 ± 240nm.
The preparation of basic zirconium phosphate two-dimensional nano piece solution：
The above-mentioned zirconium phosphate nano powders of 1g are taken to be suspended in 10mL deionized water, then ultrasonic disperse 30 minutes will
The 2.2mL TBAHs aqueous solution is added in suspension, and suspension is placed in into concussion 3~5 minutes on test tube oscillator,
Add deionized water and be diluted to ultrasound 30 minutes after 30mL, the original grain for standing 2 angel's basic zirconium phosphates effectively peels off into individual layer.
Finally, suspension is centrifuged into (4000 revs/min) 30 minutes, removes the solid that is not completely exfoliated, again to suspension from
The heart 2 hours (4000 revs/min), is layered suspension, removes bottom and zirconium phosphate nano sheet and supernatant liquor are not completely exfoliated, take
Middle level suspension is the two-dimentional zirconium phosphate nano sheet soliquid (basic zirconium phosphate two-dimensional nano piece solution) of gained individual layer.
The volume fraction 4.38% for the basic zirconium phosphate two-dimensional nano piece solution that the embodiment of the present invention 1 is prepared.To the present invention
Basic zirconium phosphate two-dimensional nano piece in the basic zirconium phosphate two-dimensional nano piece solution that embodiment 1 is prepared carries out TEM tests, test result
As shown in Fig. 2 the TEM that Fig. 2 is the basic zirconium phosphate two-dimensional nano piece that the embodiment of the present invention 1 is prepared schemes, (color contrast is deeper
Place be basic zirconium phosphate two-dimensional nano piece position), by test analysis understand, the embodiment of the present invention 1 prepare basic zirconium phosphate two
The average diameter for tieing up nanometer sheet is 1124 ± 240nm, and average thickness is 2.68nm.
Photocatalytically degradating organic dye：
Under room temperature dark room conditions, 20mg/L methylene blue standard liquid (being prepared with distilled water) is configured, 10mL is then taken
Methylene blue standard liquid, adds the nano-zinc oxide powder that 2.5mg granularities are 10nm thereto, and ultrasound 30 minutes adds 100
The above-mentioned two-dimentional basic zirconium phosphate soliquids of μ L, mixing, obtain mixed liquor.
Color such as Fig. 3 institutes of the mixed liquor that the embodiment of the present invention 1~5 is obtained sample after ultraviolet light 10 minutes
Show, 15 minutes irradiation after color sample as shown in figure 4,20 minutes irradiation after color sample as shown in figure 5,25 minutes irradiation after sample
Product color is as shown in fig. 6, the mixed liquor that Fig. 3~Fig. 6, which is respectively embodiment 1~5, to be obtained passes through 10 minutes, 15 minutes, 20 minutes
With color sample picture after 25 minutes ultraviolet lights.Because human eye is limited to color discrimination ability, tested using absorbance
Effect after method test photocatalysis.
Obtained mixed liquor is carried out into full spectrum using ultraviolet/visible light spectrophotometer (UV-9000S) as sample to sweep
Retouch, determine a length of 664nm of maximum absorption wave of methylene blue.To sample carrying out ultraviolet lighting after having tested every time, (power is
7.95J/cm2), light application time is respectively 25 minutes, 20 minutes, 15 minutes, 10 minutes and 1 minute, and the sample after illumination is entered
Row absorbance is tested, and test result passes through ultraviolet light as shown in fig. 7, Fig. 7 is the sample that the embodiment of the present invention 1~5 is obtained
Absorbance (Absorbance) afterwards.
Infrared test is carried out to obtained mixed liquor using Fourier infrared spectrograph, test result is as shown in figure 8, Fig. 8
For the infrared test spectrogram of mixed liquor in the embodiment of the present invention 1~5, (MB is that methylene blue, ZrP are that basic zirconium phosphate, ZnO are oxidation
Zinc).
Embodiment 2
Photocatalytically degradating organic dye is carried out according to the method for embodiment 1,200 μ L bis- are added as different from Example 1
Tie up zirconium phosphate nano sheet soliquid.
Embodiment 3
Photocatalytically degradating organic dye is carried out according to the method for embodiment 1,300 μ L bis- are added as different from Example 1
Tie up zirconium phosphate nano sheet soliquid.
Embodiment 4
Photocatalytically degradating organic dye is carried out according to the method for embodiment 1,400 μ L bis- are added as different from Example 1
Tie up zirconium phosphate nano sheet soliquid.
Embodiment 5
Photocatalytically degradating organic dye is carried out according to the method for embodiment 1,500 μ L bis- are added as different from Example 1
Tie up zirconium phosphate nano sheet soliquid.
As shown in Figure 7, it is less than 200 μ L (basic zirconium phosphate two-dimensional nano piece concentration in basic zirconium phosphate two-dimensional nano piece solution addition
For 0.14mg/mL) when, with the increase of ultraviolet lighting time, its absorbance is a downward trend, and less than being not added with
The light absorption curve of basic zirconium phosphate, degradation effect is better than the sample for being not added with basic zirconium phosphate two-dimensional nano piece；Addition is in 300 μ L (phosphorus
Sour zirconium two-dimensional nano piece concentration 0.21mg/mL) more than when, with the increase of addition, there is the trend of a rising in absorbance,
Degradation effect will be less than the sample for being not added with basic zirconium phosphate two-dimensional nano piece.When the addition of basic zirconium phosphate is smaller so that ZnO is being protected
While holding stable dispersion, the photocatalytic degradation of methylene blue can be effectively facilitated.When the adding too much of basic zirconium phosphate, enter
The ultraviolet-visible penetrated is shielded by the zirconium phosphate nano sheet of high concentration, weakens absorptions of the ZnO to light, it promotes light-catalysed energy
Power also weakens therewith.
As shown in Figure 8, when the addition of basic zirconium phosphate two-dimensional nano piece solution increases to 500 μ L from 0 μ L, its characteristic peak begins
Eventually in fixed position, illustrate in mixed liquor, chemical reaction is not present between basic zirconium phosphate and ZnO and methylene blue.Phosphorus
It is a physical action to the photocatalytic degradation of methylene blue that sour zirconium two-dimensional nano piece, which regulates and controls ZnO,.
As seen from the above embodiment, the invention provides a kind of photochemical catalyst, including：Solvent；Scattered oxygen in a solvent
Change zinc and basic zirconium phosphate two-dimensional nano piece；The average diameter of the basic zirconium phosphate two-dimensional nano piece is 200~2000nm；The basic zirconium phosphate
The average thickness of two-dimensional nano piece is 1~5nm.The addition of basic zirconium phosphate two-dimensional nano piece improves the suspension of zinc oxide in the present invention
Stability, makes zinc oxide spread more evenly across in a solvent, and zinc oxide is the key component of catalytic degradation organic dyestuff, so as to carry
The degree of high photocatalytically degradating organic dye；In addition, basic zirconium phosphate two-dimensional nano piece also has partly shielding effect effect, this screen to light
The effect of covering can reduce the degree of photocatalytically degradating organic dye.The present invention is using basic zirconium phosphate two-dimensional nano piece to photocatalytic degradation
Double action, adjust zinc oxide to the journey of organic dyestuff photocatalytic degradation by controlling the consumption of basic zirconium phosphate two-dimensional nano piece
Degree.
Claims (10)
1. a kind of photochemical catalyst, including：
Solvent；
Scattered zinc oxide and basic zirconium phosphate two-dimensional nano piece in a solvent；
The average diameter of the basic zirconium phosphate two-dimensional nano piece is 200~2000nm；
The average thickness of the basic zirconium phosphate two-dimensional nano piece is 1~5nm.
2. photochemical catalyst according to claim 1, it is characterised in that the average diameter of the basic zirconium phosphate two-dimensional nano piece is
350~1500nm.
3. photochemical catalyst according to claim 1, it is characterised in that the average thickness of the basic zirconium phosphate two-dimensional nano piece is
2~3nm.
4. photochemical catalyst according to claim 1, it is characterised in that the granularity of the zinc oxide is 1~100nm.
5. photochemical catalyst according to claim 1, it is characterised in that the solvent is TBAH.
6. photochemical catalyst according to claim 1, it is characterised in that the mass fraction of the zinc oxide in a solvent is 20
~30mg/mL.
7. photochemical catalyst according to claim 1, it is characterised in that the matter of the basic zirconium phosphate two-dimensional nano piece in a solvent
Amount fraction is 0.01~0.5mg/mL.
8. photochemical catalyst according to claim 7, it is characterised in that the matter of the basic zirconium phosphate two-dimensional nano piece in a solvent
Amount fraction is 0.01~0.15mg/mL.
9. a kind of method of photocatalytically degradating organic dye, it is characterised in that the light that the photocatalytically degradating organic dye is used
Catalyst is the photochemical catalyst described in any one in claim 1~8.
10. method according to claim 9, it is characterised in that the light that the photocatalytically degradating organic dye is used is purple
Outer light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710202218.9A CN106944155B (en) | 2017-03-30 | 2017-03-30 | Photocatalyst and method for degrading organic dye through photocatalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710202218.9A CN106944155B (en) | 2017-03-30 | 2017-03-30 | Photocatalyst and method for degrading organic dye through photocatalysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106944155A true CN106944155A (en) | 2017-07-14 |
| CN106944155B CN106944155B (en) | 2020-08-28 |
Family
ID=59474972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710202218.9A Expired - Fee Related CN106944155B (en) | 2017-03-30 | 2017-03-30 | Photocatalyst and method for degrading organic dye through photocatalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106944155B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113828335A (en) * | 2021-08-18 | 2021-12-24 | 天津市生态环境科学研究院(天津市环境规划院、天津市低碳发展研究中心) | Composite photo-Fenton catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421137A (en) * | 2002-12-23 | 2003-06-04 | 童忠良 | Prepn process of antibacterial nanomaterial |
-
2017
- 2017-03-30 CN CN201710202218.9A patent/CN106944155B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421137A (en) * | 2002-12-23 | 2003-06-04 | 童忠良 | Prepn process of antibacterial nanomaterial |
Non-Patent Citations (2)
| Title |
|---|
| DAZHI SUN ET AL.: "Optical Properties of ZnO Quantum Dots in Epoxy with Controlled Dispersion", 《J. PHYS. CHEM. C》 * |
| ZHUOWEI LIU ET AL.: "Stability of TiO2 Nanoparticles in Deionized Water with ZrP Nanoplatelets", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113828335A (en) * | 2021-08-18 | 2021-12-24 | 天津市生态环境科学研究院(天津市环境规划院、天津市低碳发展研究中心) | Composite photo-Fenton catalyst and preparation method thereof |
| CN113828335B (en) * | 2021-08-18 | 2023-11-21 | 天津市生态环境科学研究院(天津市环境规划院、天津市低碳发展研究中心) | Composite photo-Fenton catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106944155B (en) | 2020-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1036845C (en) | Preparation of Titanium particles and film | |
| JP5150826B2 (en) | Method for producing silica-coated zinc oxide fine particles and silica-coated zinc oxide fine particles obtained by the method | |
| Manivel et al. | CuO-TiO2 nanocatalyst for photodegradation of acid red 88 in aqueous solution | |
| CN106047343B (en) | The method for using bulk kelp to prepare fluorescent carbon nano dot for carbon source one-step method hydrothermal carbonization | |
| Wu et al. | Effect of reaction temperature on properties of carbon nanodots and their visible-light photocatalytic degradation of tetracyline | |
| AlShehri et al. | Efficient photodegradation of methylthioninium chloride dye in aqueous using barium tungstate nanoparticles | |
| CN106423153A (en) | Preparation method and oxygen indicator of silver-doped titanium dioxide nanotubes | |
| Mittal et al. | Photocatalytic studies of crystal violet dye using Mn doped and PVP capped ZnO nanoparticles | |
| Nilavazhagan et al. | Effect of an alkali hydroxide concentration on the structural, optical, and surface morphological properties of ZnO nanoparticles | |
| CN105819498A (en) | Nano SnO2 hollow microsphere, preparation method and applications thereof | |
| CN109529872A (en) | Amorphous nano titanium dioxide visible light catalyzer compound and preparation method thereof | |
| Suwarnkar et al. | Modification of TiO 2 nanoparticles by HZSM-5 for the enhancement in photodegradation of Acid Green 25 | |
| Pourahmad | Nanocomposite prepared from ZnS nanoparticles and molecular sieves nanoparticles by ion exchange method: Characterization and its photocatalytic activity | |
| CN105289457B (en) | A kind of hollow structure TiO2The preparation method and applications of nano material | |
| Mehrizad et al. | Synthesis of ZnS decorated carbon fibers nanocomposite and its application in photocatalytic removal of Rhodamine 6G from aqueous solutions | |
| CN106944155A (en) | A kind of method of photochemical catalyst and photocatalytically degradating organic dye | |
| Bhapkar et al. | Aluminium doped ZnO nanostructures for efficient photodegradation of indigo carmine and azo carmine G in solar irradiation | |
| CN103521247B (en) | A kind of preparation method of self assembly Silver-phosphate-bascomposite composite visible light photocatalytic material | |
| CN1296041A (en) | Process for preparing nanometer zinc oxide | |
| CN106881118B (en) | A kind of method of ion-exchange synthesis heterojunction photocatalyst | |
| CN110394183A (en) | A kind of ATP/Zn0.5Cd0.5The preparation method of S composite visible light catalyst | |
| CN105195145A (en) | Method of preparing PN heterogeneous composite photocatalyst | |
| Arasteh Nodeh et al. | Preparation, Characterization, and Application of Nanospherical α-Fe2O3 Supported on Silica for Photocatalytic Degradation of Methylene Blue | |
| Pei et al. | One-Pot Hydrothermal Synthesis of g-C3N4/BiPO4 Nanocomposites with Significant Photocatalytic Activity | |
| CN111154289B (en) | Preparation method and application of self-dispersion nano bismuth vanadate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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: 20200828 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |