CN105289694A - Method for preparing ZnO/ZnGaNO two-phase composite structure photocatalytic powder - Google Patents
Method for preparing ZnO/ZnGaNO two-phase composite structure photocatalytic powder Download PDFInfo
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- CN105289694A CN105289694A CN201510876332.0A CN201510876332A CN105289694A CN 105289694 A CN105289694 A CN 105289694A CN 201510876332 A CN201510876332 A CN 201510876332A CN 105289694 A CN105289694 A CN 105289694A
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Abstract
The invention discloses a method for preparing ZnO/ZnGaNO two-phase composite structure photocatalytic powder. The method comprises the following steps: preparing a hydroxide precursor containing Zn and Ga ions in an aqueous solution by utilizing a co-precipitation method for reducing the pH value; nitriding the precursor, thereby obtaining the composite structure powder of which the interior is provided with ZnO nanosheets and the surface is provided with ZnGaNO solid solution nano particles. The powder is high in photocatalytic degradation efficiency of methylene blue aqueous solution under visible light and is high in decoloring power. The method disclosed by the invention is simple in process, low in cost and suitable for large-scale production.
Description
Technical field
The present invention relates to field of photocatalytic material, particularly relate to a kind of preparation method of ZnO/ZnGaNO Two-phase composite structure photocatalytic powder.
Background technology
Global environmental pollution and ecological disruption make people give great concern to environmental improvement technology that is efficient, energy-conservation, non-secondary pollution.In recent years, photocatalysis oxidation technique demonstrates wide application prospect as the processing method of the organic pollution of poisonous or difficult for biological degradation.The general principle of photocatalysis technology is: be greater than energy gap (E when semiconductor light-catalyst is subject to energy
g) illumination when penetrating, the electrode (e in its valence band
-) excited, cross forbidden band and enter conduction band, valence band stays the hole (h of positively charged
+).Photohole has extremely strong oxidisability, can organic matter in direct oxidation water; Or the electronics can captured in water, the hydroxyl radical free radical (OH) that production oxidisability is very strong, OH can carry out the oxidation of non-selectivity to the organic pollution near electrode surface, and organic matter exhaustive oxidation is CO by so-called " electrochemical combustion " process that can occur
2and water.ZnO is the Typical Representative of high efficiency semiconductor photochemical catalyst, and ZnO has wider forbidden band (3.37eV), the light (as ultraviolet) that wavelength can only be utilized very short, and wherein there is stronger " compound " tendency in electronics and hole in addition.And the solid solution of ZnO and GaN (ZnGaNO, or ZnO/GaN), be proved to be a kind of can the catalysis material of decomposition water under visible light, and its band gap adjustable (reducing with the increase of ZnO content).Japan Patent JP2005144210-A reports one and utilizes Ga
2o
3at 850 DEG C, prepare ZnGaNO with the method for ammonia gas react with ZnO, but this method needs the pyroreaction time of more than 10 hours usually, and the ZnO content of product is usually less than 30%, makes it absorbing wavelength can only be less than the sunshine of 500nm.(the JunpengWangetal.J.Mater.Chem. such as Chinese patent application CN102166527A and WangJunpeng, 2011 (21): 4562) report the method that another prepares ZnGaNO solid solution, this method utilizes coprecipitation to obtain Zn
2+/ Ga
3+/ CO
3 2-layered double hydroxide (LDHs) presoma, then by this presoma at 800 DEG C with ammonia gas react 0.5 ~ 2 hour, obtain ZnGaNO solid solution ZnO content and be greater than 50% and be less than 80%, visible ray wavelength being greater than to more than 500nm has absorption; In LDH precursor power process, what the people such as Wang adopted is the method (rising pH method) raising pH value of solution, is about to containing NaOH and Na
2cO
3aqueous slkali instillation gallium and zinc salting liquid in, the pH of mixed solution is constantly reduced until pH is 8.Rise pH legal system for ZnGaNO solid solution internal porous, have impact on the migration of the photo-generated carrier of solid solution inside; In addition, usually there is ZnGa on the ZnGaNO solid solution surface rising pH legal system standby
2o
4deng impurity, have impact on the absorption of ZnGaNO to visible ray, hinder photo-generated carrier and contact with solution and participate in redox reaction.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, there is visible light-responded, the organic matter in the aqueous solution to be had to high light catalytic degradation speed ZnO/ZnGaNO Two-phase composite structure powder.
For achieving the above object, the invention provides a kind of ZnO/ZnGaNO Two-phase composite structure photocatalytic powder, it is characterized in that, the inside of described Two-phase composite structure photocatalytic powder is wurtzite ZnO nanometer sheet, and outside is buergerite ZnGaNO solid solution nano particles.
Further, described Two-phase composite structure photocatalytic powder is the particle of diameter 100 ~ 500nm; Inside is the ZnO laminated structure of thickness 20 ~ 40 nanometer, diameter 100 ~ 500 nanometer, outside is less than the ZnGaNO solid solution spherical particle of 50 nanometers for diameter.
Further, described wurtzite ZnO nanometer sheet is the binary ZnO nano sheet of wurtzite structure.
Further, described buergerite ZnGaNO solid solution nano particles is the quaternary ZnGaNO solid solution nano particles of wurtzite structure, and containing Zn, Ga, N, O tetra-kinds of elements, wherein the atomic percent of N is 5% ~ 70%, Zn:Ga mol ratio is 1:1 ~ 4:1.
Further, preparation method is,
(1) water-soluble gallium salt and zinc salt are dissolved in deionized water, be made into hybrid metal solution, then hybrid metal solution is poured into rapidly containing CO
3 2-accompany by stirring in the aqueous slkali of ion, the pH value of solution is adjusted between 7 ~ 9, solution is aging in atmosphere;
(2) by solution centrifugal be separated obtain sediment, by sediment deionized water cyclic washing and centrifugation, finally by washing after sediment in atmosphere drying obtain white solid, grind into powder is presoma;
(3) by the ammonification 0.5 hour in 800 DEG C of ammonia environments of above-mentioned presoma, and naturally cool to room temperature under inert gas shielding, namely obtain ZnO/ZnGaNO Two-phase composite structure photocatalytic powder.
Further, in described step (1), in hybrid metal solution, the molar concentration of gallium ion and zinc ion is 0.05M ~ 1M, and wherein the mol ratio of zinc ion and gallium ion is 1:2 ~ 5:1;
Optional, hybrid metal solution is poured into rapidly containing CO
3 2-in the aqueous slkali of ion and when accompanying by stirring, mixing velocity 1 ~ 50mL/ second, mixing speed is 500 ~ 5000rpm;
Optional, described containing CO
3 2-the CO of the aqueous slkali of ion
3 2-the concentration of ion is 0.1M ~ 2M, CO
3 2-the molal quantity of ion is Ga in hybrid metal solution
3+1.5 ~ 5 times of ion;
Optional, described solution is aging is in atmosphere stirring in water bath in atmosphere, and bath temperature is room temperature ~ 80 DEG C, and mixing time is 5 ~ 12 hours.
Further, in described step (2), sediment spends deionized water 3 ~ 5 times;
Optional, the sediment after described washing in atmosphere drying refers to 80 DEG C of air drying process 12 hours.
On the other hand, the present invention also provides a kind of preparation method of described ZnO/ZnGaNO Two-phase composite structure photocatalytic powder, and it is characterized in that, step is,
(1) water-soluble gallium salt and zinc salt are dissolved in deionized water, be made into hybrid metal solution, then hybrid metal solution is poured into rapidly containing CO
3 2-accompany by stirring in the aqueous slkali of ion, the pH value of solution is adjusted between 7 ~ 9, solution is aging in atmosphere;
(2) by solution centrifugal be separated obtain sediment, by sediment deionized water cyclic washing and centrifugation, finally by washing after sediment in atmosphere drying obtain white solid, grind into powder is presoma;
(3) by the ammonification 0.5 hour in 800 DEG C of ammonia environments of above-mentioned presoma, and naturally cool to room temperature under inert gas shielding, namely obtain ZnO/ZnGaNO Two-phase composite structure photocatalytic powder.
Further, in described step (1), in hybrid metal solution, the molar concentration of gallium ion and zinc ion is 0.05M ~ 1M, and wherein the mol ratio of zinc ion and gallium ion is 1:2 ~ 5:1;
Optional, hybrid metal solution is poured into rapidly containing CO
3 2-in the aqueous slkali of ion and when accompanying by stirring, mixing velocity 1 ~ 50mL/ second, mixing speed is 500 ~ 5000rpm;
Optional, described containing CO
3 2-the CO of the aqueous slkali of ion
3 2-the concentration of ion is 0.1M ~ 2M, CO
3 2-the molal quantity of ion is Ga in hybrid metal solution
3+1.5 ~ 5 times of ion;
Optional, described solution is aging is in atmosphere stirring in water bath in atmosphere, and bath temperature is room temperature ~ 80 DEG C, and mixing time is 5 ~ 12 hours.
Further, in described step (2), sediment spends deionized water 3-5 time;
Optional, the sediment after described washing in atmosphere drying refers to 80 DEG C of air drying process 12 hours.
The particle of gained ZnO/ZnGaNO composite construction photocatalytic powder of the present invention to be diameter be 100 ~ 500nm; Wherein powder inside is the ZnO nano sheet of thickness 20 ~ 40 nanometer, diameter 100-500 nanometer, and powder is outside is less than the ZnGaNO solid solution spherical particle of 50 nanometers for diameter.
The ZnGaNO single-phase powder granule interior that prior art rises the acquisition of pH method has hole, and there is ZnGa on surface
2o
4impurity generates; Hole and surperficial ZnGa
2o
4the Crack cause of impurity is as follows: in the codeposition process rising pH method presoma, Ga (OH)
3first deposit when pH ≈ 2, and after pH=8, just there is codeposition formation Zn in Ga and Zn
2+/ Ga
3+/ CO
3 2-lDHs, and the Ga of LDH preferentially in solution (OH)
3heterogeneous forming core on nucleus, causes granular precursor inside for Ga (OH)
3outside is LDH.When solution age, Ga (OH) residual in solution
3with Zn
2+reaction generates ZnGa
2o
4impurity, is attached to granular precursor surface; The Ga (OH) of granular precursor inside during high-temperature ammonolysis
3dewater or form cavity with ammonia gas react volume-diminished, and the ZnGa on surface
2o
4impurity due to nitridation time very short and retained.
Prepare the shortcoming of ZnGaNO solid solution for the existing pH of liter law technology, the present invention adopts and falls pH legal system for presoma.In the codeposition process of presoma, Zn (OH)
2first generate when pH is 10 ~ 12, Zn
2+/ Ga
3+/ CO
3 2-lDHs when pH=8 after generate, and preferential at existing Zn (OH)
2heterogeneous forming core on nucleus, obtaining inside is Zn (OH)
2and outside is Zn
2+/ Ga
3+/ CO
3 2-the precursor powder particle of LDHs; Under high temperature after this composite precursor of nitrogenize, obtain ZnO/ZnGaNO Two-phase composite structure powder.Whole process does not have Ga (OH)
3generate, so also do not have ZnGa
2o
4impurity generates in a large number in ageing process, falls the ZnO/ZnGaNO Two-phase composite structure powder therefore surface nothing attachment ZnGa that pH method obtains
2o
4impurity; In addition, the ZnO/ZnGaNO two-phase level structure coupling that pH method obtains is fallen, the conduction band of ZnO and valence band location are all lower than conduction band and the valence band location of ZnGaNO solid solution, once ZnGaNO creates light induced electron and hole under visible light illumination, light induced electron will move to ZnO phase and participate in reduction reaction, and photohole moves to the organic pollution of the interface direct oxidation liquid of ZnGaNO and solution.Because light induced electron and hole are moved in the opposite direction, photo-generated carrier therefore not easily compound.When the reaction speed of photoactivation degradation of methylene blue weighs the efficiency of photocatalytic powder, the single-phase ZnGaNO solid solution that the existing pH of liter law technology obtains degrades the methylene blue of 55% for 2.5 hours, and the methylene blue that the standby ZnO/ZnGaNO Two-phase composite structure of pH legal system degraded 97% in 2.5 hours falls in the present invention's utilization, its photocatalysis efficiency is the existing twice rising the ZnGaNO powder photocatalytic efficiency that pH law technology obtains.
The present invention utilizes and reduces the co-electrodeposition method of pH value and prepare hydroxide precursor containing Zn ion and Ga ion in aqueous, then by presoma at high temperature nitrogenize, can obtain inner is ZnO nano sheet, the surperficial composite construction powder for ZnGaNO solid solution nano particles.This powder is high to the photocatalytic degradation efficiency of aqueous solution of methylene blue under visible light, and decoloring ability is strong.
ZnO/ZnGaNO Two-phase composite structure powder of the present invention has the following advantages:
1, response is had to the visible ray that wavelength is greater than 500nm.
2, the ZnO of ZnO/ZnGaNO Two-phase composite structure powder inside is conducive to the light induced electron in separation of Zn GaNO solid solution, make photo-generated carrier not easily compound, therefore the reaction speed of the photocatalysis to degrade organic matter of ZnO/ZnGaNO composite is compared traditional ZnGaNO solid solution and is doubled.
3, preparation method is simple, and preparation time is short, and cost is low, has the potentiality of industrialization.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the embodiment of the present invention 1 ~ 5 gained ZnO/ZnGaNO;
Fig. 2 is the scanning electron microscope diagram of the embodiment of the present invention 1 ~ 5 gained ZnO/ZnGaNO Two-phase composite structure powder;
Fig. 3 A is the scanning transmission microscope photograph via bright field of the embodiment of the present invention 1 ~ 5 gained ZnO/ZnGaNO Two-phase composite structure powder particle;
Fig. 3 B is the distribution diagram of element of Zn and Ga in this particle of obtaining of the embodiment of the present invention 1 ~ 5 gained ZnO/ZnGaNO Two-phase composite structure powder particle scanning transmission microscope;
Fig. 3 C is the distribution diagram of element of N in this particle of obtaining of the embodiment of the present invention 1 ~ 5 gained ZnO/ZnGaNO Two-phase composite structure powder particle scanning transmission microscope;
Fig. 3 D is the distribution diagram of element of O in this particle of obtaining of the embodiment of the present invention 1 ~ 5 gained ZnO/ZnGaNO Two-phase composite structure powder particle scanning transmission microscope;
Fig. 4 is the UV-Visible diffuse spectrogram of the embodiment of the present invention 1 ~ 5 gained ZnO/ZnGaNO Two-phase composite structure powder;
Fig. 5 is the energy level schematic diagram of the embodiment of the present invention 1 ~ 5 gained ZnO/ZnGaNO Two-phase composite structure powder;
Fig. 6 is the degradation speed comparison diagram of the methylene blue under the xenon source being greater than 400nm at wavelength of the ZnGaNO powder that obtains of the embodiment of the present invention 1 gained ZnO/ZnGaNO Two-phase composite structure powder and known method irradiates.
Detailed description of the invention
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Be exemplary below by the embodiment be described with reference to the drawings, be intended to for explaining the present invention, and can not limitation of the present invention be interpreted as.Unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
The preparation of embodiment 1:ZnO/ZnGaNO Two-phase composite structure powder
(1) by the Ga (NO of 12 grams
3)
39H
2o and 12 gram of Zn (NO
3)
26H
2o is dissolved in the 100mL aqueous solution, then the hybrid metal solution of gallium and zinc is poured rapidly into the 1mol/LNa of 70mL
2cO
3in solution, constantly stir, mixing velocity 30mL/ second, mixing speed is 1500rpm, obtains white precipitate simultaneously; After whole metallic solution is finished down, with 2mol/LNaOH solution, the pH of mixed solution is adjusted to 8;
(2) mixed solution obtained is carried out water-bath 12 hours at 80 DEG C, keep constantly stirring simultaneously.
(3) precipitation and centrifugal separation is also used washed with de-ionized water, three times repeatedly; By process dry at centrifugal precipitation 80 DEG C 12 hours, obtain white solid;
(4) white solid agate mortar is pulverized lastly obtain presoma.Presoma is put into high-temperature energy-conservation tube furnace to sinter at 800 DEG C and ammonia gas react 0.5 hour, the argon shield of lifting/lowering thermophase; Finally obtain yellow powder, be ZnO/ZnGaNO composite powder.The results are shown in Figure 1-5 and table 1.
Wherein Fig. 1 is the embodiment of the present invention 1 gained photocatalytic powder X-ray diffractogram, can be used for inferring the structure of gained powder.As seen from Figure 1, all main peaks all correspond to wurtzite structure, and this structure is consistent with the structure of ZnO and GaN, and lattice paprmeter is consistent with ZnO, illustrate that the embodiment of the present invention 1 gained photocatalytic powder is the solid solution of wurtzite structure.Fig. 2 is the photocatalytic powder ESEM microphoto of the embodiment of the present invention 1 gained, can observe its surface topography.As seen from Figure 2, the photocatalytic powder of the embodiment of the present invention 1 gained is the particle of diameter 100-500nm, and powder surface has a large amount of diameter to be less than the spherical particle of 50 nanometers.
Fig. 3 A is the scanning transmission microphoto of the photocatalytic powder particle of the present embodiment gained, and Fig. 3 A shows, and the photocatalytic powder of the embodiment of the present invention 1 gained has two-phase, and inside is laminated structure, and outside is graininess aggregate; Fig. 3 B, 3C, 3D are the distribution diagram of element of Zn, Ga, N, O of the photocatalytic powder of the embodiment of the present invention 1 gained respectively.As can be seen from these distribution diagram of element, the photocatalytic powder inside of the embodiment of the present invention 1 gained is the rich Zn phase of sheet, and outside is the rich Ga phase of a large amount of Nanoparticulate.
The atomic percent constituent analysis table of table 1.ZnO/ZnGaNO Two-phase composite structure powder
| at.％ | Zn | Ga | N | O |
| A | 49.84 | 7.01 | 2.81 | 40.34 |
| B | 23.83 | 21.01 | 3.29 | 51.87 |
Note: the position of A, B difference corresponding diagram 3 li mark, represents position and the tie element of ZnO and ZnGaNO respectively.
Table 1 is the elemental composition percentage utilizing EDS to measure: position " A " place is inner sheet phase, containing a large amount of Zn and O, a small amount of Ga and N, illustrate that in fact inner sheet should be binary buergerite ZnO phase mutually, a small amount of Ga and N may come from impact and the measure error of adjacent material; Position " B " is external nanoparticles, and its composition is for containing Zn, Ga, N, O tetra-kinds of elements, and wherein Zn:Ga is 3% than the atomic percent close to 1:1, N, and remaining is O; Illustrate that position " B " place should be ZnGaNO quaternary buergerite solid solution nano particles habitat.Inner ZnO phase and outside quaternary ZnGaNO solid solution are wurtzite structure, and lattice paprmeter closely.
Fig. 4 is the UV-Visible diffuse spectrogram of the photocatalytic powder of the present embodiment gained, shows the change of absorbance with wavelength of powder; As seen from Figure 4, the photocatalytic powder of the present embodiment gained can absorbing wavelength be all light between 200 ~ 520 nanometers, shows that the photocatalytic powder of the present embodiment gained has visible light-responded.
Fig. 5 is ZnO/ZnGaNO two-phase level structure schematic diagram.As seen from Figure 5, the conduction band of ZnO and valence band location are all lower than conduction band and the valence band location of ZnGaNO solid solution; Once ZnGaNO creates light induced electron and hole under visible light illumination, light induced electron will move to ZnO phase and participate in reduction reaction, and photohole moves to the organic pollution of the interface direct oxidation liquid of ZnGaNO and solution.Because light induced electron and hole are moved in the opposite direction, photo-generated carrier therefore not easily compound.This explains relative to single-phase ZnGaNO solid solution, the reason that ZnO/ZnGaNO Two-phase composite structure powder photocatalytic degraded water pollutant efficiency is higher.
The preparation of embodiment 2:ZnO/ZnGaNO Two-phase composite structure powder
(1) by the Ga (NO of 12 grams
3)
39H
2o and 17.82 gram of Zn (NO
3)
26H
2o is dissolved in the 100mL aqueous solution, then the hybrid metal solution of gallium and zinc is poured into the 1MNa of 70mL
2cO
3in solution, mixing velocity 10mL/ second, mixing speed is 1000rpm; After whole metallic solution is finished down, with 2MNaOH solution, the pH of mixed solution is adjusted to 7;
(2) mixed solution obtained is carried out water-bath 12 hours at 80 DEG C, keep constantly stirring simultaneously.
(3) precipitation and centrifugal separation is also used washed with de-ionized water, three times repeatedly; By process dry at centrifugal precipitation 80 DEG C 12 hours, obtain white solid;
(4) white solid agate mortar is pulverized lastly obtain presoma.Presoma is put into high-temperature energy-conservation tube furnace to sinter at 800 DEG C and ammonia gas react 0.5 hour, the argon shield of lifting/lowering thermophase; Finally obtain yellow powder, be ZnO/ZnGaNO composite powder.The results are shown in Figure 1 ~ 5 and table 1.
The preparation of embodiment 3:ZnO/ZnGaNO Two-phase composite structure powder
(1) by the Ga (NO of 2 grams
3)
39H
2o and 7.4 gram of Zn (NO
3)
26H
2o is dissolved in the 100mL aqueous solution, then the hybrid metal solution of gallium and zinc is poured into the 0.1MNa of 75mL
2cO
3in solution, mixing velocity 1mL/ second, mixing speed is 500rpm; After whole metallic solution is finished down, with 2MNaOH solution, the pH of mixed solution is adjusted to 9;
(2) mixed solution obtained is carried out water-bath 12 hours at 80 DEG C, keep constantly stirring simultaneously.
(3) precipitation and centrifugal separation is also used washed with de-ionized water, three times repeatedly; By process dry at centrifugal precipitation 80 DEG C 12 hours, obtain white solid;
(4) white solid agate mortar is pulverized lastly obtain presoma.Presoma is put into high-temperature energy-conservation tube furnace to sinter at 800 DEG C and ammonia gas react 0.5 hour, the argon shield of lifting/lowering thermophase; Finally obtain yellow powder, be ZnO/ZnGaNO composite powder.The results are shown in Figure 1 ~ 5 and table 1.
The preparation of embodiment 4:ZnO/ZnGaNO Two-phase composite structure powder
(1) by the Ga (NO of 40 grams
3)
39H
2o and 14.8 gram of Zn (NO
3)
26H
2o is dissolved in the 100mL aqueous solution, then the hybrid metal solution of gallium and zinc is poured into the 2MNa of 100mL
2cO
3in solution, mixing velocity 50mL/ second, mixing speed is 2000rpm, obtains white precipitate; After whole metallic solution is finished down, with 2MNaOH solution, the pH of mixed solution is adjusted to 8;
(2) mixed solution obtained is carried out water-bath 12 hours at 80 DEG C, keep constantly stirring simultaneously.
(3) precipitation and centrifugal separation is also used washed with de-ionized water, three times repeatedly; By process dry at centrifugal precipitation 80 DEG C 12 hours, obtain white solid;
(4) white solid agate mortar is pulverized lastly obtain presoma.Presoma is put into high-temperature energy-conservation tube furnace to sinter at 800 DEG C and ammonia gas react 0.5 hour, the argon shield of lifting/lowering thermophase; Finally obtain yellow powder, be ZnO/ZnGaNO composite powder.The results are shown in Figure 1 ~ 5 and table 1.
The preparation of embodiment 5:ZnO/ZnGaNO Two-phase composite structure powder
(1) by the Ga (NO of 12 grams
3)
39H
2o and 29.6 gram of Zn (NO
3)
26H
2o is dissolved in the 100mL aqueous solution, then the hybrid metal solution of gallium and zinc is poured into the 0.5MNa of 300mL
2cO
3in solution, mixing velocity 10mL/ second, mixing speed is 3000rpm; After whole metallic solution is finished down, with 2MNaOH solution, the pH of mixed solution is adjusted to 8;
(2) solution containing precipitation obtained is carried out water-bath 12 hours at 80 DEG C, keep constantly stirring simultaneously.
(3) precipitation and centrifugal separation is also used washed with de-ionized water, three times repeatedly; By process dry at centrifugal precipitation 80 DEG C 12 hours, obtain white solid;
(4) white solid agate mortar is pulverized lastly obtain presoma.Presoma is put into high-temperature energy-conservation tube furnace to sinter at 800 DEG C and ammonia gas react 0.5 hour, the argon shield of lifting/lowering thermophase; Finally obtain yellow powder, be ZnO/ZnGaNO composite powder.The results are shown in Figure 1 ~ 5 and table 1.
The Piglet s colibacillosis of embodiment 5:ZnO/ZnGaNO Two-phase composite structure powder
Under the irradiation of visible ray, the photodegradable speed of methylene blue weighs the photocatalysis efficiency of three kinds of photocatalytic powder.These three kinds of photocatalytic powder are respectively: ZnGaNO photocatalytic powder prepared by Japan Patent JP2005144219-A method, press the ZnGaNO photocatalytic powder rising pH method (CN102166527A) and prepare, and by the ZnO/ZnGaNO Two-phase composite structure photocatalytic powder prepared by embodiment 1.Often kind of photocatalytic powder is added certain density RuCl
3in ethanolic solution, heating mixed solution is until all ethanol evaporates to dryness; Will with RuCl
3photocatalytic powder heat treatment 1 hour under 350 degree in Muffle furnace, obtain load 5%RuO
2the photocatalytic powder of (percentage by weight) co-catalyst.By ground 0.1 gram of RuO
2/ photocatalytic powder adds the methylene blue solution of 100mL15g/L, with visible ray (xenon source, filter plate with 400 nanometers) illumination is carried out to methylene blue solution system, methylene blue solution outer circulation cold water cool to room temperature, additional magnetic agitation.Every 30 minutes, UV-Visible absorption test is carried out to methylene blue solution.
Fig. 6 is the curve map that the degradation rate of methylene blue solution containing different photocatalytic powder changes with light application time.The degradation rate of methylene blue is by formulae discovery below:
Degradation rate=(A
0-A
t)/A
0
In formula, A
0for initial methylene blue solution is in the absorbance at 664nm place, A
tfor methylene blue solution when degradation time is t is in the absorbance at 664nm place.Illumination is after 2.5 hours, and the degradation rate of ZnO/ZnGaNO composite powder prepared by embodiment 1 reaches 97.4%; And ZnGaNO powder degradation rate prepared by Japan Patent JP2005144210-A method is 70.1%, be 55.2% by the degradation rate rising ZnGaNO powder prepared by ZnGaNO prepared by pH method (Chinese patent application CN102166527A), and methylene blue only have 27% from degrading.Illustrate relative to additive method, ZnO/ZnGaNO composite powder prepared by the embodiment of the present invention 1 is respond well to the light degradation of methylene blue under visible light, decoloring ability is strong, and the disposal efficiency of the single-phase ZnGaNO solid solution prepared relative to additive method is higher.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention when not departing from principle of the present invention and aim, revising, replacing and modification.
Claims (9)
1. a ZnO/ZnGaNO Two-phase composite structure photocatalytic powder, is characterized in that, the inside of described Two-phase composite structure photocatalytic powder is wurtzite ZnO nanometer sheet, and outside is buergerite ZnGaNO solid solution nano particles.
2. ZnO/ZnGaNO Two-phase composite structure photocatalytic powder according to claim 1, is characterized in that, described Two-phase composite structure photocatalytic powder is the particle of diameter 100 ~ 500nm; Inside is the ZnO nano sheet of thickness 20 ~ 40 nanometer, diameter 100 ~ 500 nanometer, outside is less than the ZnGaNO solid solution spherical nanoparticles of 50 nanometers for diameter.
3. ZnO/ZnGaNO Two-phase composite structure photocatalytic powder according to claim 1, it is characterized in that, described buergerite ZnGaNO solid solution nano particles is the quaternary ZnGaNO solid solution nano particles of wurtzite structure, containing Zn, Ga, N, O tetra-kinds of elements, wherein the atomic percent of N is 5% ~ 70%, Zn:Ga mol ratio is 1:1 ~ 4:1.
4. ZnO/ZnGaNO Two-phase composite structure photocatalytic powder according to any one of claim 1-3, is characterized in that, preparation method is,
(1) water-soluble gallium salt and zinc salt are dissolved in deionized water, be made into hybrid metal solution, then hybrid metal solution is poured into rapidly containing CO
3 2-accompany by stirring in the aqueous slkali of ion, the pH value of solution is adjusted between 7 ~ 9, solution is aging in atmosphere;
(2) by solution centrifugal be separated obtain sediment, by sediment deionized water cyclic washing and centrifugation, finally by washing after sediment in atmosphere drying obtain white solid, grind into powder is presoma;
(3) by the ammonification 0.5 hour in 800 DEG C of ammonia environments of above-mentioned presoma, and naturally cool to room temperature under inert gas shielding, namely obtain ZnO/ZnGaNO Two-phase composite structure photocatalytic powder.
5. ZnO/ZnGaNO Two-phase composite structure photocatalytic powder according to claim 4, it is characterized in that, in described step (1), in hybrid metal solution, the molar concentration of gallium ion and zinc ion is 0.05M ~ 1M, and wherein the mol ratio of zinc ion and gallium ion is 1:2 ~ 5:1;
Optional, hybrid metal solution is poured into rapidly containing CO
3 2-in the aqueous slkali of ion and when accompanying by stirring, mixing velocity 1 ~ 50mL/ second, mixing speed is 500 ~ 5000rpm; Optional, described containing CO
3 2-cO in the aqueous slkali of ion
3 2-the concentration of ion is 0.1M ~ 2M, CO
3 2-the molal quantity of ion is Ga in hybrid metal solution
3+1.5 ~ 5 times of ion;
Optional, described solution is aging is in atmosphere stirring in water bath in atmosphere, and bath temperature is room temperature ~ 80 DEG C, and mixing time is 5 ~ 12 hours.
6. ZnO/ZnGaNO Two-phase composite structure photocatalytic powder according to claim 4, it is characterized in that, in described step (2), sediment spends deionized water 3 ~ 5 times;
Optional, the sediment after described washing in atmosphere drying refers to 80 DEG C of air drying process 12 hours.
7. a preparation method for ZnO/ZnGaNO Two-phase composite structure photocatalytic powder described in any one of claim 1-3, is characterized in that, step is,
(1) water-soluble gallium salt and zinc salt are dissolved in deionized water, be made into hybrid metal solution, then hybrid metal solution is poured into rapidly containing CO
3 2-accompany by stirring in the aqueous slkali of ion, the pH value of solution is adjusted between 7 ~ 9, solution is aging in atmosphere;
(2) by solution centrifugal be separated obtain sediment, by sediment deionized water cyclic washing and centrifugation, finally by washing after sediment in atmosphere drying obtain white solid, grind into powder is presoma;
(3) by the ammonification 0.5 hour in 800 DEG C of ammonia environments of above-mentioned presoma, and naturally cool to room temperature under inert gas shielding, namely obtain ZnO/ZnGaNO Two-phase composite structure photocatalytic powder.
8. ZnO/ZnGaNO Two-phase composite structure photocatalytic powder according to claim 7, it is characterized in that, in described step (1), in hybrid metal solution, the molar concentration of gallium ion and zinc ion is 0.05M ~ 1M, and wherein the mol ratio of zinc ion and gallium ion is 1:2 ~ 5:1;
Optional, hybrid metal solution is poured into rapidly containing CO
3 2-in the aqueous slkali of ion and when accompanying by stirring, mixing velocity 1 ~ 50mL/ second, mixing speed is 500 ~ 5000rpm;
Optional, described containing CO
3 2-cO in the aqueous slkali of ion
3 2-the concentration of ion is 0.1M ~ 2M, CO
3 2-the molal quantity of ion is Ga in hybrid metal solution
3+1.5 ~ 5 times of ion;
Optional, described solution is aging is in atmosphere stirring in water bath in atmosphere, and bath temperature is room temperature ~ 80 DEG C, and mixing time is 5 ~ 12 hours.
9. ZnO/ZnGaNO Two-phase composite structure photocatalytic powder according to claim 7, it is characterized in that, in described step (2), sediment spends deionized water 3 ~ 5 times;
Optional, the sediment after described washing in atmosphere drying refers to 80 DEG C of air drying process 12 hours.
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| JP2017213510A (en) * | 2016-05-31 | 2017-12-07 | 富士通株式会社 | Light excitation material |
| CN107649165A (en) * | 2017-10-20 | 2018-02-02 | 秦永泽 | Photocatalysis film and preparation method in a kind of foam metal graphene compound substrate |
| CN113389044A (en) * | 2021-06-28 | 2021-09-14 | 厦门求特新材料有限公司 | Anti-infrared camouflage ribbon with coating |
| CN113828343A (en) * | 2021-10-29 | 2021-12-24 | 厦门理工学院 | GaN ZnO solid solution powder subjected to surface treatment and surface treatment method thereof |
| CN113941356A (en) * | 2021-10-29 | 2022-01-18 | 南方科技大学 | Photocatalyst, and synthesis method and application thereof |
| CN113973839A (en) * | 2021-10-25 | 2022-01-28 | 厦门理工学院 | Carbon fiber loaded GaN/ZnO nanowire composite material, preparation method and sterilization device |
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| JP2017213510A (en) * | 2016-05-31 | 2017-12-07 | 富士通株式会社 | Light excitation material |
| CN107649165A (en) * | 2017-10-20 | 2018-02-02 | 秦永泽 | Photocatalysis film and preparation method in a kind of foam metal graphene compound substrate |
| CN113389044A (en) * | 2021-06-28 | 2021-09-14 | 厦门求特新材料有限公司 | Anti-infrared camouflage ribbon with coating |
| CN113389044B (en) * | 2021-06-28 | 2022-08-09 | 厦门求特新材料有限公司 | Anti-infrared camouflage ribbon with coating |
| CN113973839A (en) * | 2021-10-25 | 2022-01-28 | 厦门理工学院 | Carbon fiber loaded GaN/ZnO nanowire composite material, preparation method and sterilization device |
| CN113828343A (en) * | 2021-10-29 | 2021-12-24 | 厦门理工学院 | GaN ZnO solid solution powder subjected to surface treatment and surface treatment method thereof |
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| CN113941356B (en) * | 2021-10-29 | 2023-11-28 | 南方科技大学 | Photocatalyst, and synthesis method and application thereof |
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