CN103878011A - Method for synthesizing GaN: ZnO solid solution photocatalyst - Google Patents
Method for synthesizing GaN: ZnO solid solution photocatalyst Download PDFInfo
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- CN103878011A CN103878011A CN201410155199.5A CN201410155199A CN103878011A CN 103878011 A CN103878011 A CN 103878011A CN 201410155199 A CN201410155199 A CN 201410155199A CN 103878011 A CN103878011 A CN 103878011A
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Abstract
The invention relates to a method for synthesizing GaN: ZnO solid solution photocatalyst, relates to a method for synthesizing a photocatalyst, and solves the technical problems that the appearance and granularity of a nitride synthesized by adopting a high-temperature nitriding method are difficult to control. The method comprises the following steps of I, weighing Ga2O3, ZnO and fused salt to be placed in a agate mortar, and grinding the Ga2O3, ZnO and fused salt for 30 to 60 minutes under the room temperature to obtain solid powder; II, calcining the solid powder for 6h to 24h under the condition that the flow rate of ammonia gas is 100 to 250mL/min and the temperature is 800 to 1000 DEG C; and III, cooling the solid powder to the room temperature under the ammonia gas atmosphere and taking out, and washing and drying the solid powder to obtain the GaN: ZnO solid solution photocatalyst. The composite photocatalyst is in a hollow polygonal body, raw materials are low in price, the reaction pressure is low, the device is simple, simplicity in operation is realized, no heavy metal is loaded, the granularity of material powder is uniform, and the purity is high. The method for synthesizing the GaN: ZnO solid solution photocatalyst belongs to the preparation field of photocatalysts.
Description
Technical field
The present invention relates to a kind of method of synthetic photochemical catalyst.
Background technology
Along with becoming increasingly conspicuous of the aggravation of contradictions between limited fossil fuel and the energy demand of mankind's sharp increase and environmental problem, exploitation is clean, efficient renewable new forms of energy are very urgent.Hydrogen Energy has the advantages such as high combustion value, combustion product is pollution-free, odorless is nontoxic, is the desirable energy of solution present stage energy crisis and environmental pollution.H
2can, directly as the fuel of fuel cell, for electric motor car provides power, solve current tail gas pollution problem, also Hydrogen Energy can be converted into electric energy, for electrical appliance power supply, solve energy problem.And water electrolysis hydrogen production cost is higher, high temperature pyrolysis water hydrogen manufacturing energy conversion efficiency is low, feasibility is poor, is all difficult to develop into the technology of large-scale production hydrogen.Solar energy is inexhaustible regenerative resource, utilizes solar energy photocatalytic hydrogen production by water decomposition, and low energy density, dispersed strong solar energy is converted into Hydrogen Energy, then by fuel cell by the H generating
2and O
2carry out electrochemical reaction, produce electric energy, its product water can be used as again the raw material of solar hydrogen making, and can not produce any pollution to environment, can form eucyclic energy system.And the solar energy resources of China is very abundant, potentiality to be exploited is huge.In solar spectrum, ultraviolet light accounts for 5% of gross energy, and the visible ray of wavelength X >420nm accounts for 43%, therefore utilizes visible ray to carry out the emphasis that photocatalytic hydrogen production by water decomposition is following hydrogen manufacturing research, is subject to showing great attention to of international community.
Decades in the past, the photochemical catalyst of metal nitride and oxynitrides is widely studied to water decomposition.But, the current synthetic controlled chemical composition that has, size and the good single dispersion metal nitride of pattern and the photochemical catalyst of oxynitrides remain a challenge.Wherein, add the modification GaN:ZnO solid solution of rhodium chromium mixed oxide co-catalyst to demonstrate high-performance and the stability of decomposition water under radiation of visible light.At high temperature nitriding and oxidizing gallium and Zinc oxide powder are a kind of conventional methods of preparing GaN:ZnO solid solution, and the pattern of the sample of preparation is unmanageable by this method.In recent years, some method of modifying have been developed the solid solution for the preparation of GaN:ZnO.Someone reports and prepares nanocrystalline and hexagonal nanometer sheet GaN:ZnO solid solution.But, in these preparation process, need some presomas.And high-temperature ammonolysis method synthesizing nitride pattern and particle diameter problem rambunctious.
Summary of the invention
The object of the invention is, in order to solve the synthetic Morphology of Nitrides of high-temperature ammonolysis method and particle diameter technical problem rambunctious, provides a kind of method of synthetic GaN:ZnO mischcrystal photocatalyst.
The method of synthetic GaN:ZnO mischcrystal photocatalyst is as follows:
One, take Ga
2o
3, ZnO and fused salt be placed in agate mortar, at room temperature grinds 30～60 minutes, obtains pressed powder;
Two, be that 100～250mL/min, temperature are to calcine 6～24 hours under the condition of 800～1000 ℃ by pressed powder at ammonia flow velocity;
Three, take out be cooled to room temperature under ammonia atmosphere after, through wash dry after, obtain GaN:ZnO mischcrystal photocatalyst;
Ga in step 1
2o
3, ZnO and fused salt mass ratio be 0.47:0.54:0.505～2.02.
It is a kind of using molten salt as medium that the salt fusing that the present invention adopts is synthesized, and conventional liquid phase is synthesized and developed into a kind of important synthetic method.And compared with traditional hydro-thermal, solvent-thermal method, molten-salt growth method can effectively shorten reaction time, reduce the advantages such as equipment requirement and technology difficulty, raising degree of crystallinity.
The composite photo-catalyst that the present invention obtains is hollow polyhedron, and the cost of material of the inventive method is low, and reaction pressure is little, installs simple and easyly, and simple to operate, and without carried noble metal, and material powder uniform particles, purity are high.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the GaN:ZnO mischcrystal photocatalyst of experiment one preparation;
Fig. 2 is the SEM figure of the GaN:ZnO mischcrystal photocatalyst of experiment one preparation;
Fig. 3 is the SEM figure of the GaN:ZnO mischcrystal photocatalyst of experiment one preparation;
Fig. 4 is the TEM figure of the GaN:ZnO mischcrystal photocatalyst of experiment one preparation;
Fig. 5 is the SAED figure of the GaN:ZnO mischcrystal photocatalyst of experiment one preparation;
Fig. 6 is the GaN:ZnO mischcrystal photocatalyst nitrogen adsorption/desorption isotherms of experiment one preparation, and in figure, ■ represents desorption curve, ● represent adsorption curve;
Fig. 7 is the corresponding pore size distribution curve figure of GaN:ZnO mischcrystal photocatalyst of experiment one preparation;
Fig. 8 is the uv-visible absorption spectra figure of the GaN:ZnO mischcrystal photocatalyst of experiment one preparation;
Fig. 9 is the spectrogram of the photocatalytic activity of the different photochemical catalysts of the GaN:ZnO mischcrystal photocatalyst of experiment one preparation.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the method for the synthetic GaN:ZnO mischcrystal photocatalyst of present embodiment is as follows:
One, take Ga
2o
3, ZnO and fused salt be placed in agate mortar, at room temperature grinds 30～60 minutes, obtains pressed powder;
Two, be that 100～250mL/min, temperature are to calcine 6～24 hours under the condition of 800～1000 ℃ by pressed powder at ammonia flow velocity;
Three, take out be cooled to room temperature under ammonia atmosphere after, through wash dry after, obtain GaN:ZnO mischcrystal photocatalyst;
Ga in step 1
2o
3, ZnO and fused salt mass ratio be 0.47:0.54:0.505～2.02.
The specific embodiment two: what present embodiment was different from the specific embodiment one is that the fused salt described in step 1 is sodium chloride, potassium chloride, sodium carbonate or potash.Other is identical with the specific embodiment one.
The specific embodiment three: the milling time that what present embodiment was different from one of specific embodiment one or two is in step 1 is 40 minutes.Other is identical with one of specific embodiment one or two.
The specific embodiment four: that present embodiment is different from one of specific embodiment one to three is Ga in step 1
2o
3, ZnO and fused salt mass ratio be 0.47:0.54:1.Other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is that in step 2, ammonia flow velocity is 120～220mL/min.Other is identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to five is that in step 2, ammonia flow velocity is 200mL/min.Other is identical with one of specific embodiment one to five.
The specific embodiment seven: what present embodiment was different from one of specific embodiment one to six is in step 2 calcines under temperature is the condition of 820～950 ℃.Other is identical with one of specific embodiment one to six.
The specific embodiment eight: what present embodiment was different from one of specific embodiment one to seven is in step 2 calcines under temperature is the condition of 900 ℃.Other is identical with one of specific embodiment one to seven.
The specific embodiment nine: what present embodiment was different from one of specific embodiment one to eight is that in step 2, calcination time is 10～20 hours.Other is identical with one of specific embodiment one to eight.
The specific embodiment ten: what present embodiment was different from one of specific embodiment one to nine is that in step 2, calcination time is 15 hours.Other is identical with one of specific embodiment one to nine.
Adopt following experimental verification effect of the present invention:
Experiment one:
The method of the synthetic GaN:ZnO mischcrystal photocatalyst of present embodiment is as follows:
One, take Ga
2o
3, ZnO and sodium chloride is placed in agate mortar, at room temperature grinds 30 minutes, obtains pressed powder;
Two, pressed powder being contained in porcelain boat, being placed in tube furnace and passing into ammonia, is that 150mL/min, temperature are to calcine 15 hours under the condition of 850 ℃ at ammonia flow velocity;
Three, take out be cooled to room temperature under ammonia atmosphere after, first with distilled water washing 3 times, then use absolute ethanol washing 3 times, be then placed in darkroom and dry up, obtain GaN:ZnO mischcrystal photocatalyst;
Ga in step 1
2o
3, ZnO and sodium chloride mass ratio be 0.47:0.54:1.
The GaN:ZnO mischcrystal photocatalyst of being found out this experiment preparation by Fig. 1, peak is sharp-pointed and intensity is high, and better crystallinity degree is described.
The GaN:ZnO mischcrystal photocatalyst of being found out this experiment preparation by Fig. 2-Fig. 5 is particle.
Fig. 6, Fig. 7 are for this experiment gained GaN:ZnO mischcrystal photocatalyst nitrogen adsorption/desorption isotherms and corresponding aperture dividing
Cloth curve map, further illustrates that prepared catalyst has cavernous structure and specific area is large.
Fig. 8 is the spectrogram of the photocatalytic activity of this experiment gained GaN:ZnO mischcrystal photocatalyst.As seen from the figure, prepared photochemical catalyst has absorption at 430nm, demonstrate and absorb the ability of visible ray, there is no obvious difference at the uv-visible absorption spectra of all samples, the impact of the optical characteristics of the sample of the mass ratio that this means salt on synthesized is little.The photocatalytic activity of sample is generated and is evaluated by the photocatalysis oxygen from water.
The method of the synthetic GaN:ZnO mischcrystal photocatalyst of present embodiment is as follows:
One, take Ga
2o
3, ZnO and sodium chloride is placed in agate mortar, at room temperature grinds 30 minutes, obtains pressed powder;
Two, pressed powder being contained in porcelain boat, being placed in tube furnace and passing into ammonia, is that 150mL/min, temperature are to calcine 15 hours under the condition of 850 ℃ at ammonia flow velocity;
Three, take out be cooled to room temperature under ammonia atmosphere after, first with distilled water washing 3 times, then use absolute ethanol washing 3 times, be then placed in darkroom and dry up, obtain GaN:ZnO mischcrystal photocatalyst;
Ga in step 1
2o
3, ZnO and sodium chloride mass ratio be 0.47:0.54:0.505～2.02.
Fig. 9 has provided the photocatalytic activity (λ >400nm) of the sample of the mass ratio of different N aCl under visible ray condition.Its result shows, this photocatalyst activity can be effectively by NaCl content influence.And the quality of the NaCl obtaining and Ga
2o
3the sample activity that is 1.0 with the total mass ratio of ZnO is the highest, the throughput rate 31.2 μ mol/h of oxygen.
Claims (10)
1. the method for synthetic GaN:ZnO mischcrystal photocatalyst, is characterized in that the method for synthetic GaN:ZnO mischcrystal photocatalyst is as follows:
One, take Ga
2o
3, ZnO and fused salt be placed in agate mortar, at room temperature grinds 30～60 minutes, obtains pressed powder;
Two, be that 100～250mL/min, temperature are to calcine 6～24 hours under the condition of 800～1000 ℃ by pressed powder at ammonia flow velocity;
Three, take out be cooled to room temperature under ammonia atmosphere after, through wash dry after, obtain GaN:ZnO mischcrystal photocatalyst;
Ga in step 1
2o
3, ZnO and fused salt mass ratio be 0.47:0.54:0.505～2.02.
2. the method for synthesizing according to claim 1 GaN:ZnO mischcrystal photocatalyst, is characterized in that the fused salt described in step 1 is sodium chloride, potassium chloride, sodium carbonate or potash.
3. according to the method for synthetic GaN:ZnO mischcrystal photocatalyst described in claim 1 or 2, it is characterized in that the milling time in step 1 is 40 minutes.
4. according to the method for synthetic GaN:ZnO mischcrystal photocatalyst described in claim 1 or 2, it is characterized in that Ga in step 1
2o
3, ZnO and fused salt mass ratio be 0.47:0.54:1.
5. according to the method for synthetic GaN:ZnO mischcrystal photocatalyst described in claim 1 or 2, it is characterized in that in step 2, ammonia flow velocity is 120～220mL/min.
6. according to the method for synthetic GaN:ZnO mischcrystal photocatalyst described in claim 1 or 2, it is characterized in that in step 2, ammonia flow velocity is 200mL/min.
7. according to the method for synthetic GaN:ZnO mischcrystal photocatalyst described in claim 1 or 2, it is characterized in that in step 2 calcining under temperature is the condition of 820～950 ℃.
8. according to the method for synthetic GaN:ZnO mischcrystal photocatalyst described in claim 1 or 2, it is characterized in that in step 2 calcining under temperature is the condition of 900 ℃.
9. according to the method for synthetic GaN:ZnO mischcrystal photocatalyst described in claim 1 or 2, it is characterized in that in step 2, calcination time is 10～20 hours.
10. according to the method for synthetic GaN:ZnO mischcrystal photocatalyst described in claim 1 or 2, it is characterized in that in step 2, calcination time is 15 hours.
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Cited By (8)
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|---|---|---|---|---|
| CN105233852A (en) * | 2015-11-10 | 2016-01-13 | 上海理工大学 | GaN/CQDS composite photocatalyst and preparing method and application thereof |
| CN106319557A (en) * | 2015-07-07 | 2017-01-11 | 中国科学院大连化学物理研究所 | Photoelectrochemistry water decomposition GaN:ZnO photo-anode preparing method |
| CN106582769A (en) * | 2016-12-29 | 2017-04-26 | 南京工业大学 | Preparation method of noble metal-free composite optical catalytic material |
| CN106824242A (en) * | 2017-01-19 | 2017-06-13 | 京东方科技集团股份有限公司 | The preparation method and material for air purification of a kind of material for air purification |
| CN108117052A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院金属研究所 | A kind of 2 D mesopore (GaN) 1-x (ZnO) x solid solution nano materials and preparation method thereof |
| CN109746019A (en) * | 2018-12-28 | 2019-05-14 | 西安交通大学 | A kind of preparation method and applications of gallium indium-zinc ternary nitrogen oxides |
| CN112675890A (en) * | 2020-12-21 | 2021-04-20 | 中国医科大学附属第一医院 | Visible light catalytic nano antibacterial material and preparation method thereof |
| CN115072774A (en) * | 2022-07-16 | 2022-09-20 | 桂林理工大学 | Tetragonal phase layered nitride and low-cost high-efficiency preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319557A (en) * | 2015-07-07 | 2017-01-11 | 中国科学院大连化学物理研究所 | Photoelectrochemistry water decomposition GaN:ZnO photo-anode preparing method |
| CN106319557B (en) * | 2015-07-07 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of GaN of optical electro-chemistry decomposition water:The preparation method of ZnO photo-anode |
| CN105233852A (en) * | 2015-11-10 | 2016-01-13 | 上海理工大学 | GaN/CQDS composite photocatalyst and preparing method and application thereof |
| CN108117052A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院金属研究所 | A kind of 2 D mesopore (GaN) 1-x (ZnO) x solid solution nano materials and preparation method thereof |
| CN108117052B (en) * | 2016-11-29 | 2020-10-16 | 中国科学院金属研究所 | Two-dimensional mesoporous (GaN)1-x (ZnO) x solid solution nano material and preparation method thereof |
| CN106582769A (en) * | 2016-12-29 | 2017-04-26 | 南京工业大学 | Preparation method of noble metal-free composite optical catalytic material |
| CN106824242A (en) * | 2017-01-19 | 2017-06-13 | 京东方科技集团股份有限公司 | The preparation method and material for air purification of a kind of material for air purification |
| CN109746019A (en) * | 2018-12-28 | 2019-05-14 | 西安交通大学 | A kind of preparation method and applications of gallium indium-zinc ternary nitrogen oxides |
| CN112675890A (en) * | 2020-12-21 | 2021-04-20 | 中国医科大学附属第一医院 | Visible light catalytic nano antibacterial material and preparation method thereof |
| CN112675890B (en) * | 2020-12-21 | 2021-11-19 | 中国医科大学附属第一医院 | Visible light catalytic nano antibacterial material and preparation method thereof |
| CN115072774A (en) * | 2022-07-16 | 2022-09-20 | 桂林理工大学 | Tetragonal phase layered nitride and low-cost high-efficiency preparation method thereof |
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Application publication date: 20140625 |