CN104645980A - Noble metal-zinc oxide composite material and preparation method and application thereof - Google Patents
Noble metal-zinc oxide composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a noble metal-zinc oxide composite material and a preparation method and an application thereof, and belongs to the field of inorganic nonmetallic material preparation, environment protection technology and solar energy utilization technology. The composite material is composed of zinc oxide and noble metal nanoparticles. The zinc oxide covers the surface of the noble metal nanoparticles so as to form a rodlike structure with one end shaped as a pointed cone. By using dimethylamine-borane as a reducing agent and under the catalysis of the noble metal particles, nitrate is reduced so as to produce a lot of hydroxyls. Then, zinc ion is deposited in the form of zinc oxide on the surface of the noble metal particles, and a reaction is carried out at a certain temperature so as to obtain the noble metal-zinc oxide composite material. The noble metal-zinc oxide composite material can be directly applied to solve problems such as photocatalytic degradation of organic pollutants in water and efficient utilization of solar energy, especially the problem that photocatalytic efficiency of existing photocatalyst materials is low under full spectrum.
Description
Technical field
The invention belongs to inorganic nonmetallic nanometer material preparation and water purification environmental protection technical field; be specially a kind of noble metal-zinc oxide composite and its preparation method and application; particularly be made up of noble metal nano particles and bar-shaped zinc oxide; noble metal nano particles is wrapped in bar-shaped zinc oxide, and forming one end is the club shaped structure of pointed cone.
Background technology
Energy crisis and environmental pollution are two hang-ups that the current era mankind face; photocatalysis technology is because effectively can utilize solar energy; almost any organic molecule can be oxidized; mineralising is carbon dioxide and inorganic ions; organic pollution in degradation water, kills the microorganism such as bacterium, virus aspect in water and gets more and more people's extensive concerning.In numerous photochemical catalysts, feature is widely used in the fields such as photolysis water hydrogen, solar cell and environment remediation because low toxicity, cheapness, stability is high and environmentally friendly etc. for the n-type semiconductor of some broad stopbands such as titanium dioxide, zinc oxide, tin oxide etc.
Improve the efficiency of photochemical catalyst, key problem is the separation rate improving electron-hole.It is generally acknowledged and by the means of compound, by introducing knot effect and field-effect, thus electron-hole better can be separated, so just fundamentally improve the utilization rate of photocatalysis efficiency and sunshine.
After noble metal contacts with n-type semiconductor, semiconductor energy gap can be made to produce bending, introduce schottky junction simultaneously, be considered to the separative efficiency that can improve electron-hole.Although zinc oxide and titanium dioxide have band structure about the same, simultaneously as polar crystal, can form stable junction structure with noble metal, but relative to traditional photochemical catalyst titanium dioxide, the research of the compound aspect of noble metal and zinc oxide is reported less.The compound of zinc oxide and noble metal is applied to catalytic field usually, and the research of photocatalysis field is less.So, study a kind of simple possible, and the complex method of the noble metal-zinc oxide that can industrially apply, thus the application of this composite of research in photocatalysis water-purifying field further, be the important directions preparing high-efficiency photocatalysis material.
Summary of the invention
The object of the present invention is to provide a kind of noble metal-zinc oxide composite and its preparation method and application, this noble metal-zinc oxide composite can directly apply to the low difficult problem of photocatalysis efficiency under the problem, the particularly full spectrum of existing photocatalyst material solving the photocatalytic degradation of organic pollution in water and the efficiency utilization of solar energy.
Technical scheme of the present invention is:
A kind of noble metal-zinc oxide composite, this composite is made up of zinc oxide and noble metal nano particles, and described oxide coated by zinc is in noble metal nano particles surface, and forming one end is the club shaped structure of pointed cone; Wherein: the mol ratio of described zinc oxide and noble metal nano particles is 100:(0.1-1).
Described noble metal nano particles is gold, platinum, silver or palladium particle, and its size is less than 100 nanometers, can be one or more in graininess, sheet, bar-shaped and polyhedral.
The preparation method of above-mentioned noble metal-zinc oxide composite is: first noble metal nano particles is scattered in absolute ethyl alcohol the suspension being mixed with noble metal nano particles, then added in the desired amount in the mixed solution of zinc nitrate and dimethylamine borane, after ultrasonic disperse, react at the temperature of 60 ~ 200 DEG C, obtain noble metal-zinc oxide composite.Concrete preparation process comprises the steps:
(1) by noble metal nano particles ultrasonic disperse in absolute ethyl alcohol, in every milliliter of absolute ethyl alcohol, the addition of noble metal nano particles is 0.1-1 milligram, forms the suspension of noble metal nano particles;
(2) (0 DEG C) preparation mother liquor in ice bath, in described mother liquor, zinc nitrate concentration is 10 ~ 30 grams per liters, and dimethylamine borane concentration is 1 ~ 10 grams per liter, and all the other are solvent;
(3) according to the suspension of noble metal nano particles: the suspension of noble metal nano particles adds in mother liquor by the volume ratio of mother liquor=(0.1-1): 100, after ultrasonic disperse, at the temperature of 60 ~ 200 DEG C, be incubated 1 ~ 10 hour, obtain noble metal-zinc oxide composite.
Solvent described in step (2) is be liquid alcohols or water under room temperature.
Above-mentioned noble metal-zinc oxide composite can directly apply to the photocatalytic degradation of organic pollution under sunshine.
Design principle of the present invention is as follows:
Dimethylamine borane is the reducing agent of a kind of common, reducing property gentleness in electroplating industry, and this reducing agent, under the catalysis of noble metal, can reduce nitrate anion, and then makes to produce a large amount of hydroxyls in solution.Utilize the above-mentioned characteristic of dimethylamine borane, the composite of noble metal and zinc oxide can be obtained by a kind of simple liquid phase reactor method.Therefore, the present invention is by a kind of method of simple precious metal catalyst reduction nitrate anion, and ingenious noble metal of preparing is wrapped in composite in zinc oxide.
The invention has the advantages that:
1. the present invention's dimethylamine borane is as reducing agent, issues raw reduction reaction in the existence of noble metal, and a large amount of hydroxyls that reaction produces the zinc ion precipitation around noble metal, can be wrapped in precious metal surface.Meanwhile, the zinc oxide in solution can be grown up further, forms club shaped structure, and final acquisition one end is the noble metal-zinc oxide composite of the club shaped structure of pointed cone, and this recombination process is simple to operate, is easy to control, is easy to suitability for industrialized production.
2. the present invention is by under precious metal catalyst, and the principle of dimethylamine borane reduction nitrate anion obtains noble metal-zinc oxide composite, and catalytic reduction reaction occurs at precious metal surface, is so just beneficial to and obtains wrapping up composite completely.
3. the present invention is reducing agent by material dimethylamine borane, simultaneously also as precipitating reagent, obtains noble metal-zinc oxide composite.This reducing agent can be dissolved in organic and inorganic solution, and catalytic process is gentle, is convenient to control and commercial introduction.
4. noble metal-zinc oxide composite of the present invention can directly apply to the purification degraded of organic pollution under sunshine.
5. the complex method of the present invention's employing, well can protect noble metal, prevent the loss of noble metal in Separation of Solid and Liquid and photocatalytic process.
Accompanying drawing explanation
Fig. 1 is palladium of the present invention-zinc oxide composite TEM photo.
Fig. 2 is the X ray diffracting spectrum of palladium-zinc oxide composite of the present invention.
Fig. 3 is palladium of the present invention-zinc oxide composite absorption curves.
Fig. 4 is the degradation curve of palladium-zinc oxide composite of the present invention for aqueous solution Methylene Blue.
Detailed description of the invention
The technological process of noble metal of the present invention-zinc oxide composite preparation method is as follows:
Noble metal nano particles is scattered in absolute ethyl alcohol and is configured to suspension, then in required ratio, suspension is added in zinc nitrate and dimethylamine borane mixed solution, ultrasonic disperse, finally reacts at the temperature of 60 ~ 200 DEG C, obtains noble metal-zinc oxide composite.
Embodiment 1
First, by 1 milligram of Pd nano particle (graininess) ultrasonic disperse in 4 milliliters of absolute ethyl alcohols, obtain the suspension of Pd nano particle; Then, in ice bath, configuration is containing the solution of zinc nitrate 15 grams per liter, dimethylamine borane 3 grams per liter, and solvent is water, obtains mother liquor; Finally, in 100 milliliters of mother liquors, add the suspension of 300 microlitre Pd nano particles, after ultrasonic disperse, at the temperature of 120 DEG C, be incubated 6 hours, obtain palladium-zinc oxide composite.
Figure 1 shows that the present embodiment gained palladium-zinc oxide composite TEM photo.As seen from Figure 1, palladium-zinc oxide composite that the present invention obtains, is wrapped in bar-shaped zinc oxide by the palladium particle of 20 ran, forms the club shaped structure pattern that one end is pointed cone.
Figure 2 shows that the X ray diffracting spectrum of palladium-zinc oxide composite.Obtained by Fig. 2 analysis, zinc oxide with the form of buergerite phase exist, due to palladium content very little, do not detect the peak of palladium.
Figure 3 shows that the absorption curves of palladium-zinc oxide composite.As seen from Figure 3, by the compound of palladium and zinc oxide, make material in visible region and infrared light region, have light absorption.
The present embodiment gained palladium-zinc oxide composite is used for photocatalytic degradation of methylene blue, and this experimentation is as follows:
Take the palladium-zinc oxide composite 100 milligrams of acquisition, being scattered in 100 ml concns under dark is in the methylene blue solution of 6ppm, is placed in light intensity and is about 100mW/cm
2illumination penetrate down, to sample at regular intervals, the remaining methylene blue concentration of centrifugal rear mensuration supernatant, obtain the photocatalytic degradation curve of this material under full spectrum; The light of visibility region and ultraviolet region is kept off respectively with optical filter, under the condition of identical material dosage, sample at regular intervals, the remaining methylene blue concentration of centrifugal rear mensuration supernatant, obtain the photocatalytic degradation curve of this material under ultraviolet light, radiation of visible light respectively.
The methylene blue degradation curve of palladium-zinc oxide composite as shown in Figure 4.As seen from Figure 4, no matter this palladium-zinc oxide composite is when ultraviolet light, visible ray irradiate separately, Quan or spectral illumination when, all show excellent Photocatalytic Degradation Property.
The x-ray photoelectron power spectrum of table 1 palladium-zinc oxide composite
Table 1 is the x-ray photoelectron power spectrum of the present embodiment palladium-zinc oxide composite, and as can be seen from Table 1, palladium exists with the form of simple substance.Composition graphs 4, can find out, even if the content of palladium is little, but palladium-zinc oxide composite also can be made to have excellent photocatalysis performance.
When noble metal nano particles selects gold, platinum or the nano grain of silver period of the day from 11 p.m. to 1 a.m, according to the operation of embodiment 1 experimental procedure, obtain the technique effect that same embodiment 1 is identical.
Embodiment result shows, the present invention utilizes dimethylamine borane can reduce nitrate anion under the catalysis of noble metal, and then produces a large amount of characteristic hydroxy, by regulating experiment parameter and solution ratio, achieves the compound of noble metal and zinc oxide.Its recombination process is simple, is easy to industrialization promotion, for providing a kind of photocatalyst compound material efficiently containing the protection of the dirty water purification of organic matter and environment.
Claims (8)
1. noble metal-zinc oxide composite, is characterized in that: this composite is made up of zinc oxide and noble metal nano particles, and described oxide coated by zinc is in noble metal nano particles surface, and forming one end is the club shaped structure of pointed cone.
2. according to noble metal-zinc oxide composite according to claim 1, it is characterized in that: the mol ratio of described zinc oxide and noble metal nano particles is 100:(0.1-1).
3. according to noble metal-zinc oxide composite according to claim 1, it is characterized in that: described noble metal nano particles is gold, platinum, silver or palladium particle, its size is less than 100 nanometers.
4. according to noble metal-zinc oxide composite according to claim 1, it is characterized in that: described noble metal nano particles is one or more in graininess, sheet, bar-shaped and polyhedral.
5. according to the preparation method of noble metal-zinc oxide composite according to claim 1, it is characterized in that: first noble metal nano particles is scattered in absolute ethyl alcohol the suspension being mixed with noble metal nano particles by the method, then added in the desired amount in the mixed solution of zinc nitrate and dimethylamine borane, after ultrasonic disperse, react at the temperature of 60 ~ 200 DEG C, obtain noble metal-zinc oxide composite.
6. according to the preparation method of noble metal-zinc oxide composite according to claim 5, it is characterized in that: the concrete preparation process of the method comprises the steps:
(1) by noble metal nano particles ultrasonic disperse in absolute ethyl alcohol, in every milliliter of absolute ethyl alcohol, the addition of noble metal nano particles is 0.1-1 milligram, forms the suspension of noble metal nano particles;
(2) in ice bath, prepare mother liquor, in described mother liquor, zinc nitrate concentration is 10 ~ 30 grams per liters, and dimethylamine borane concentration is 1 ~ 10 grams per liter, and all the other are solvent;
(3) according to the suspension of noble metal nano particles: the suspension of noble metal nano particles adds in mother liquor by the volume ratio of mother liquor=(0.1-1): 100, after ultrasonic disperse, at the temperature of 60 ~ 200 DEG C, be incubated 1 ~ 10 hour, obtain noble metal-zinc oxide composite.
7. according to the preparation method of noble metal-zinc oxide composite according to claim 6, it is characterized in that: solvent described in step (2) is be liquid alcohols or water under room temperature.
8. according to the application of noble metal-zinc oxide composite according to claim 1, it is characterized in that: the photocatalytic degradation described noble metal-zinc oxide composite being directly applied to organic pollution under sunshine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195144A (en) * | 2015-10-15 | 2015-12-30 | 吉林大学 | Method for synthetizing Au/ZnO bar-shaped heterojunction photocatalyst |
| CN113731387A (en) * | 2020-05-28 | 2021-12-03 | 长春理工大学 | Cheap metal/semiconductor composite photocatalyst for treating organic pollutants in water and preparation method thereof |
| CN114602466A (en) * | 2022-04-06 | 2022-06-10 | 华南师大(清远)科技创新研究院有限公司 | Carbon/zinc oxide/noble metal composite material, photocatalyst, preparation method and application thereof |
| CN115739121A (en) * | 2022-11-14 | 2023-03-07 | 中国科学院福建物质结构研究所 | Metal-coated composite semiconductor material and preparation method and application thereof |
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2013
- 2013-11-21 CN CN201310594469.8A patent/CN104645980B/en active Active
Non-Patent Citations (2)
| Title |
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| H. R. LIU ET AL.: "《Worm-Like Ag/ZnO Core−Shell Heterostructural Composites:Fabrication, Characterization, and Photocatalysis》", 《THE JOURNAL OF PHYSICAL CHEMISTRY》 * |
| YUANZHI CHEN ET AL: "《Au–ZnO hybrid nanoflowers, nanomultipods and nanopyramids: one-pot reaction synthesis and photocatalytic properties》", 《ROYAL SOCITEY OF CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195144A (en) * | 2015-10-15 | 2015-12-30 | 吉林大学 | Method for synthetizing Au/ZnO bar-shaped heterojunction photocatalyst |
| CN113731387A (en) * | 2020-05-28 | 2021-12-03 | 长春理工大学 | Cheap metal/semiconductor composite photocatalyst for treating organic pollutants in water and preparation method thereof |
| CN114602466A (en) * | 2022-04-06 | 2022-06-10 | 华南师大(清远)科技创新研究院有限公司 | Carbon/zinc oxide/noble metal composite material, photocatalyst, preparation method and application thereof |
| CN115739121A (en) * | 2022-11-14 | 2023-03-07 | 中国科学院福建物质结构研究所 | Metal-coated composite semiconductor material and preparation method and application thereof |
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