CN104096560B - The heterogeneous nano array structure material of a kind of ZnO/Pt, preparation method and application thereof - Google Patents

The heterogeneous nano array structure material of a kind of ZnO/Pt, preparation method and application thereof Download PDF

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CN104096560B
CN104096560B CN201410348512.7A CN201410348512A CN104096560B CN 104096560 B CN104096560 B CN 104096560B CN 201410348512 A CN201410348512 A CN 201410348512A CN 104096560 B CN104096560 B CN 104096560B
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solution
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array structure
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CN104096560A (en
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吴正翠
薛业静
余浩
王欢
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Anhui Normal University
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Anhui Normal University
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Abstract

The invention provides the heterogeneous nano array structure material of a kind of ZnO/Pt, preparation method and application thereof.The present invention compared with prior art, has synthesized the heterogeneous nano array structure of ZnO/Pt of supporting Pt nano particle on hierarchical Z nO nanometer rods/ZnO nano sheet in zinc metal sheet substrate by simple chemical liquid deposition.ZnO/Pt provided by the invention heterogeneous nano array structure photochemical catalyst has the advantage that catalytic activity is high and technique is simple, cost is low.

Description

The heterogeneous nano array structure material of a kind of ZnO/Pt, preparation method and application thereof
Technical field
The invention belongs to preparation method of nano material and Environmental Chemistry cross-application field, be specifically related to the heterogeneous nano array structure material of a kind of ZnO/Pt, preparation method and application thereof.
Background technology
Along with industrial expansion, dyestuff (from fabric, paper and other industry) residual in sewage becomes a source of environmental problem.Semiconductor is used to become the promising method of one of wastewater pollutants process as photochemical catalyst light auxiliary catalysis degradable organic pollutant.In the semiconductors, TiO 2be widely used as photochemical catalyst.ZnO has similar band gap (3.2eV) and relative large quantum efficiency, and cost is low, can substitute TiO 2.ZnO even has the efficiency of higher photocatalysis to degrade organic matter in aqueous.
In light-catalysed process, the quick compound of electron-hole pair is the main reason hindering ZnO to improve catalytic performance.The combination of ZnO semiconductor substrate and noble metal cluster can be caught Photoinduced Charge carrier improve charge transfer process and promote photocatalytic activity.In different metals, precious metals pt has high electron affinity and high Schottky barrier, is used for forming Metal Zn O compound photochemical catalyst and is conducive to improving photocatalytic activity.ZnO is a kind of n-type semiconductor, and work content is about 4.3eV, precious metals pt work content 5.65eV, when the two contacts, will form Schottky barrier, and be conducive to electron capture in interface.Usually carry out making ZnO/Pt heterojunction structure by the method for the ZnO nano-structure modifying synthesis at present, but be generally difficult to the spontaneous nucleation avoiding Pt nano particle completely, thus affect photocatalytic activity.Use zinc metal sheet to be substrate and reactant, the heterogeneous nano array structure of ZnO/Pt of synthesis high yield, directly utilizes the research that array structure is not still correlated with as photochemical catalyst.This very has practical value to research photocatalytic applications.
Summary of the invention
The object of the present invention is to provide heterogeneous nano array structure material of a kind of ZnO/Pt and preparation method thereof, utilize chemical liquid deposition, technique is simple, cost is low.
A further object of the invention, provides the heterogeneous nano array structure of ZnO/Pt to apply as the photocatalytic degradation of organic dyestuff.
The heterogeneous nano array structure material of a kind of ZnO/Pt, at diameter be 150nm ZnO rod on grow the pliable and tough ZnO nano sheet that is of a size of 150nm and on ZnO nano sheet the Pt nano particle of even attachment 2-4nm.
The preparation method of the heterogeneous nano array structure material of a kind of ZnO/Pt provided by the invention, comprises the following steps:
(1) at polytetrafluoroethylene (PTFE) be liner stainless steel autoclave in, add deionized water, then add 1,6-hexamethylene diamine, obtain solution A, then, clean zinc metal sheet is placed in this solution obliquely, adds thermal response, after end, naturally cool to room temperature, the white product on zinc metal sheet respectively cleans 3 times with deionized water and absolute ethyl alcohol respectively, then 50 DEG C of vacuum drying 6h.
(2) product that step (1) is obtained is placed in the solution B formed by water and 1,6-hexamethylene diamine, then adds H 2ptCl 6solution, finally transfers to this reaction solution in the reactor of 50mL, adds thermal response, and finally at room temperature naturally cool, the black product deionized water that zinc metal sheet covers and absolute ethyl alcohol respectively wash 3 times, then 50 DEG C of vacuum drying 6h.
Step obtains solution A described in (1), and the volume ratio of deionized water and 1,6-hexamethylene diamine is 10-4.5:1;
Thermal response is added, temperature 150-180 DEG C, reaction time 5-8h described in step (1);
Solution B described in step (2), deionized water and 1,6-hexamethylene diamine volume ratio 28:10;
H described in step (2) 2ptCl 6solution concentration 3.0 × 10 -3mol/L, H 2ptCl 6the volume ratio of solution and solution B is 1:19;
In step (2), described adds thermal response, temperature 180 DEG C, reaction time 5h.
The present invention also provides the heterogeneous nano array structure material of a kind of ZnO/Pt to apply as the photocatalytic degradation of organic dyestuff rhodamine B (RhB).
The heterogeneous nano array structure product of ZnO/Pt the present invention prepared is cut into 1 × 1.5cm size, and putting into 5mL concentration is 1.0 × 10 -5also stir 1h in the dark in the RhB solution of mol/L, make catalyst surface reach the attached balance of absorption-desorption.Afterwards, 100W high-pressure sodium lamp is used to irradiate.Use ultraviolet-visible spectrophotometer (ShimadzuUV-2550) to measure the absorption spectrum of solution every 3min, determined the concentration of RhB by the characteristic absorption peak at 554nm place.
The present invention compared with prior art, by simple chemical liquid deposition, at ZnO nano-rod array body structure surface growth ZnO nano sheet, and uniform deposition Pt nano particle, obtain the heterogeneous nano array structure of ZnO/Pt of Deposition of Pt nanoparticles on hierarchical Z nO nanometer rods/ZnO nano sheet.The photochemical catalyst that the invention provides for the degraded of organic dyestuff rhodamine B has the advantage that activity is high and technique is simple, cost is low.
Accompanying drawing explanation
Fig. 1 is SEM (SEM) figure of the heterogeneous nano array structure material of ZnO/Pt prepared by embodiment 1;
Fig. 2 is X-ray energy spectrum (EDX) figure of the heterogeneous nano array structure material of ZnO/Pt prepared by embodiment 1;
Fig. 3 is transmission electron microscope (TEM) figure of single ZnO nanorod/ZnO nano sheet/Pt nano particle heterojunction structure in the ZnO/Pt heterogeneous nano array structure material of embodiment 1 preparation;
Fig. 4 is high resolution transmission electron microscopy (HRTEM) figure of shell ZnO nano sheet/Pt nano particle in the heterogeneous nano array structure material of ZnO/Pt of embodiment 1 preparation;
Fig. 5 is the ultra-violet absorption spectrum of embodiment 2ZnO/Pt heterogeneous nano array structure material ultraviolet catalytic degraded RhB solution;
Fig. 6 is the concentration changes with time curve of the heterogeneous nano array structure material of embodiment 2ZnO/Pt, ZnO nano-rod array structural material ultraviolet catalytic degraded RhB.
Detailed description of the invention
Embodiment 1
A preparation method for the heterogeneous nano array structure material of ZnO/Pt, comprises the following steps:
(1) at polytetrafluoroethylene (PTFE) be liner stainless steel autoclave in, add the deionized water of 40mL to 36mL, then add 1, the 6-hexamethylene diamine of 4mL to 8mL, obtain solution A.Then, clean zinc metal sheet (99.9%1 × 3cm) is placed in this solution obliquely.React 5-8h at autoclave being sealed in 150-180 DEG C, after reaction terminates, naturally cool to room temperature.White product on zinc metal sheet respectively rinses 3 times with deionized water and absolute ethyl alcohol respectively, then 50 DEG C of vacuum drying 6h.
(2), in the solution that 1, the 6-hexamethylene diamine product that the first step obtains being placed at 28mL water and 10mL is formed, then 2mLH is added 2ptCl 6solution (concentration 3.0 × 10 -3mol/L).Finally this solution is transferred in the reactor of 50mL, add thermal response, temperature 180 DEG C of lasting 5h.After reaction terminates, naturally cool to room temperature.The black product deionized water that zinc metal sheet covers and absolute ethyl alcohol respectively rinse 3 times, then 50 DEG C of vacuum drying 6h.
The structure of product and morphology characterization
Carry out morphology analysis by SEM to embodiment 1 products therefrom, result as shown in Figure 1.Show that prepared sample is nanometer rods/nanometer sheet classifying nano array structure.Analyze product component with X-ray energy spectrum, result as shown in Figure 2.Show that Pt element is successfully coupled on ZnO.Carried out morphology analysis to embodiment 1 products therefrom further with transmission electron microscope, result as shown in Figure 3.Show prepared sample nanometer rods/nanometer sheet classification nanostructure further.Analyze the nanometer sheet of embodiment 1 products therefrom shell further with high resolution transmission electron microscopy, result as shown in Figure 4.Wherein the interplanar distance of 0.281nm can index be (100) face of six side phase ZnO, and the interplanar distance of 0.227nm can index be (111) crystal face of Emission in Cubic Pt.Show that sample is that ZnO nano sheet adheres to Pt nano particle.
Embodiment 2
The application of a kind of ZnO/Pt heterogeneous nano array structure material light catalysis degradating organic dye.
Heterogeneous for the ZnO/Pt of above-mentioned preparation nano array structure product is cut into 1 × 1.5cm size, and putting into 5mL concentration is 1.0 × 10 -5also stir 1h in the dark in the RhB solution of mol/L, make catalyst surface reach the attached balance of absorption-desorption.Afterwards, irradiate with 100W high-pressure sodium lamp.Use ultraviolet-visible spectrophotometer (ShimadzuUV-2550) to measure the absorption spectrum of solution every 3min, determined the concentration of RhB by the characteristic absorption peak at 554nm place.As shown in Figure 5, degradation process concentration over time curve (provides the photocatalysis result of ZnO nano-rod array to compare) to the UV absorption spectrogram of photocatalytic degradation rhodamine B result as shown in Figure 6 simultaneously.After UV-irradiation 18min, the heterogeneous nano array structure photochemical catalyst of ZnO/Pt makes the rhodamine B degradation rate in solution reach 97.8%, is significantly higher than 87.5% of ZnO nano-rod array structure.Obviously, cooperative effect between hetero nano structure component significantly enhances photocatalytic activity, the distribution density that array structure is high in addition can farthest embody the photocatalytic activity relevant to its structure with spacing wide between adjacent nanostructures, the destruction of the micro-structural effectively avoiding powder catalyst often to face and reunion, for photocatalytic degradation applies the guarantee provided advantageously.

Claims (6)

1. a preparation method for the heterogeneous nano array structure material of ZnO/Pt, it is characterized in that, it comprises the following steps:
(1) at polytetrafluoroethylene (PTFE) be liner stainless steel autoclave in, add deionized water, then add 1,6-hexamethylene diamine, obtain solution A, then, clean zinc metal sheet is placed in this solution obliquely, adds thermal response, after end, naturally cool to room temperature, the white product on zinc metal sheet respectively cleans 3 times with deionized water and absolute ethyl alcohol respectively, then 50 DEG C of vacuum drying 6h;
(2) product that step (1) is obtained is placed in the solution B formed by water and 1,6-hexamethylene diamine, then adds H 2ptCl 6solution, transfers to this reaction solution in the reactor of 50mL, adds thermal response, and finally at room temperature naturally cool, the black product deionized water that zinc metal sheet covers and absolute ethyl alcohol respectively wash 3 times, then 50 ° of C vacuum drying 6h;
The structure of described ZnO/Pt heterogeneous nano array structure material is: at diameter be 150nm ZnO rod on grow the pliable and tough ZnO nano sheet that is of a size of 150nm and on ZnO nano sheet the Pt nano particle of even attachment 2-4nm.
2. preparation method according to claim 1, is characterized in that, step obtains solution A described in (1), and the volume ratio of deionized water and 1,6-hexamethylene diamine is 10-4.5:1.
3. preparation method according to claim 1, is characterized in that, adds thermal response, temperature 150-180 DEG C, reaction time 5-8h described in step (1).
4. preparation method according to claim 1, is characterized in that, solution B described in step (2), deionized water and 1,6-hexamethylene diamine volume ratio 28:10.
5. preparation method according to claim 1, is characterized in that, H described in step (2) 2ptCl 6solution concentration 3.0 × 10 -3mol/L, H 2ptCl 6the volume ratio of solution and solution B is 1:19.
6. preparation method according to claim 1, is characterized in that, in step (2), described adds thermal response, temperature 180 DEG C, reaction time 5h.
CN201410348512.7A 2014-07-21 2014-07-21 The heterogeneous nano array structure material of a kind of ZnO/Pt, preparation method and application thereof Expired - Fee Related CN104096560B (en)

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