CN101947454A - Transitional metal-doped zinc oxide mesoporous material with visible light catalytic activity and preparation method thereof - Google Patents
Transitional metal-doped zinc oxide mesoporous material with visible light catalytic activity and preparation method thereof Download PDFInfo
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- CN101947454A CN101947454A CN 201010275787 CN201010275787A CN101947454A CN 101947454 A CN101947454 A CN 101947454A CN 201010275787 CN201010275787 CN 201010275787 CN 201010275787 A CN201010275787 A CN 201010275787A CN 101947454 A CN101947454 A CN 101947454A
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Abstract
The invention discloses a transitional metal-doped ZnO mesoporous material with a visible light catalytic activity and a preparation method thereof. The component of the transitional metal-doped ZnO mesoporous material is as follows: Zn1-xRexO, wherein, Re is Mn, Fe, Co and Cu; and x is 0.1mol-6mol%. The preparation method comprises the following steps: dissolving zinc salt, urea and metal salt used for doping into distilled water for stirring to obtain a presoma solution; controlling the total concentration of the metal ion to be 0.05mol/L-0.2mol/L; controlling the molar ratio of the urea to the metal ion to be 5-15; placing into a high-pressure reactor to carry out seal reaction; cooling, and washing with deionized water; and carrying out vacuum drying and roasting to obtain the transitional metal-doped ZnO mesoporous material, wherein the mesoporous channel diameter is 2.5nm-15nm; the specific surface area is 32.6m<2/>g-50m<2>/g; and the mesoporous material has stronger light absorption and light response at a visible light range of 400-700nm as well as high visible light catalysis activity, and can be widely used for light catalysis to eliminate the organic pollutants in air and water.
Description
Technical field
The present invention relates to transition metal doping zinc oxide mesoporous material that has visible light catalysis activity and preparation method thereof, belong to catalysis material, field of environment protection.
Background technology
Process of industrialization develops when bringing glad tidings to people fast, and shortage of resources and environmental pollution have become the global severe challenge that people face.Environmental pollution not only has influence on the sustainable development of China's economic society, also has influence on the people's Health and Living quality highlightedly.Human disease of digestive system, effective control of respiratory system environmental pollution have become the countries in the world government face significant problem to be solved with letter with improvement, and air cleaning and water treatment etc. also becomes one of important research content of researcher thus.The traditional processing method of present China, as physisorphtion, chemiadsorption and biological degradation method etc., though technical maturity, but generally speaking treatment effeciency is low, particularly can not remove the low concentration that exists in the water body effectively but the organic pollution of bio-refractory, can not satisfy the needs of economic development and life, the water pollution treatment method of therefore developing a kind of new practicality remains people's current target.Conductor photocatalysis can be converted into highdensity chemical energy and electric energy with low-density solar energy, simultaneously can directly utilize low-density sunshine degradation water and airborne all contaminations, so photocatalysis has great potential aspect the depollution of environment and the new energy development.Photocatalysis can be passed through the speed and the selectivity of condition control reactions such as light intensity, optical wavelength, realizes by the unavailable chemical reaction of thermal response.This method can at room temperature be utilized solar energy fully, has low cost, free of contamination advantage, to fundamentally solving environmental pollution and the energy shortage problem has immeasurable meaning.ZnO is good semiconductor light-catalyst, has good photoelectric characteristic, stable chemical performance, feature such as cheap, nontoxic.But the ZnO semiconductor has the broad stopband width of about 3.2eV, can only absorbing wavelength less than the ultraviolet light of 387nm.Therefore, the visible light-responded zno-based catalysis material that must development can utilize sunshine, usually by doped transition metal ions such as Co, Ni and Mn or the non-metal N doped absorbability that improves visible light, still there is the inefficient problem of visible light photocatalysis at present at present.Present many experiments all prove TiO
2After mesoporousization under certain condition photocatalysis performance obviously improve mesoporous TiO
2The raising of photocatalysis performance mainly is because the design feature of mesoporous material determines, the bigger serface of mesoporous material increases the reflecting point of catalytic reaction, pore passage structure helps reactant more in the absorption of catalysis material surface simultaneously, the mesopore orbit structure can make the easier arrival catalysis material of electronics and the hole surface participation surface chemical reaction that optical excitation produces in addition, thereby improves conversion quantum efficiency.But relevant transition metal doping zinc oxide mesoporous material is as catalysis material and preparation method thereof, and not seeing has pertinent literature report and patent application.
Summary of the invention
One of purpose of the present invention provides the high transition metal doping zinc oxide mesoporous photocatalytic material of a kind of visible light catalysis activity.
Two of purpose of the present invention provides the high transition metal doping zinc oxide mesoporous photocatalytic preparation methods of a kind of visible light catalysis activity.
The objective of the invention is to realize in the following manner:
The transition metal doping zinc oxide mesoporous material component that the present invention has visible light catalysis activity is: Zn
1-xRe
xO, wherein Re comprises Mn, Fe, Co or Cu; X=0.1mol-6mol%; The mesopore orbit diameter of its mesoporous material is 2.5nm-15nm, and specific area is 32.6m
2/ g-50m
2/ g.
Described transition metal doping zinc oxide mesoporous material component is preferably: Zn
1-xRe
xO, wherein Re comprises Mn, Fe, Co or Cu; X=5mol%.
Described transition metal doping zinc oxide mesoporous material component can also be preferably: Zn
1-xCu
xO, x=0.1mol-6mol% wherein, more preferably: Zn
1-xCu
xO, wherein x=5mol%.
Have the preparation method of the transition metal doping zinc oxide mesoporous material of visible light catalysis activity, may further comprise the steps:
(1) with zinc salt, urea and be selected from manganese, iron, cobalt and the copper any slaine and be dissolved in to stir in the distilled water and obtain precursor solution;
(2) precursor solution is placed autoclave, sealing, 100-130 ℃ of reaction 1～24h;
(3) reaction finishes and is cooled to room temperature, product deionized water cyclic washing, vacuum drying 2-8h;
(4) then at 400～600 ℃ of roasting 2-4h.
The described zinc salt of step (1) comprises zinc acetate, zinc sulfate, zinc nitrate or zinc chloride; Described manganese salt comprises manganese acetate, manganese sulfate, manganese nitrate or manganese chloride; Described molysite comprises ferrous sulfate or frerrous chloride; Described cobalt salt comprises cobalt acetate, cobaltous sulfate, cobalt nitrate or cobalt chloride; Described mantoquita comprises copper acetate, copper sulphate, copper nitrate or copper chloride.
The described metal ion total concentration of step (1) is controlled to be 0.05mol/L-0.2mol/L;
The described urea of step (1) is controlled to be 5-15 with the ratio of the mole of metal ion;
The described vacuum drying temperature of step (3) is 80～100 ℃.
The present invention first with metal-doped in the zinc oxide mesopore material, be applied to have in the catalysis material preparation of visible light catalysis activity; Improve the visible absorption ability by transition metal doping zinc oxide on the one hand, utilize the unique texture characteristics of mesoporous material to improve visible light catalysis activity simultaneously, use it for catalysis material, help reactant in the absorption of catalysis material surface, the mesopore orbit structure can make the easier arrival catalysis material of electronics and the hole surface participation surface chemical reaction that optical excitation produces in addition, thereby improves conversion quantum efficiency.
The material of preparation gained characterizes its structure and performance with XRD, nitrogen adsorption desorption curve, UV-vis absorption spectrum etc. respectively, the results are shown in Figure 1～Fig. 3, and the bright prepared material of the XRD figure stave of Fig. 1 is single hexagonal wurtzite type ZnO structure.Fig. 2 is the nitrogen adsorption/desorption curve map and the corresponding pore-size distribution of 5mol%Cu doping zinc-oxide, and shown in figure, this material has tangible mesoporous feature, and the mesopore orbit diameter of mesoporous material is 2.5nm-15nm, and specific area is 50m
2/ g.Fig. 3 is the low power TEM figure (a) and the HRTEM figure (b) of 5mol%Cu doping zinc-oxide, as seen from the figure this material good crystallinity and have pore structure.Fig. 4 is the UV-vis absorption spectrum, and all transition metal doping zinc oxide mesoporous materials all have absorption more by force in visible-range 400～700nm from scheming as can be known.The transition metal doping zinc oxide mesoporous material is measured the photocatalytic activity of its degraded xanthate under radiation of visible light with photocatalyst, experimental result shows that all material all has visible light catalysis activity, and especially the copper doped zinc oxide sample demonstrates good visible light catalysis activity.
Characteristics of the present invention are:
(1) the prepared transition metal doping zinc oxide of this method has tangible mesoporous feature, and the mesopore orbit diameter is 2.5nm-15nm, and specific area is 32.6m
2/ g-50m
2/ g.
(2) all transition metal doping zinc oxide mesoporous materials all have absorption more by force in visible-range 400～700nm, have improved the utilization ratio of sunshine greatly.
(3) the transition metal doping zinc oxide mesoporous material of this method preparation is measured the photocatalytic activity of its degraded xanthate under radiation of visible light, the result shows that all material all has visible light catalysis activity, and especially the copper doped zinc oxide sample demonstrates good visible light catalysis activity.
(4) preparation technology of this method and equipment are simple, and great industrial production prospects is arranged.
Description of drawings
Fig. 1 mixes up the XRD figure spectrum of zinc oxide for transition metal;
It among the figure (a) pure zinc oxide; (b) 5mol% manganese doping zinc-oxide; (c) 5mol% iron doping zinc-oxide; (d) 5mol% cobalt doping zinc-oxide; (e) 5mol% copper doped zinc oxide;
Fig. 2 is the nitrogen adsorption/desorption curve map (a) of 5mol%Cu doping zinc-oxide, and graph of pore diameter distribution (b);
Fig. 3 is the low power TEM figure (a) and the HRTEM figure (b) of 5mol%Cu doping zinc-oxide;
Fig. 4 mixes up the UV-vis absorption spectrum of zinc oxide for transition metal.
The specific embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
With 1.425 * 10
-2Mol zinc nitrate, 0.075 * 10
-2Mol manganese nitrate and 0.15mol urea are dissolved in to stir in the 150ml distilled water and obtain precursor solution; Precursor solution is placed autoclave, sealing, 120 ℃ of reaction 6h; Reaction finishes and is cooled to room temperature, and product deionized water cyclic washing is 100 ℃ of following vacuum drying; At 450 ℃ of roasting 2h, make 5mol% manganese doping zinc-oxide mesoporous material then with visible light catalysis activity.
Embodiment 2:
Change the zinc nitrate among the embodiment 1 into zinc acetate or zinc sulfate or zinc chloride, corresponding manganese acetate or manganese sulfate or the manganese chloride of changing into of manganese nitrate, remaining reaction process and condition are constant, and the gained result is identical with embodiment 1.
Embodiment 3:
With 1.425 * 10
-2Mol zinc nitrate, 0.075 * 10
-2Mol ferrous sulfate and 0.15mol urea are dissolved in to stir in the 150ml distilled water and obtain precursor solution; Precursor solution is placed autoclave, sealing, 120 ℃ of reaction 6h; Reaction finishes and is cooled to room temperature, and product deionized water cyclic washing is 100 ℃ of following vacuum drying; At 450 ℃ of roasting 2h, make 5mol% iron doping zinc-oxide mesoporous material then with visible light catalysis activity.
Embodiment 4:
Change the zinc nitrate among the embodiment 3 into zinc acetate or zinc sulfate or zinc chloride, ferrous sulfate changes frerrous chloride into, and remaining reaction process and condition are constant, and the gained result is identical with embodiment 3.
Embodiment 5:
With 1.425 * 10
-2Mol zinc nitrate, 0.075 * 10
-2Mol cobalt nitrate and 0.15mol urea are dissolved in to stir in the 150ml distilled water and obtain precursor solution; Precursor solution is placed autoclave, sealing, 120 ℃ of reaction 6h; Reaction finishes and is cooled to room temperature, and product deionized water cyclic washing is 100 ℃ of following vacuum drying; At 450 ℃ of roasting 2h, make 5mol% cobalt doping zinc-oxide mesoporous material then with visible light catalysis activity.
Embodiment 6:
Change the zinc nitrate among the embodiment 5 into zinc acetate or zinc sulfate or zinc chloride, corresponding cobalt acetate or cobaltous sulfate or the cobalt chloride of changing into of cobalt nitrate, remaining reaction process and condition are constant, and the gained result is identical with embodiment 5.
Embodiment 7:
With 1.425 * 10
-2Mol zinc nitrate, 0.075 * 10
-2Mol copper nitrate and 0.15mol urea are dissolved in to stir in the 150ml distilled water and obtain precursor solution; Precursor solution is placed autoclave, sealing, 120 ℃ of reaction 6h; Reaction finishes and is cooled to room temperature, and product deionized water cyclic washing is 100 ℃ of following vacuum drying; At 450 ℃ of roasting 2h, make 5mol% copper doped zinc oxide mesoporous material then with visible light catalysis activity.
Embodiment 8:
Change the zinc nitrate among the embodiment 1 into zinc acetate or zinc sulfate or zinc chloride, corresponding copper acetate or copper sulphate or the copper chloride of changing into of copper nitrate, remaining reaction process and condition are constant, and the gained result is identical with embodiment 7.
Embodiment 9:
Utilize 5mol% manganese to mix up zinc oxide visible light photocatalytic degradation xanthate:
The 5mol% manganese of 100mg embodiment 1 preparation is mixed up among the xanthate aqueous solution 100ml that zinc oxide is scattered in 10mg/L (the pH value is about 7), then scattered mixed liquor is placed under the 100W tungsten lamp, regularly getting mixed liquor places the centrifugal 10min of supercentrifuge (rotating speed is 10000r/min), gets the characteristic absorption peak (λ of supernatant in xanthate
Max=301nm) locate to measure solution absorbency, thus the photocatalytic degradation rate obtained.Its result is as shown in table 1, and under the light irradiation of visible light, through 90 minutes, xanthate degraded 10%.
Use the 5mol% manganese of embodiment 2 preparations to mix up zinc oxide, carry out the photocatalysis experiment of xanthate again by above-mentioned experiment condition respectively,, also can reach with the 5mol% manganese of embodiment 1 preparation and mix up the identical effect of zinc oxide through illumination 90 minutes.
Embodiment 10:
Utilize 5mol% iron to mix up zinc oxide visible light photocatalytic degradation xanthate:
The 5mol% iron of 100mg embodiment 3 preparation is mixed up among the xanthate aqueous solution 100ml that zinc oxide is scattered in 10mg/L (the pH value is about 7), then scattered mixed liquor is placed under the 100W tungsten lamp, regularly getting mixed liquor places the centrifugal 10min of supercentrifuge (rotating speed is 10000r/min), gets the characteristic absorption peak (λ of supernatant in xanthate
Max=301nm) locate to measure solution absorbency, thus the photocatalytic degradation rate obtained.Its result is as shown in table 1, and under the light irradiation of visible light, through 90 minutes, xanthate degraded 27%.
Use the 5mol% iron of embodiment 4 preparations to mix up zinc oxide, carry out the photocatalysis experiment of xanthate again by above-mentioned experiment condition respectively,, also can reach with the 5mol% iron of embodiment 4 preparations and mix up the identical effect of zinc oxide through illumination 90 minutes.
Embodiment 11:
Utilize the 5mol% cobalt to mix up zinc oxide visible light photocatalytic degradation xanthate:
The 5mol% cobalt of 100mg embodiment 5 preparation is mixed up among the xanthate aqueous solution 100ml that zinc oxide is scattered in 10mg/L (the pH value is about 7), then scattered mixed liquor is placed under the 100W tungsten lamp, regularly getting mixed liquor places the centrifugal 10min of supercentrifuge (rotating speed is 10000r/min), gets the characteristic absorption peak (λ of supernatant in xanthate
Max=301nm) locate to measure solution absorbency, thus the photocatalytic degradation rate obtained.Its result is as shown in table 1, and under the light irradiation of visible light, through 90 minutes, xanthate degraded 58%.
Use the 5mol% cobalt of embodiment 6 preparations to mix up zinc oxide, carry out the photocatalysis experiment of xanthate again by above-mentioned experiment condition respectively,, also can reach with the 5mol% cobalt of embodiment 6 preparations and mix up the identical effect of zinc oxide through illumination 90 minutes.
Embodiment 12:
Utilize 5mol% copper to mix up zinc oxide visible light photocatalytic degradation xanthate:
The 5mol% copper of 50mg embodiment 7 preparation is mixed up among the xanthate aqueous solution 100ml that zinc oxide is scattered in 40mg/L (the pH value is about 7), then scattered mixed liquor is placed under the 100W tungsten lamp, regularly getting mixed liquor places the centrifugal 10min of supercentrifuge (rotating speed is 10000r/min), gets the characteristic absorption peak (λ of supernatant in xanthate
Max=301nm) locate to measure solution absorbency, thus the photocatalytic degradation rate obtained; Simultaneously, adopt total organic carbon analyzer to measure the total organic carbon amount (TOC) of supernatant, thereby can obtain mineralization rate.Its result is as shown in table 1, and under the light irradiation of visible light, through 90 minutes, xanthate degraded 100%, and the TOC mineralization rate reaches 68%.
Use the 5mol% copper of embodiment 8 preparations to mix up zinc oxide, carry out the photocatalysis experiment of xanthate again by above-mentioned experiment condition respectively,, also can reach with the 5mol% copper of embodiment 8 preparations and mix up the identical effect of zinc oxide through illumination 90 minutes.
Table 1 transition metal mixes up the result of zinc oxide mesopore material light catalysis degraded xanthate
Claims (10)
1. have the transition metal doping zinc oxide mesoporous material of visible light catalysis activity, it is characterized in that, described transition metal doping zinc oxide mesoporous material component is: Zn
1-xRe
xO, wherein Re comprises Mn, Fe, Co or Cu; X=0.1mol-6mol%.
2. the transition metal doping zinc oxide mesoporous material with visible light catalysis activity according to claim 1 is characterized in that the mesopore orbit diameter of described mesoporous material is 2.5nm-15nm, and specific area is 32.6m
2/ g-50m
2/ g.
3. the transition metal doping zinc oxide mesoporous material with visible light catalysis activity according to claim 1 and 2 is characterized in that, described transition metal doping zinc oxide mesoporous material component is: Zn
1-xRe
xO, wherein Re comprises Mn, Fe, Co or Cu; X=5mol%.
4. the transition metal doping zinc oxide mesoporous material with visible light catalysis activity according to claim 1 and 2 is characterized in that, described transition metal doping zinc oxide mesoporous material component is: Zn
1-xCu
xO, wherein x=0.1mol-6mol%.
5. the transition metal doping zinc oxide mesoporous material with visible light catalysis activity according to claim 4 is characterized in that, described transition metal doping zinc oxide mesoporous material component is: Zn
1-xCu
xO, wherein x=5mol%.
6. have the preparation method of the transition metal doping zinc oxide mesoporous material of visible light catalysis activity, it is characterized in that, may further comprise the steps:
(1) with zinc salt, urea and be selected from manganese, iron, cobalt and the copper any slaine and be dissolved in to stir in the distilled water and obtain precursor solution;
(2) precursor solution is placed autoclave, sealing, 100-130 ℃ of reaction 1～24h;
(3) reaction finishes and is cooled to room temperature, product deionized water cyclic washing, vacuum drying 2-8h;
(4) then at 400～600 ℃ of roasting 2-4h.
7. the preparation method of transition metal doping zinc oxide mesoporous material according to claim 6 is characterized in that: the described zinc salt of step (1) comprises zinc acetate, zinc sulfate, zinc nitrate or zinc chloride; Described manganese salt comprises manganese acetate, manganese sulfate, manganese nitrate or manganese chloride; Described molysite comprises ferrous sulfate or frerrous chloride; Described cobalt salt comprises cobalt acetate, cobaltous sulfate, cobalt nitrate or cobalt chloride; Described mantoquita comprises copper acetate, copper sulphate, copper nitrate or copper chloride.
8. the preparation method of transition metal doping zinc oxide mesoporous material according to claim 6 is characterized in that: the described metal ion total concentration of step (1) is controlled to be 0.05mol/L-0.2mol/L;
9. the preparation method of transition metal doping zinc oxide mesoporous material according to claim 6 is characterized in that: the described urea of step (1) is controlled to be 5-15 with the ratio of the mole of metal ion;
10. the preparation method of transition metal doping zinc oxide mesoporous material according to claim 6 is characterized in that: the described vacuum drying temperature of step (3) is 80～100 ℃.
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| CN101947454B (en) | 2012-08-15 |
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