CN104056644A - ZnO/ZnSe nano material, and preparation method and application thereof - Google Patents
ZnO/ZnSe nano material, and preparation method and application thereof Download PDFInfo
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- CN104056644A CN104056644A CN201410348485.3A CN201410348485A CN104056644A CN 104056644 A CN104056644 A CN 104056644A CN 201410348485 A CN201410348485 A CN 201410348485A CN 104056644 A CN104056644 A CN 104056644A
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Abstract
The invention provides a ZnO/ZnSe nano material, and a preparation method and application thereof. Compared with the prior art, the method is characterized in that a ZnO/ZnSe nano wall heterogenous array structure is synthesized on a zinc chip substrate by a simple low-temperature chemical liquid phase conversion method. A visible light catalyst with the ZnO/ZnSe nano wall heterogenous array structure, which is provided by the invention, has the advantages of high catalytic activity, good circulation stability, simplicity in process and low cost.
Description
Technical field
The invention belongs to nano-heterogeneous structure material preparation method and Environmental Chemistry cross-application field, be specifically related to a kind of photocatalysis ZnO/ZnSe nano-heterogeneous structure material preparation and application.
Background technology
Along with industrial expansion, in sewage, residual dyestuff (from fabric, paper and other industry) becomes a source of environmental problem.Use semiconductor to become as photochemical catalyst light auxiliary catalysis degradable organic pollutant a kind of promising method that wastewater pollutants is processed.ZnO is as a kind of important wide with gap and direct with gap semiconductor (the with gap of block ZnO is 3.37eV), electronics mobility (205～300cm
2v s
-1) surpassed TiO
2(0.1 – 4cm
2v s
-1), thering is catalytic efficiency high, the low and Environmental Sustainability of cost, is widely regarded as a kind of very promising photochemical catalyst.Yet, zno-based originally can only utilize ultraviolet light (only account for reach the earth solar spectrum 3～5%), and can not utilize visible ray (account for solar spectrum 44～47%).In addition, right quick compound in the light induced electron hole in ZnO photocatalytic process is a major obstacle that improves its photocatalysis efficiency.Therefore, the key of raising ZnO photocatalytic activity is to use another material to modify ZnO surface to improve sunshine utilization ratio and to promote separation that light produces electric charge.The narrow with gap semiconductor that is coupled on ZnO surface is extended to visible-range by light absorption and reduces charge recombination tendency is a kind of very promising method.
ZnSe belongs to environmentally friendly narrow gap semiconductor, form ZnO/ZnSe nano-heterogeneous structure with ZnO and there is visible light catalysis activity, but the report of correlative study is at present less, still not about the synthetic of the heterogeneous array structure of ZnO/ZnSe nm wall and for the report of visible light catalytic, the therefore synthetic heterogeneous array structure of ZnO/ZnSe nm wall, for visible light photocatalytic degradation organic dyestuff, tool has very important significance.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of ZnO/ZnSe nano material and preparation method thereof, utilize cryochemistry liquid phase transformation approach, technique is simple, cost is low.
A further object of the invention, provides the visible light photocatalytic degradation application of ZnO/ZnSe nano material as organic dyestuff.
A kind of ZnO/ZnSe nano material provided by the invention, on the ZnO nano sheet for diameter 500nm, adhering to size is the ZnSe nanometer sheet of 50nm.
The preparation method of a kind of ZnO/ZnSe nano material provided by the invention, comprises the following steps:
(1) 1,6-hexamethylene diamine is added in deionized water, stir, obtain solution A; Nine hydrated sodium sulfides are dissolved in solution A, obtain solution B, solution B is poured in the stainless steel autoclave that polytetrafluoroethylene (PTFE) is liner, clean zinc metal sheet is placed in this solution obliquely, add thermal response, after reaction finishes, naturally cool to room temperature, gray product on zinc metal sheet is respectively cleaned 3 times with deionized water and absolute ethyl alcohol respectively, then 50 ℃ of vacuum drying 6h;
(2) selenium powder is joined in the mixed solution of ammoniacal liquor and deionized water, constantly stir and form homogeneous solution, add sodium borohydride, continue to stir after 30min, the zinc metal sheet that is coated with product of inserting step (1) gained, adds thermal response, after end, the zinc metal sheet that is coated with product is respectively cleaned 3 times with deionized water and absolute ethyl alcohol, and 50 ℃ of vacuum drying 6h, obtain the heterogeneous array structure of ZnO/ZnSe nm wall.
In step (1), the volume ratio of deionized water and 1,6-hexamethylene diamine is 19-7:1;
The concentration that obtains vulcanized sodium in solution B described in step (1) is 0.025-0.035mol/L;
Described in step (1), add thermal response, temperature 120-150 ℃, reaction time 8-10h;
In step (2), the volume ratio of ammoniacal liquor used and deionized water is 0.6-1:1;
In step (2), the concentration of selenium powder in the mixed solution of ammoniacal liquor and deionized water is 0.003-0.005mol/L;
In step (2), the mol ratio 2-2.1:1 of sodium borohydride and selenium powder;
In step (2), described thermal response, temperature 60-90 ℃, the reaction time 5-8h of adding;
The present invention also provides the photocatalytic applications of a kind of ZnO/ZnSe nano material as visible light photocatalytic degradation organic dyestuff rhodamine B (RhB).
The heterogeneous array structure sample of ZnO/ZnSe nm wall prepared by the present invention is cut into 1 * 1.5cm size, and putting into 5mL concentration is 1.0 * 10
-5in the RhB solution of mol/L, also stir in the dark 1h, make catalyst surface reach the attached balance of absorption-desorption.Afterwards, use 300W xenon lamp to carry out radiation of visible light.Every 20min, use ultraviolet-visible spectrophotometer (Shimadzu UV-2550) to measure the absorption spectrum of solution, by the characteristic absorption peak at 554nm place, determine the concentration of RhB.
The present invention compared with prior art, by simple cryochemistry liquid phase transformation approach, forms novel ZnSe nano-sheet shell structurre on the surface of ZnO nano chip arrays structure, obtain the heterogeneous array structure of ZnO/ZnSe nm wall.Visible light catalyst for organic dyestuff rhodamine B photocatalytic degradation provided by the invention has advantages of that catalytic activity is high, good cycling stability and technique is simple, cost is low.
Accompanying drawing explanation
Fig. 1 is X-ray powder diffraction (XRD) figure of the ZnO/ZnSe nano material of embodiment 1 preparation;
Fig. 2 is SEM (SEM) figure of the ZnO/ZnSe nano material of embodiment 1 preparation;
Fig. 3 is transmission electron microscope (TEM) figure of single ZnO/ZnSe nm wall in the ZnO/ZnSe nano material of embodiment 1 preparation;
Fig. 4 is high resolution transmission electron microscopy (HRTEM) figure of shell ZnSe nanometer sheet in the ZnO/ZnSe nano material of embodiment 1 preparation;
Fig. 5 is the ultra-violet absorption spectrum of embodiment 2ZnO/ZnSe nano material visible light photocatalytic degradation RhB;
Fig. 6 is the concentration changes with time curve of embodiment 2ZnO/ZnSe nano material and ZnO nano chip arrays visible light photocatalytic degradation RhB.
The specific embodiment
Embodiment 1
A preparation method for ZnO/ZnSe nano material, comprises the following steps:
(1), by 1 of 2mL, 6-hexamethylene diamine is added drop-wise in the deionized water of 38mL, stirs, and obtains solution A; 0.297g nine hydrated sodium sulfides are dissolved in solution A, obtain solution B.Solution B is poured in the stainless steel autoclave that polytetrafluoroethylene (PTFE) is liner.Then, clean zinc metal sheet (99.9%1 * 3cm) is placed in this solution obliquely.Autoclave is sealed at 150 ℃ and reacts 10h.After reaction finishes, naturally cool to room temperature.Gray product on zinc metal sheet is respectively rinsed 3 times with deionized water and absolute ethyl alcohol respectively, then 50 ℃ of vacuum drying 6h.
(2) 0.01g selenium powder joins in the mixed solution of 20mL ammoniacal liquor and 20mL deionized water, in 100mL glass reaction bottle, constantly stirs and forms homogeneous solution, then adds 0.01g sodium borohydride.Stir after 30min the zinc metal sheet that is coated with product of inserting step (1) gained.Reaction bulb is added at 90 ℃ to thermal response 5h.After reaction finishes, the zinc metal sheet that is coated with product is respectively rinsed 3 times to 50 ℃ of vacuum drying 6h with deionized water and absolute ethyl alcohol.
The structure of product and morphology characterization:
With Rigaku TTRIII X-ray powder diffraction instrument (Cu target), embodiment 1 products therefrom is carried out to the thing identification of phases, as shown in Figure 1.Except the diffraction maximum of zinc metal sheet substrate and ZnO, corresponding to the diffraction maximum of 2 θ angle 27.5o and 54.2o, can belong to respectively (111), (311) crystal face (JCPDS No:80-0021) of Emission in Cubic ZnSe.XRD analysis result shows, the sample of preparing in zinc metal sheet substrate is to consist of ZnO and ZnSe two-phase.
By SEM, product has been carried out to morphology analysis, result as shown in Figure 2.Show that sample is nm wall array structure.
With transmission electron microscope, the ultrasonic product getting off from substrate has been carried out to morphology analysis, result as shown in Figure 3.Show that sample is in nanometer sheet, to adhere to the structure of less nanometer sheet.
With high resolution transmission electron microscopy, further the shell of product is analyzed, result as shown in Figure 4.The interplanar distance of 0.32nm can index be (111) crystal face of Emission in Cubic ZnSe.
Embodiment 2
A kind of visible light photocatalytic degradation organic dyestuff application of ZnO/ZnSe nano material.
The heterogeneous array structure product of the ZnO/ZnSe nm wall of above-mentioned preparation is cut into 1 * 1.5cm size, and putting into 5mL concentration is 1.0 * 10
-5in the RhB solution of mol/L, also stir in the dark 1h, make catalyst surface reach the attached balance of absorption-desorption.Afterwards, use 300W xenon lamp to carry out radiation of visible light.Every 20min, use ultraviolet-visible spectrophotometer (ShimadzuUV-2550) to measure the absorption spectrum of solution, by the characteristic absorption peak at 554nm place, determine the concentration of RhB.As shown in Figure 5, curve is as shown in Figure 6 over time for degradation process concentration for the UV absorption spectrogram of degradation results.After radiation of visible light 120min, degradation rate reaches 93%.Obviously, cooperative effect between nm wall heterojunction structure component has significantly strengthened photocatalytic activity, between the distribution density that the heterogeneous array structure of nm wall is high in addition and adjacent nanostructured, wide spacing can farthest embody the photocatalytic activity relevant to its structure, effectively avoid destruction and the reunion of the micro-structural that powder catalyst often faces, this provides more favourable guarantee for photocatalytic degradation application.
Embodiment 3
A kind of ZnO/ZnSe nano material is as the cycle performance of visible light catalyst rhodamine B degradation.
Array structure catalyst after photocatalytic degradation is taken out with tweezers, with deionized water and absolute ethyl alcohol, rinse several times, be reentered in fresh RhB solution and carry out photocatalytic degradation experiment, result is as shown in table 1.After result of study shows this photochemical catalyst circulation 10 times, degradation rate still reaches 91.2%, shows that this photochemical catalyst has good photocatalysis cyclical stability to RhB, and this is very attractive for practical application.
Table 1 is the circulation result of the heterogeneous array structure visible light photocatalytic degradation of embodiment 3ZnO/ZnSe nm wall RhB.
Table 1
Embodiment 4
A preparation method for ZnO/ZnSe nano material, comprises the following steps:
(1), by 1 of 5mL, 6-hexamethylene diamine is added drop-wise in the deionized water of 35mL, stirs, and obtains solution A; 0.336g nine hydrated sodium sulfides are dissolved in solution A, obtain solution B.Solution B is poured in the stainless steel autoclave that polytetrafluoroethylene (PTFE) is liner.Then, clean zinc metal sheet (99.9%1 * 3cm) is placed in this solution obliquely.Autoclave is sealed at 120 ℃ and reacts 9h.After reaction finishes, naturally cool to room temperature.Gray product on zinc metal sheet is respectively rinsed 3 times with deionized water and absolute ethyl alcohol respectively, then 50 ℃ of vacuum drying 6h.
(2) 0.015g selenium powder joins in the mixed solution of 20mL ammoniacal liquor and 20mL deionized water, in 100mL glass reaction bottle, constantly stirs and forms homogeneous solution, then adds 0.015g sodium borohydride.Stir after 30min the zinc metal sheet that is coated with product of inserting step (1) gained.Reaction bulb is added at 70 ℃ to thermal response 8h.After reaction finishes, the zinc metal sheet that is coated with product is respectively rinsed 3 times to 50 ℃ of vacuum drying 6h with deionized water and absolute ethyl alcohol.
Claims (10)
1. a ZnO/ZnSe nano material, is characterized in that, on the ZnO nano sheet for diameter 500nm, adhering to size is the ZnSe nanometer sheet of 50nm.
2. a preparation method for ZnO/ZnSe nano material claimed in claim 1, is characterized in that, described preparation method comprises the following steps:
(1) 1,6-hexamethylene diamine is added in deionized water, stir, obtain solution A; Nine hydrated sodium sulfides are dissolved in solution A, obtain solution B, solution B is poured in the stainless steel autoclave that polytetrafluoroethylene (PTFE) is liner, clean zinc metal sheet is placed in this solution obliquely, add thermal response, after reaction finishes, naturally cool to room temperature, gray product on zinc metal sheet is respectively cleaned 3 times with deionized water and absolute ethyl alcohol respectively, then 50 ℃ of vacuum drying 6h;
(2) selenium powder is joined in the mixed solution of ammoniacal liquor and deionized water, constantly stir and form homogeneous solution, add sodium borohydride, continue to stir after 30min, the zinc metal sheet that is coated with product of inserting step (1) gained, adds thermal response, after end, the zinc metal sheet that is coated with product is respectively cleaned 3 times with deionized water and absolute ethyl alcohol, and 50 ℃ of vacuum drying 6h, obtain the heterogeneous array structure of ZnO/ZnSe nm wall.
3. preparation method according to claim 2, is characterized in that, in step (1), the volume ratio of deionized water and 1,6-hexamethylene diamine is 19-7:1.
4. preparation method according to claim 2, is characterized in that, the concentration that obtains vulcanized sodium in solution B described in step (1) is 0.025-0.035mol/L.
5. preparation method according to claim 2, is characterized in that, described in step (1), adds thermal response, temperature 120-150 ℃, reaction time 8-10h.
6. preparation method according to claim 2, is characterized in that, in step (2), the concentration of selenium powder in the mixed solution of ammoniacal liquor and deionized water is 0.003-0.005mol/L.
7. preparation method according to claim 2, is characterized in that, in step (2), the volume ratio of ammoniacal liquor used and deionized water is 0.6-1:1.
8. according to preparation method claimed in claim 2, it is characterized in that, in step (2), the mol ratio 2-2.1:1 of sodium borohydride and selenium powder.
9. preparation method according to claim 2, is characterized in that, in step (2), and described thermal response, temperature 60-90 ℃, the reaction time 5-8h of adding.
10. a ZnO/ZnSe nano material claimed in claim 1 is as the photocatalytic applications of visible light photocatalytic degradation organic dyestuff rhodamine B (RhB).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104384527A (en) * | 2014-12-10 | 2015-03-04 | 黑龙江大学 | Preparation method of self-supporting two-dimensional transition metal/metal oxide mixed-phase nanosheet |
| CN107138170A (en) * | 2017-05-03 | 2017-09-08 | 吉林师范大学 | A kind of preparation method of ZnO/ZnSe hetero-junctions nanobelt photocatalyst film |
| CN112007668A (en) * | 2020-08-13 | 2020-12-01 | 西安工程大学 | Preparation method of ZnO ternary composite photocatalyst |
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| CN101786609A (en) * | 2010-01-11 | 2010-07-28 | 云南大学 | Method for synthesizing bar-shaped ZnSe fluorescence nanocrystalline |
| CN102602898A (en) * | 2012-02-24 | 2012-07-25 | 长春理工大学 | Method for preparing monodisperse zinc selenide particles |
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2014
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Patent Citations (3)
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| JPS59112841A (en) * | 1982-12-21 | 1984-06-29 | Toshiba Corp | Catalyst for photochemical reaction |
| CN101786609A (en) * | 2010-01-11 | 2010-07-28 | 云南大学 | Method for synthesizing bar-shaped ZnSe fluorescence nanocrystalline |
| CN102602898A (en) * | 2012-02-24 | 2012-07-25 | 长春理工大学 | Method for preparing monodisperse zinc selenide particles |
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| HEEYEON PARK ET AL.: "Synthesis of ultrathin wurtzite ZnSe nanosheets", 《MATERIALS LETTERS》 * |
| ZHIMING WU ET AL.: "An all-inorganic type-II heterojunction array with nearly full solar spectral response based on ZnO/ZnSe core/shell nanowires", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104384527A (en) * | 2014-12-10 | 2015-03-04 | 黑龙江大学 | Preparation method of self-supporting two-dimensional transition metal/metal oxide mixed-phase nanosheet |
| CN104384527B (en) * | 2014-12-10 | 2016-06-01 | 黑龙江大学 | The preparation method of the two-dimentional transition metal/metal oxides mixed phase nanometer sheet of a kind of self-supporting |
| CN107138170A (en) * | 2017-05-03 | 2017-09-08 | 吉林师范大学 | A kind of preparation method of ZnO/ZnSe hetero-junctions nanobelt photocatalyst film |
| CN112007668A (en) * | 2020-08-13 | 2020-12-01 | 西安工程大学 | Preparation method of ZnO ternary composite photocatalyst |
| CN112007668B (en) * | 2020-08-13 | 2023-02-07 | 西安工程大学 | Preparation method of ZnO ternary composite photocatalyst |
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