CN107626315A - A kind of preparation method of the ZnO photocatalyst of Fe doping - Google Patents
A kind of preparation method of the ZnO photocatalyst of Fe doping Download PDFInfo
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- CN107626315A CN107626315A CN201710994607.XA CN201710994607A CN107626315A CN 107626315 A CN107626315 A CN 107626315A CN 201710994607 A CN201710994607 A CN 201710994607A CN 107626315 A CN107626315 A CN 107626315A
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Abstract
The present invention relates to a kind of preparation method of the ZnO photocatalyst of Fe doping, comprise the following steps：1) nano-zinc oxide powder is added in the soluble iron salt solutions prepared；2) inorganic alkali solution is added dropwise into mixture obtained by step 1) while stirring after, system is placed in crystallization in water bath chader after being added dropwise；3) product is centrifuged, is placed in baking oven and dries after washing, obtain catalyst precarsor；4) by catalyst precarsor be calcined Fe doping ZnO photocatalyst.The present invention utilizes the properties of crystal lattice and structural property of hydrotalcite, crystallization has synthesized the houghite precursor that structure is ZnFe/LDHs on the surface of nano zine oxide, ZnO photocatalyst its photo-quantum efficiency after fired obtained doping is improved, absorbable 400 760nm visible light source is lifted as energy, photocatalytic activity.
Description
Technical field
The present invention relates to a kind of preparation method of ZnO photocatalyst, more particularly to a kind of ZnO photocatalysis of Fe and Co doping
The preparation method of agent, belong to photocatalysis technology field.
Background technology
The high speed development of social economy brings the substantial increase of the problem of serious environmental degradation, particularly industrial wastewater
Make water pollution problem extremely serious.At present, national governments have been fully recognized that the seriousness of water pollution problems, therefore to this
The research and technology exploitation in field receives much concern.Representative of the solar energy source as green energy resource, there is popularity, adequate, length
The characteristics of other conventional energy resources such as long property, spatter property and security are difficult to possess.Convert solar energy into and can be used for being catalyzed
Chemical energy turned into people's study hotspot of interest since nearly half a century.Fujishima seminar reported first in 1979
Road using the photocatalytic process of inorganic semiconductor material result of study, recently as going deep into for research, it has been found that light
Catalysis and its correlation technique are before all many-sides such as environmental pollution treatment technology, solar energy conversion all show tempting application
Scape, and photocatalysis oxidation technique is a kind of brand-new " green technology ", so that its energy consumption is low, simple to operate, reaction condition is gentle, oxygen
The features such as property changed is strong, cost is low, non-secondary pollution, the most attention of people is increasingly subject in terms of environmental improvement, and as each
State's industrial circle and the focus of academia's research.
ZnO is broad stopband direct band-gap semicondictor material, and band gap is about 3.37eV at room temperature, and ZnO has nonhazardous, environment
Close friend, bio-compatible, it is easily prepared the advantages that.Under the irradiation of light, ZnO excite after caused by electron-hole pair have oxidation,
The ability of reduction, there is very strong destruction to organic molecule structure, long-chain molecule is become short chain molecule, (some are organic
Thing even can finally be broken down into carbon dioxide and water).
With conventional TiO2Photochemical catalyst is similar, ZnO band gap 3.37eV cause it to absorb ultraviolet band (wavelength is short
In 370nm) light, and the light of ultraviolet band only accounts for 4% of gross energy or so in sunshine, it is seen that optical band (400~760nm)
Light account for the 45~50% of gross energy.How sunshine is effectively utilized, it is currently to grind to realize the degraded to organic pollution
The focus studied carefully.
Research is found, passes through Fe3+、Cu2+、Ni2+And Mn2+Doping vario-property Deng transition metal ions to ZnO photocatalyst,
ZnO band-gap energy can be changed, produce impurity energy level and lattice defect, improve photo-quantum efficiency and redox ability, so as to
Improve photocatalytic activity.In addition, transition metal ions and Zn in ZnO crystal2+Atomic radius be more or less the same, be easy to doping enter
In ZnO lattices, therefore it is the conventional means for improving ZnO photocatalysis performances to be modified using doped transition metal ionses.
But the distribution for product its doped chemical that the doping method for being disclosed the ZnO of report at present is produced is simultaneously uneven
It is even, in ZnO lattices with oxygen atom be bonded and it is insecure, therefore adulterate to ZnO band-gap energy, produce impurity energy level and lattice
The influence of defect is very limited, thus the photo-quantum efficiency of catalyst and redox ability are limited, the raising of photocatalytic activity
Limited extent.
The content of the invention
Present invention deficiency existing for existing ZnO doping method, there is provided a kind of ZnO photocatalyst of Fe and Co doping
Preparation method.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method of the ZnO photocatalyst of Fe doping, comprises the following steps：
1) nano-zinc oxide powder that particle diameter is 10~50nm is added to the 0.1~0.5mol/L prepared solubility
Iron salt solutions in, it is (2~5) to control the nano-zinc oxide powder and the mass ratio of molysite：1, stir under ultrasound condition
It is well mixed；
2) inorganic alkali solution that concentration is 1~5wt%, control volume is added dropwise after into mixture obtained by step 1) while stirring
It is that pH is 9~10, system is placed in 12~24h of crystallization in 50~60 DEG C of water bath chader after being added dropwise, that is, received
The surface in situ of rice zinc oxide grows hydrotalcite-like compound；
3) by step 2) products therefrom centrifuge, be washed to pH=7~8, after be placed in baking oven dry, before obtaining catalyst
Body；
4) catalyst precarsor obtained by step 3) is placed under 500~650 DEG C of environment and be calcined 6~8 hours, obtain Fe doping
ZnO photocatalyst.
Further, molysite described in step 1) is answering for any one or more in iron chloride, ferric nitrate, ferric sulfate
Match somebody with somebody.
Further, the aqueous slkali described in step 2) is appointing in ammonia spirit, sodium hydroxide solution, potassium hydroxide solution
Meaning is a kind of.
Further, the temperature dried in step 3) is 80~120 DEG C.
The Principle of Process of the inventive method is described below：
Because the particle diameter of nano zine oxide is sufficiently small, therefore surface has many exposed Zn atoms, the Fe of doping3+Pass through
Acted on the lattice of Zn atoms, bond together to form LDHs positively charged laminate in order each other, adsorbed between laminate negatively charged
Anion forms houghite precursor, the ZnO photocatalyst after obtained houghite precursor is calcined after the doping of gained
Because its doped chemical is evenly distributed, ZnO band-gap energy, generation impurity energy level and lattice defect are changed due to doping
It is kind, and then its photo-quantum efficiency and redox ability are largely increased, photocatalytic activity is lifted.
The beneficial effects of the invention are as follows：
1) present invention utilizes the properties of crystal lattice and structural property of hydrotalcite, and crystallization synthesizes on the surface of nano zine oxide
Structure is ZnFe/LDHs houghite precursor, and ZnO photocatalyst its photo-quantum efficiency after fired obtained doping obtains
Improve, can absorb 400-760nm visible light source as energy, can effectively utilize sunshine, photocatalytic activity is able to
Lifting, and its redox ability is largely increased.
2) method of the invention is simple and easy, and easy to operate, raw material is cheap and easy to get, it is easy to accomplish large-scale application.
Embodiment
The principle and feature of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
Embodiment 1：
A kind of preparation method of the ZnO photocatalyst of Fe doping, comprises the following steps：
1) nano-zinc oxide powder that 100g particle diameters are 10~30nm is added to the 0.25mol/L's that 1000ml prepares
FeCl3In solution, it is 2.5 to control the nano-zinc oxide powder and the mass ratio of iron chloride：1, stir under ultrasound condition mixed
Close uniform；
2) ammonia spirit that 1000ml concentration is 2wt% is added dropwise after into mixture obtained by step 1) while stirring, makes gold
Belong to ion precipitation, control system pH is 9~10, and system is placed in into crystallization in 50 DEG C of water bath chader after being added dropwise
24h, i.e., grow hydrotalcite-like compound in the surface in situ of nano zine oxide；
3) by step 2) products therefrom centrifuge, be washed to pH=7~8, after be placed in 80 DEG C of baking oven dry 24h,
Obtain catalyst precarsor；
4) catalyst precarsor obtained by step 3) is placed under 500 DEG C of environment and be calcined 8 hours, the ZnO light for obtaining Fe doping is urged
Agent A1.
Embodiment 2：
A kind of preparation method of the ZnO photocatalyst of Fe doping, comprises the following steps：
1) nano-zinc oxide powder that 200g particle diameters are 10~30nm is added to the 0.1mol/L's that 1000ml prepares
Fe(NO3)3In solution, it is 5 to control the nano-zinc oxide powder and the mass ratio of ferric nitrate：1, stir under ultrasound condition mixed
Close uniform；
2) sodium hydroxide solution that 2000ml concentration is 1wt% is added dropwise after into mixture obtained by step 1) while stirring,
Make precipitation by metallic ion, control system pH is 9~10, and it is anti-that system is placed in into crystallization in 60 DEG C of water bath chader after being added dropwise
24h is answered, i.e., grows hydrotalcite-like compound in the surface in situ of nano zine oxide；
3) by step 2) products therefrom centrifuge, be washed to pH=7~8, after be placed in 100 DEG C of baking oven dry 24h,
Obtain catalyst precarsor；
4) catalyst precarsor obtained by step 3) is placed under 550 DEG C of environment and be calcined 8 hours, the ZnO light for obtaining Fe doping is urged
Agent A2.
Embodiment 3：
A kind of preparation method of the ZnO photocatalyst of Fe doping, comprises the following steps：
1) nano-zinc oxide powder that 240g particle diameters are 30~50nm is added to the 0.5mol/L's that 1000ml prepares
FeCl3In solution, it is 3 to control the nano-zinc oxide powder and the mass ratio of ferric nitrate：1, it is stirred under ultrasound condition
Uniformly；
2) potassium hydroxide solution that 2000ml concentration is 5wt% is added dropwise after into mixture obtained by step 1) while stirring,
Make precipitation by metallic ion, control system pH is 9~10, and it is anti-that system is placed in into crystallization in 60 DEG C of water bath chader after being added dropwise
12h is answered, i.e., grows hydrotalcite-like compound in the surface in situ of nano zine oxide；
3) by step 2) products therefrom centrifuge, be washed to pH=7~8, after be placed in 100 DEG C of baking oven dry 24h,
Obtain catalyst precarsor；
4) catalyst precarsor obtained by step 3) is placed under 600 DEG C of environment and be calcined 6 hours, the ZnO light for obtaining Fe doping is urged
Agent A3.
Embodiment 4：
A kind of preparation method of the ZnO photocatalyst of Fe doping, comprises the following steps：
1) nano-zinc oxide powder that 320g particle diameters are 30~50nm is added to the 0.4mol/L's that 1000ml prepares
Fe2(SO4)3In solution, it is 2 to control the nano-zinc oxide powder and the mass ratio of ferric nitrate：1, stir under ultrasound condition mixed
Close uniform；
2) ammonia spirit that 1000ml concentration is 3wt% is added dropwise after into mixture obtained by step 1) while stirring, makes gold
Belong to ion precipitation, control system pH is 9~10, and system is placed in into crystallization in 60 DEG C of water bath chader after being added dropwise
12h, i.e., grow hydrotalcite-like compound in the surface in situ of nano zine oxide；
3) by step 2) products therefrom centrifuge, be washed to pH=7~8, after be placed in 120 DEG C of baking oven dry 24h,
Obtain catalyst precarsor；
4) catalyst precarsor obtained by step 3) is placed under 650 DEG C of environment and be calcined 6 hours, obtain the ZnO of Fe and Co doping
Photochemical catalyst A4.
Embodiment 5：
A kind of preparation method of the ZnO photocatalyst of Fe doping, comprises the following steps：
1) nano-zinc oxide powder that 100g particle diameters are 30~50nm is added to the 0.15mol/L's that 1000ml prepares
FeCl3In solution, it is uniformly mixed under ultrasound condition；
2) ammonia spirit that 1000ml concentration is 1wt% is added dropwise after into mixture obtained by step 1) while stirring, makes gold
Belong to ion precipitation, control system pH is 9~10, and system is placed in into crystallization in 60 DEG C of water bath chader after being added dropwise
12h, i.e., grow hydrotalcite-like compound in the surface in situ of nano zine oxide；
3) by step 2) products therefrom centrifuge, be washed to pH=7~8, after be placed in 120 DEG C of baking oven dry 24h,
Obtain catalyst precarsor；
4) catalyst precarsor obtained by step 3) is placed under 650 DEG C of environment and be calcined 6 hours, obtain the ZnO of Fe and Co doping
Photochemical catalyst A5.
In order to verify the technique effect of the catalyst obtained by the inventive method, our catalyst obtained by by embodiment 1-5
The methylene blue and rhodamine B, specific experiment process that A1-A5 is used in degrading waste water are as follows：
1st, catalyst A1-A5 obtained by embodiment 1-5 is weighed and oxide powder and zinc that unmodified particle diameter is 10~30nm
Each 50mg in end is placed in 50ml test tube, then adds the methylene blue solution (10mg/L) prepared, lucifuge ultrasound 30min, then
It is positioned under 500w tribute lamp, is sampled per 15min, with UV725 types visible spectrophotometer in the maximum absorption wave of methylene blue
Its absorbance is surveyed at long 664nm.
The photodegradation rate D of methylene blue solution calculates according to equation below：
D=C0-Ct/C0, C0：Initial absorbance；Ct：Absorbance when the time is t, experimental results are as shown in table 1.
The degradation rate of the catalyst A1-A5 of table 1 and Zinc oxide powder in different time to methylene blue
From the data in table 1, the catalyst A1-A5 obtained by the inventive method can be by methylene in 45min
The degraded of base indigo plant 100% finishes, and in 15min, the degradation rate of methylene blue has reached more than 85%, with simple zinc oxide
Nanometer powder is compared, and the ZnO photocatalyst after the method doping of the present invention, its degradation rate and degradation capability have reached significantly
Improve.
2nd, catalyst A1-A5 obtained by embodiment 1-5 is weighed and oxide powder and zinc that unmodified particle diameter is 10~30nm
Each 50mg in end, it is put into the rhodamine B aqueous solution that 150ml concentration is 8mg/L, is positioned under xenon lamp, makes 400nm using color filter
To the visible light exposure of 800nm wavelength, sample within every 30 minutes, with Hitach U-3900 type ultraviolet-uisible spectrophotometer sieve Yu
Its absorbance is measured at red bright B maximum absorption wavelengths 554nm.
The degradation rate D of rhodamine B solution calculates according to equation below：
D=C0-Ct/C0, C0：Initial absorbance；Ct：Absorbance when the time is t, experimental results are as shown in table 2：
The degradation rate of the catalyst A1-A5 of table 2 and Zinc oxide powder in different time to rhodamine B
From the data in table 2, the catalyst A1-A5 of present invention gained can degrade rhodamine B in 120min
Finish, and Zinc oxide powder is only capable of the rhodamine B of degraded 65% in 120min, catalyst A1-A5 can be with 90min
More than 80% rhodamine B is decomposed, thus it was found from above-mentioned data comparison, compared with simple Zinc oxide powder, through this hair
ZnO photocatalyst after bright method doping, its degradation rate and degradation capability, which have reached, to be greatly improved.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (5)
1. a kind of preparation method of the ZnO photocatalyst of Fe doping, it is characterised in that comprise the following steps：
1) nano-zinc oxide powder that particle diameter is 10~50nm is added to the 0.1~0.5mol/L prepared soluble iron
In salting liquid, it is (2~5) to control the nano-zinc oxide powder and the mass ratio of molysite：1, it is stirred under ultrasound condition
Uniformly；
2) inorganic alkali solution that concentration is 1~5wt%, control system pH is added dropwise after into mixture obtained by step 1) while stirring
For 9~10, system is placed in 12~24h of crystallization in 50~60 DEG C of water bath chader after being added dropwise, i.e., in nano oxygen
The surface in situ for changing zinc grows hydrotalcite-like compound；
3) by step 2) products therefrom centrifuge, be washed to pH=7~8, after be placed in baking oven dry, obtain catalyst precarsor；
4) catalyst precarsor obtained by step 3) is placed under 500~650 DEG C of environment and be calcined 6~8 hours, obtain the ZnO of Fe doping
Photochemical catalyst.
2. preparation method according to claim 1, it is characterised in that molysite described in step 1) be iron chloride, ferric nitrate,
The compounding of any one or more in ferric sulfate.
3. preparation method according to claim 1, it is characterised in that aqueous slkali described in step 2) is ammonia spirit,
Any one in sodium hydroxide solution, potassium hydroxide solution.
4. preparation method according to claim 1, it is characterised in that the temperature dried in step 3) is 80~120 DEG C.
5. the ZnO photocatalyst for the Fe doping that the preparation method described in claim any one of 1-5 is prepared is in the drop of waste water
Solve the application of process field.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554412A (en) * | 2018-05-11 | 2018-09-21 | 江西理工大学 | A kind of preparation method and applications of large scale high porosity Fe doping photocatalyzing magnetic porous microsphere |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103611543A (en) * | 2013-11-28 | 2014-03-05 | 沈阳化工大学 | Method for preparing ZnFeCr hydrotalcite photocatalyst |
| CN105195155A (en) * | 2015-09-30 | 2015-12-30 | 河北工程大学 | Preparation method of sheet-shaped alpha-Fe2O3/ZnO composite photocatalyst |
| CN105727963A (en) * | 2016-04-18 | 2016-07-06 | 盐城工学院 | Fe and Cu co-doped nano-sized ZnO photocatalyst and preparation method thereof |
-
2017
- 2017-10-23 CN CN201710994607.XA patent/CN107626315A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103611543A (en) * | 2013-11-28 | 2014-03-05 | 沈阳化工大学 | Method for preparing ZnFeCr hydrotalcite photocatalyst |
| CN105195155A (en) * | 2015-09-30 | 2015-12-30 | 河北工程大学 | Preparation method of sheet-shaped alpha-Fe2O3/ZnO composite photocatalyst |
| CN105727963A (en) * | 2016-04-18 | 2016-07-06 | 盐城工学院 | Fe and Cu co-doped nano-sized ZnO photocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴诗德等: "铁掺杂氧化锌的制备及其对甲基橙的光催化降解", 《人工晶体学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554412A (en) * | 2018-05-11 | 2018-09-21 | 江西理工大学 | A kind of preparation method and applications of large scale high porosity Fe doping photocatalyzing magnetic porous microsphere |
| CN108554412B (en) * | 2018-05-11 | 2020-10-30 | 江西理工大学 | Preparation method and application of large-size high-porosity Fe-doped photocatalytic magnetic porous microspheres |
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Application publication date: 20180126 |