CN104275203A - Preparation method of halloysite nanotube loaded nitrogen doped nano-zinc oxide photocatalyst - Google Patents
Preparation method of halloysite nanotube loaded nitrogen doped nano-zinc oxide photocatalyst Download PDFInfo
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- CN104275203A CN104275203A CN201410590178.6A CN201410590178A CN104275203A CN 104275203 A CN104275203 A CN 104275203A CN 201410590178 A CN201410590178 A CN 201410590178A CN 104275203 A CN104275203 A CN 104275203A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a preparation method of a halloysite nanotube loaded nitrogen doped nano-zinc oxide photocatalyst, belonging to the technical field of sewage photocatalytic treatment. The preparation method comprises the following steps: mixed solution of urea and zinc salt is adsorbed on a dried powdery halloysite nanotube in a saturation adsorption manner, the reaction is carried out at 60-120 DEG C, roasting is carried out in a muffle furnace, then cooling is performed to obtain the HNTs (halloysite nanotubes) loaded nitrogen doped nano-zinc oxide photocatalyst. The synthetic route is short, the condition is mild, the operation is simple, the mole content of nitrogen in nitrogen doped nano-zinc oxide is about 0.5-1.2%, and the prepared nitrogen doped nano-zinc oxide has good photocatalytic performance to methyl orange under simulated sunlight, and has the degradation rate up to 60-95%.
Description
Technical field
The invention belongs to the photocatalysis treatment technical field of sewage, be specifically related to the production technical field of photochemical catalyst wherein.
Background technology
Along with progress and the development of science and technology, the energy and problem of environmental pollution cause the extensive concern of people gradually, particularly in industrial organic waste water process.Because semi-conducting material is carbon dioxide and water as the organic matter afterproduct in photochemical catalytic oxidation waste water, secondary pollution is not produced to environment, so the catalyst that preparation has visible light photocatalysis efficiency has very important using value to process organic wastewater.
Zinc oxide (ZnO) is a kind of semi-conducting material with photocatalysis characteristic, and especially the photocatalysis performance of nano zine oxide enjoys the concern of researcher.Simple ZnO only possesses Photocatalytic activity under ultraviolet light conditions, and at visible ray without response.Doping or modification are the important method of the visible light catalysis activity improving zinc oxide, are wherein representative with nitrating.Nitrating nanometer zinc oxide is the catalyst that in photochemical catalyst, visible light catalytic efficiency is higher, not only has ultraviolet catalytic activity, and has good visible light photocatalysis active, and cost is low simultaneously, preparation is simple and be easy to large-scale production.But Zinc oxide powder particle is easily reunited in suspension system, not easily separated, be difficult to reclaim, translucidus can be poor, and the harm of nano particle to environment in suspension causes secondary pollution more greatly, easily.In addition, the recombination probability of the electron-hole pair that powder granule photochemical catalyst light produces after irradiating is very high, and photon utilization ratio is low, photocatalytic activity is lower.
Load is the best approach solved the problem.The preparation method of current support type nitrating nano zinc oxide material mainly contains chemical vapour deposition technique, sol-gel process, template, coprecipitation, solvent-thermal method etc.These method ubiquity cost of material are higher, utilization rate is low, easy reunion, not easily separated, shaping poor, the shortcoming such as complex process equipment, production cost are higher.In addition, in the carrier of load zinc oxide, the support type zinc oxide photocatalysis effect being carrier with CNT or carbon nano-fiber is best, nanotube is generally carbon nano-fiber or CNT, because these material prices are expensive, poor heat stability and cannot scale mass production, so be difficult to realize commercial application.
Summary of the invention
Object of the present invention aims to provide the preparation method of low, the effective HNTs load nitrating nanometer photocatalyst of zinc oxide of a kind of production cost.
The mixed solution of urea and zinc salt is adsorbed on the powdery halloysite nanotubes of oven dry with saturated extent of adsorption by the present invention, after reaction under 60 ~ 120 DEG C of temperature conditions, be placed in Muffle furnace roasting, after cooling, namely obtain HNTs load nitrating nanometer photocatalyst of zinc oxide.
The present invention adopts the hollow tubular structure of halloysite nanotubes (HNTs) to be template, with zinc salt, nitrogen-containing compound for raw material, saturated extent of adsorption is utilized to fill the method for load oxide, by filling method in halloysite nanotubes tube chamber, synthesize nitrating nanometer photocatalyst of zinc oxide, the method synthetic route is short, mild condition, simple to operate, the molar content of nitrogen about 0.5 ~ 1.2% in nitrating zinc oxide, obtained nitrating nanometer zinc oxide is under simulated solar irradiation, have good photocatalysis performance to methyl orange, degradation rate can reach 60 ~ 95%.
The invention has the advantages that: the carrier that (1) the present invention adopts is galapectite nano-silicon aluminum pipe, CNT of comparing is not only with low cost, and good stability, can large-scale production.(2) the filling legal system of dropping of the present invention is for nitrating nanometer zinc oxide, and its preparation method not only simply, raw material availability is high, easy to operate, preparation cost is low, and do not produce waste water.
In addition, the present invention's circulation carries out following steps 2 ~ 4 times: to be adsorbed on powdery halloysite nanotubes with the mixed solution of labile nitrogen-containing compound and zinc salt and to react under 60 ~ 120 DEG C of temperature conditions.The object of circulation has just right photocatalytic activity nanometer nitrating zinc oxide active component ratio in order to better in the filling of halloysite nanotubes inside.
The length of described halloysite nanotubes is 200 ~ 500 nm, and aperture is 20 ~ 30 nm, and specific area is 30 ~ 50 m
2/ g, main composition is silica and aluminium oxide.Halloysite nanotubes has natural nano pore, larger inner surface, be applicable to filling nano particle, and the high temperature problem that the conventional nano particles such as the gathering of nano particle, sintering can be stoped to exist, simultaneously, provide the reaction compartment of nanometer, be conducive to nano particle and play nano-catalytic effect.
The temperature of roasting is 300 ~ 600 DEG C, and roasting time is 2 ~ 3 h.This sintering temperature and roasting time can effectively decompose zinc salt and nitrogen-containing compound, become nitrogenous photocatalyst of zinc oxide active component.
In the mixed solution of described urea and zinc salt, the nitrogen of nitrogen-containing compound and the zinc mol ratio of zinc salt are 1 ~ 4:1.This mol ratio can make the nitrogen content in nitrating zinc oxide significantly improve, and improves visible light photocatalysis active.
The first step of each circulation for adsorb the mixed solution of urea and zinc salt the insulating box of powdery halloysite nanotubes prior to 30 ~ 80 DEG C in dry isothermal holding.Because halloysite nanotubes has very strong moisture absorption, the water in the easy absorbed air of nano pore, is unfavorable for the absorption of mixed solution like this, and therefore, halloysite nanotubes must put into baking oven before using dries, and takes out fast and adds mixed solution.
Described zinc salt is zinc sulfate, zinc nitrate, zinc acetate or zinc chloride, and advantage has thermal decomposition ability, is conducive to being decomposed into metal oxide in sintering temperature and roasting time.
Described easy decomposition itrogenous organic substance is urea, ammonium carbonate, carbonic hydroammonium, ammonium nitrate or n-butylamine, and advantage can decompose to discharge ammonia under 60 ~ 120 DEG C of degrees of reaction.
Accompanying drawing explanation
Fig. 1 is methyl orange and the ultraviolet-visible spectrogram adopting the HNTs load nitrating nanometer photocatalyst of zinc oxide of above-mentioned preparation degraded methyl orange, direct employing halloysite nanotubes (HNTs) degrades methyl orange.
Detailed description of the invention
The natural halloysite nanotubes length selected in following example is about 200 ~ 500 nm, and aperture is about 20 ~ 30 nm, and specific area is about 30 ~ 50 m
2/ g.
Example 1:
Powdery halloysite nanotubes is put into 30 DEG C of insulating boxs dry and be incubated for subsequent use.
Preparation molar concentration is the zinc sulfate solution of 0.3mol/L, and add urea under stirring and be dissolved to clarification, the zinc mol ratio of the nitrogen in urea and zinc sulfate is 1:1.
Above-mentioned solution is slowly added drop-wise in the halloysite nanotubes powder through drying, until close to the saturated extent of adsorption of galapectite, powder presents moistening semi-wet state, reacts 30min under then putting into 60 DEG C of temperature.
Finally the halloysite nanotubes of load zinc salt is put into Muffle furnace, roasting 2 h under sintering temperature is 300 DEG C of conditions.Namely halloysite nanotubes (HNTs) load nitrating nanometer photocatalyst of zinc oxide (N-doped ZnO/HNTs) is obtained after cooling.
Application:
Take the above-mentioned photochemical catalyst powder of 10 mg, put into and the reagent bottle that 30 mL concentration are the methyl orange solution of 20 mg/L is housed, under xenon lamp power is 200W condition, simulated solar irradiation light source irradiation, irradiation time is 150min, and degradation rate reaches 60%.
Example 2:
Powdery halloysite nanotubes is put into 50 DEG C of insulating boxs dry and be incubated for subsequent use.
Preparation molar concentration is the zinc acetate aqueous solution of 0.8mol/L, adds ammonium carbonate and be dissolved to clarification under stirring, and the mol ratio of the zinc in ammonium carbonate in nitrogen and zinc acetate is 2:1.
The mixed solution of above-mentioned urea and zinc salt is slowly added drop-wise in the halloysite nanotubes powder through drying, until close to the saturated extent of adsorption of galapectite, powder presents moistening semi-wet state, reacts 60min under then putting into 80 DEG C of temperature.Repeat the above-mentioned mixed solution by urea and zinc salt to be added drop-wise to halloysite nanotubes powder, at 80 DEG C of temperature, to react the process 3 times of 60min.
Finally the halloysite nanotubes of load zinc salt is put into Muffle furnace, roasting 3 h under sintering temperature is 350 DEG C of conditions.Namely HNTs load nitrating nanometer photocatalyst of zinc oxide (N-doped ZnO/HNTs) is obtained after cooling.
Application:
Take the above-mentioned photochemical catalyst powder of 5 mg, put into and the reagent bottle that 30 mL concentration are the methyl orange solution of 60 mg/L is housed, under xenon lamp power is 150W condition, simulated solar irradiation light source irradiation declines and separates methyl orange aqueous solution, irradiation time is 120min, and degradation rate reaches 95%.
Record is carried out with ultraviolet-visible spectrogram, as the uv-vis spectra that curve a, the curve b of Fig. 1, curve c respectively illustrate methyl orange and adopt the HNTs load nitrating nanometer photocatalyst of zinc oxide (N-doped ZnO/HNTs) of above-mentioned preparation, directly adopt halloysite nanotubes (HNTs) to process in processing procedure.
As can be seen from Fig. 1: HNTs load nitrating nanometer photocatalyst of zinc oxide (N-doped ZnO/HNTs) prepared by the inventive method reaches 95% to the degradation rate of methyl orange, and be obviously better than the effect that directly adopts halloysite nanotubes (HNTs) to process.
Example 3
Powdery halloysite nanotubes is put into 60 DEG C of insulating boxs dry and be incubated for subsequent use.
Preparation molar concentration is the zinc nitrate aqueous solution of 1mol/L, and add n-butylamine or ammonium nitrate under stirring and be dissolved to clarification, wherein, the mol ratio of the nitrogen in n-butylamine and the zinc in zinc nitrate is 3:1.
Above-mentioned solution is slowly added drop-wise in the halloysite nanotubes powder through drying, until close to the saturated extent of adsorption of galapectite, powder presents moistening semi-wet state, reacts 90min under then putting into 120 DEG C of temperature.Repeat said process 3 times.
Finally the halloysite nanotubes of load zinc salt is put into Muffle furnace, roasting 2.5 h under sintering temperature is 450 DEG C of conditions.Namely HNTs load nitrating nanometer photocatalyst of zinc oxide (N-doped ZnO/HNTs) is obtained after cooling.
Application:
Take the above-mentioned photochemical catalyst powder of 10 mg, put into and the reagent bottle that 30 mL concentration are the methyl orange solution of 80 mg/L is housed, under xenon lamp power is 250W condition, simulated solar irradiation light source irradiation declines and separates methyl orange aqueous solution, irradiation time is 90min, and degradation rate reaches 85%.
Example 4
Powdery halloysite nanotubes is put into 80 DEG C of insulating boxs dry and be incubated for subsequent use.
Preparation molar concentration is the solder(ing)acid of 2mol/L, and add carbonic hydroammonium under stirring and be dissolved to clarification, the mol ratio of the nitrogen in carbonic hydroammonium and the zinc in zinc chloride is 4:1.
Above-mentioned solution is slowly added drop-wise in the halloysite nanotubes powder through drying, until close to the saturated extent of adsorption of galapectite, powder presents moistening semi-wet state, reacts 80min under then putting into 90 DEG C of temperature.Repeat said process 4 times.
Finally the halloysite nanotubes of load zinc salt is put into Muffle furnace, roasting 3 h under sintering temperature is 500 DEG C of conditions.Namely HNTs load nitrating nanometer photocatalyst of zinc oxide (N-doped ZnO/HNTs) is obtained after cooling.
Application:
Take the above-mentioned photochemical catalyst powder of 20 mg, put into and the reagent bottle that 30 mL concentration are the methyl orange solution of 50 mg/L is housed, under xenon lamp power is 300W condition, simulated solar irradiation light source irradiation declines and separates methyl orange aqueous solution, irradiation time is 120min, and degradation rate reaches 92%.
Claims (8)
1. halloysite nanotubes load nitrating is mixed the preparation method of nano zinc oxide photocatalyst, the mixed solution of labile nitrogen-containing compound and zinc salt is it is characterized in that to be adsorbed on the powdery halloysite nanotubes of oven dry with saturated extent of adsorption, after reaction under 60 ~ 120 DEG C of temperature conditions, be placed in Muffle furnace roasting, after cooling, namely obtain galapectite load nitrating nanometer photocatalyst of zinc oxide.
2. preparation method according to claim 1, is characterized in that circulating and carries out being adsorbed on powdery halloysite nanotubes with the mixed solution of labile nitrogen-containing compound and zinc salt and reacting 2 ~ 4 times under 60 ~ 120 DEG C of temperature conditions.
3. preparation method according to claim 1 or 2, it is characterized in that the length of described halloysite nanotubes is 200 ~ 500 nm, aperture is 20 ~ 30 nm, and specific area is 30 ~ 50 m
2/ g, mainly consists of silica and aluminium oxide.
4. preparation method according to claim 1 or 2, it is characterized in that the temperature of roasting is 300 ~ 600 DEG C, roasting time is 2 ~ 3 h.
5. preparation method according to claim 1 or 2, is characterized in that in the mixed solution of described labile nitrogen-containing compound and zinc salt, and the nitrogen of nitrogen-containing compound and the zinc mol ratio of zinc salt are 1 ~ 4:1.
6. preparation method according to claim 1 or 2, it is characterized in that first time for adsorb the mixed solution of urea and zinc salt the insulating box of powdery halloysite nanotubes prior to 30 ~ 80 DEG C in dry isothermal holding.
7. preparation method according to claim 1, is characterized in that described zinc salt is zinc sulfate, zinc nitrate, zinc acetate or zinc chloride.
8. preparation method according to claim 1, is characterized in that described easy decomposition itrogenous organic substance is urea, ammonium carbonate, carbonic hydroammonium, ammonium nitrate or n-butylamine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816267A (en) * | 2018-06-26 | 2018-11-16 | 西北师范大学 | A kind of loess load nitrogen-doped zinc oxide photochemical catalyst and preparation method thereof |
| CN109603825A (en) * | 2019-02-02 | 2019-04-12 | 西北师范大学 | A kind of halloysite nanotubes load plasma resonance photochemical catalyst and preparation method thereof |
| CN114713214A (en) * | 2022-04-29 | 2022-07-08 | 合肥职业技术学院 | Halloysite nanotube-based composite photocatalyst and preparation method and application thereof |
| CN114956157A (en) * | 2021-02-23 | 2022-08-30 | 中科院广州化学有限公司 | Porous hollow zinc oxide with electromagnetic shielding effect and preparation method and application thereof |
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| CN103301827A (en) * | 2013-06-26 | 2013-09-18 | 常州大学 | Halloysite-based photocatalytic composite material and preparation method of halloysite-based photocatalytic composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101711971A (en) * | 2009-10-23 | 2010-05-26 | 北京化工大学 | Zinc-containing multielement metallic oxide/carbon nanotube complex as well as preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816267A (en) * | 2018-06-26 | 2018-11-16 | 西北师范大学 | A kind of loess load nitrogen-doped zinc oxide photochemical catalyst and preparation method thereof |
| CN109603825A (en) * | 2019-02-02 | 2019-04-12 | 西北师范大学 | A kind of halloysite nanotubes load plasma resonance photochemical catalyst and preparation method thereof |
| CN114956157A (en) * | 2021-02-23 | 2022-08-30 | 中科院广州化学有限公司 | Porous hollow zinc oxide with electromagnetic shielding effect and preparation method and application thereof |
| CN114713214A (en) * | 2022-04-29 | 2022-07-08 | 合肥职业技术学院 | Halloysite nanotube-based composite photocatalyst and preparation method and application thereof |
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