CN101850251B - Preparation method of magnetic separation titanium dioxide visible light catalyst - Google Patents

Preparation method of magnetic separation titanium dioxide visible light catalyst Download PDF

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CN101850251B
CN101850251B CN2010102030499A CN201010203049A CN101850251B CN 101850251 B CN101850251 B CN 101850251B CN 2010102030499 A CN2010102030499 A CN 2010102030499A CN 201010203049 A CN201010203049 A CN 201010203049A CN 101850251 B CN101850251 B CN 101850251B
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visible light
preparation
light catalyst
magnetic separation
catalyst
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CN101850251A (en
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张秀玲
孙东峰
袁学德
王静
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Dalian University
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Dalian University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention relates to a preparation method of magnetic separation titanium dioxide visible light catalyst, aiming at overcoming the defects of the prior art for preparing the magnetic separation titanium dioxide photochemical catalyst. The invention provides a method for preparing the magnetic separation visible light catalyst by one-step synthesis, thus greatly shortening the preparation period. The method mainly takes titanium tetrachloride, trivalent iron salt and bivalent cobalt salt as main raw materials, and comprises the steps of: adjusting the pH value by ammonia water at a certain temperature, carrying out mechanical stirring and ultrasonic dispersion together on the obtained solid product, washing by water, washing by alcohol, drying, calcining and obtaining the composite visible light catalyst taking TiO2 and CoFe2O4 as main components. The catalyst can be effectively separated from the treated liquid under the applied magnetic field, is convenient for recovery and recycling, has higher visible light catalytic activity, and has the advantages of easily obtained raw materials, low cost, simple preparation technique, short preparation period, low calcination temperature and the like. The invention can be applied to the field of industrial sewage and urban domestic sewage treatment.

Description

But the preparation method of magnetic separation titanium dioxide visible light catalyst
Technical field
Separate NEW TYPE OF COMPOSITE photochemical catalyst that reclaims and preparation method thereof but the present invention relates to a kind of sunshine and magnetic of utilizing, belong to the photochemical catalyst preparing technical field.
Background technology
Semiconductor gas phase photocatalytic oxidation degradation organic matter has become the research focus of environmental pollution improvement, as a kind of widely used photochemical catalyst, TiO 2Nontoxic with it, catalytic activity is high, oxidability is strong, good stability and the most commonly used.At sewage treatment area, outstanding slurry type photo catalysis reactor is subjected to common attention because of its high-specific surface area and good dispersiveness.Yet, owing to be subjected to from water, reclaiming nano-TiO 2The puzzlement of particulate, outstanding slurry type photo catalysis reactor still is very restricted.In order to overcome the difficulty of catalyst separation, the researcher is with TiO 2Load on the carriers such as bead, glass fibre, zeolite and prepare loaded photocatalyst.Because the less specific area of these carrier of photocatalyst greatly reduces TiO 2Load capacity and photocatalytic activity.On the other hand, because TiO 2Band gap big (～3.2ev), can only absorb ultraviolet light, and ultraviolet light only accounts for the 3-5% of sunshine, visible light has but accounted for 45% of solar energy, therefore, has the TiO of recuperability 2The preparation of visible light catalyst becomes the key issue of wastewater treatment industryization.
In recent years, there is the researcher to point out, is developed into the magnetic suspension loaded photocatalyst, both possessed the high efficiency that suspended phase light is urged agent, can utilize magnetic recovery again, overcome suspension TiO if adopt superparamagnetism, corrosion resistant ferromagnetic particle as carrier 2The shortcoming of Powder Recovery difficulty, this type of catalyst will be with a wide range of applications.A kind of megnetic nano composite photocatalyst of patent and preparation method thereof (CN 200610011122.6) with a kind of magnetic photocatalyst and preparation method thereof (CN 1935358 A) but all related to magnetic and separated TiO 2The preparation of photochemical catalyst, but they to prepare the magnetic photocatalytic agent method be to adopt two-step method, promptly at first make magnetic-particle, then at the outer TiO that coats of magnetic-particle 2, complicated process of preparation, the cycle is longer.
In order to solve TiO 2Photochemical catalyst visible light utilization rate problem, lot of documents reported utilize metal-modified to improve TiO 2The method of photocatalytic activity.Chinese patent CN 101209412A, CN1724146A, reported with metal ions such as iron, tin titanium deoxide catalyst has been carried out modification, the scope that excites of handling rear catalyst light is moved to visible light wave range by the ultraviolet light wave band, under visible light, have advantages of high catalytic activity, make full use of the solar energy of green non-pollution.
Summary of the invention
The object of the invention is to overcome the deficiency of now existing magnetic separated light catalyst preparation technology, but the preparation method of the magnetic separation titanium dioxide photochemical catalyst that a kind of preparation technology is simple, the cycle is short is provided.
Another object of the present invention is to provide a kind of titanium dioxide optical catalyst that has than high visible light catalytic activity.
We are primary raw material with titanium tetrachloride, solubility trivalent iron salt, solubility divalent cobalt, regulate pH value with ammoniacal liquor, obtain solid product under mechanical agitation and the ultrasonic dispersion acting in conjunction, then by wash, ethanol is washed, oven dry, roasting, one-step method makes TiO 2-CoFe 2O 4Composite visible light catalyst.
Described preparation method specifically can adopt following steps: under ice-water bath and mechanical agitation condition, the titanium tetrachloride adding is dissolved with in the deionized water of hydrolysis inhibitor, obtains flaxen titanium tetrachloride aqueous solution; In the above-mentioned titanium tetrachloride aqueous solution with mol ratio nTi 4+: nFe 3+: nCo 2+=1～5: add solubility trivalent iron salt, divalent cobalt at 2: 1, continuing mechanical agitation mixes reaction system, system temperature is risen to 68-80 ℃, start ultrasonic wave and carry out ultrasonic dispersion, in 8～10 scopes, mechanical agitation and ultrasonic dispersion acting in conjunction reaction down obtained solid sample in 0.8-1 hour with ammoniacal liquor regulation system pH value; With above-mentioned solid sample through washing, ethanol washes, oven dry, roasting, promptly is able to TiO 2And CoFe 2O 4TiO for main component 2-CoFe 2O 4Composite visible light catalyst;
Described sintering temperature scope is 300-500 ℃.
A kind of in the preferred hydrochloric acid of described hydrolysis inhibitor, nitric acid, the acetic acid.
The preferred FeCl of described solubility trivalent iron salt 36H 2O, Fe 2(SO 4) 3XH 2O, Fe (NO 3) 39H 2A kind of among the O.
The preferred CoCl of described solubility divalent cobalt 26H 2O, Co (NO 3) 26H 2A kind of among the O.
But the preparation method of magnetic separation titanium dioxide visible light catalyst provided by the invention compares with the method that prepared the core-shell type composite photo-catalyst in the past.Show that at first its preparation method is that a step is synthetic, preparation technology is simple, and the cycle is short.This novel photochemical catalyst is by TiO 2And CoFe 2O 4Form, thereby catalyst can effectively separate by externally-applied magnetic field, is convenient to recovery and reuse.Simultaneously, micro Fe in preparation process 3+, Co 2+Replace part Ti by warm-up movement 4+Obtain doped titanium dioxide photocatalyst, thereby obtained having the catalyst of higher visible light activity.
This catalyst can be under externally-applied magnetic field effectively with handled fluid separation applications, be convenient to recovery and reuse, have higher visible light catalysis activity again, have simultaneously raw material be easy to get, with low cost, advantages such as preparation technology is simple, and manufacturing cycle is short, and sintering temperature is low.Can be used for trade effluent and city domestic sewage process field.
Description of drawings
The present invention has accompanying drawing 3 width of cloth.
Fig. 1 is Fig. 1 embodiment one sample 2 hours XRD spectras of roasting under different sintering temperatures: 500 ℃ of (a) 300 ℃, (b) 400 ℃, (c) and (d) 600 ℃;
Fig. 2 is the TiO of embodiment one preparation 2-CoFe 2O 4Composite visible light catalyst carries out the magnetic property curve;
Fig. 3 is sample catalyst degradation methyl orange empirical curve under sunshine.
The specific embodiment
Embodiment one:
Under ice-water bath mechanical agitation condition, get 6mlTiCl 4Adding is dissolved with in the 100ml deionized water of 2ml HCl, obtains flaxen titanium tetrachloride aqueous solution, adds 6g FeCl 36H 2O and 3.5gCo (NO 3) 26H 2O (nTi 4+: nFe 3+: nCo 2+=5: 2: 1), continue stirring reaction system is mixed, and start heater; When system temperature to 72 ℃; Start ultrasonic wave and carry out ultrasonic dispersion, in the 8-10 scope, reaction obtained solid sample in 1 hour under mechanical agitation and the ultrasonic peptizaiton with ammoniacal liquor regulation system pH; After the cooling above-mentioned solid sample is washed each three times through washing, ethanol, 80-100 ℃ of oven dry, 400 ℃ of roastings 2 hours promptly get TiO 2-CoFe 2O 4Composite visible light catalyst.
Embodiment two:
Under ice-water bath mechanical agitation condition, get 6ml TiCl 4Adding is dissolved with in the 100ml deionized water of 2ml HAc, obtains flaxen titanium tetrachloride aqueous solution, adds 8gFe 2(SO 4) 3XH 2O and 6gCo (NO 3) 26H 2O (nTi 4+: nFe 3+: nCo 2+=2.76: 2: 1), continue stirring reaction system is mixed, and start heater; When system temperature to 80 ℃; Start ultrasonic wave and carry out ultrasonic dispersion, in the 8-10 scope, reaction obtained solid sample in 0.8 hour under mechanical agitation and the ultrasonic peptizaiton with ammoniacal liquor regulation system pH; After the cooling above-mentioned solid sample is washed each three times through washing, ethanol, 80-100 ℃ of oven dry, 500 ℃ of roastings 2 hours promptly get TiO 2-CoFe 2O 4Composite visible light catalyst.
Embodiment three:
Under ice-water bath mechanical agitation condition, get 6ml TiCl 4Adding is dissolved with in the 100ml deionized water of 2ml HCl, obtains flaxen titanium tetrachloride aqueous solution, adds 9.8gFe (NO 3) 39H 2O and 3.5gCo (NO 3) 26H 2O (nTi 4+: nFe 3+: nCo 2+=2.76: 2: 1), continue stirring reaction system is mixed, and start heater; When system temperature to 72 ℃; Start ultrasonic wave and carry out ultrasonic dispersion, in the 8-10 scope, reaction obtained solid sample in 1 hour under mechanical agitation and the ultrasonic peptizaiton with ammoniacal liquor regulation system pH; After the cooling above-mentioned solid sample is washed each three times through washing, ethanol, 80-100 ℃ of oven dry, 400 ℃ of roastings 2 hours promptly get TiO 2-CoFe 2O 4Composite visible light catalyst.
Embodiment four:
Under ice-water bath mechanical agitation condition, get 6ml TiCl 4Add and be dissolved with 2ml HNO 3The 100ml deionized water in, obtain flaxen titanium tetrachloride aqueous solution, add 8g Fe 2(SO 4) 3XH 2O and 5g CoCl 26H 2O, (nTi 4+: nFe 3+: nCo 2+=2.76: 2: 1) continue stirring reaction system is mixed, and start heater; When system temperature to 72 ℃; Start ultrasonic wave and carry out ultrasonic dispersion, in the 8-10 scope, reaction obtained solid sample in 1 hour under mechanical agitation and the ultrasonic peptizaiton with ammoniacal liquor regulation system pH; After the cooling above-mentioned solid sample is washed each three times through washing, ethanol, 80-100 ℃ of oven dry, 400 ℃ of roastings 2 hours promptly get TiO 2-CoFe 2O 4Composite visible light catalyst.
Embodiment five:
Other conditions are with embodiment one, and sintering temperature is 300 ℃, gained TiO 2-CoFe 2O 4Composite visible light catalyst.
Embodiment six:
Other conditions are with embodiment one, and sintering temperature is 500 ℃, gained TiO 2-CoFe 2O 4Composite visible light catalyst.
Embodiment seven:
With embodiment one sample respectively 300 ℃ (a), 400 ℃ (b), 500 ℃ (c) and 600 ℃ of (d) roasting temperatures 2 hours.Sample XRD characterization result as shown in Figure 1.From collection of illustrative plates, see and when temperature is lower than 300 ℃, only have tangible CoFe 2O 4Diffraction maximum, match with PDF standard card, wherein CoFe 2O 4Exist with spinel structure.When temperature is higher than more than 400 ℃, in the XRD of the sample spectrum tangible TiO has appearred 2Anatase (101) characteristic diffraction peak (2 θ=25.4 °).Because a small amount of assorted peak appears in different alternate Elements Diffusion in the collection of illustrative plates, but in the whole crystallization process of complex, there is not other middle all the time mutually as CoTiO 3Or Fe 2(TiO 3) 3Diffraction maximum occur, draw TiO in the complex thus 2And CoFe 2O 4Growth separately, not reacting generates new thing phase.
Embodiment eight:
TiO with embodiment one preparation 2-CoFe 2O 4Composite visible light catalyst carries out the magnetic property analysis, and the result as shown in Figure 2.TiO 2-CoFe 2O 4The hysteresis that composite visible light catalyst does not show ferromagnetic material substantially and had, and coercivity and remanent magnetism almost can ignore, and photocatalysis of this explanation preparation has certain superparamagnetism.When externally-applied magnetic field intensity dropped to zero, the remanent magnetism of prepared particle also almost dropped to zero.Therefore, when giving light-catalyzed reaction system externally-applied magnetic field, can be easily with catalyst recovery; When removing external magnetic field, catalyst can be dispersed in the reaction system at an easy rate again, has solved the recycling difficult problem of photochemical catalyst.
Embodiment nine:
Under ice-water bath mechanical agitation condition, get 6ml TiCl 4Adding is dissolved with in the 100ml deionized water of 2ml HCl, obtains flaxen titanium tetrachloride aqueous solution, regulates making system pH in the 8-10 scope with ammoniacal liquor, and reaction obtained solid sample in 1 hour under mechanical agitation and the ultrasonic peptizaiton; Washing, ethanol are washed each three times, and 80-100 ℃ of oven dry, 400 ℃ of roastings 2 hours promptly get TiO 2Photochemical catalyst.
Embodiment ten:
The 1g TiO that under sunshine, embodiment one is made 2-CoFe 2O 4Composite visible light catalyst adds and to fill in the methyl orange solution that 50ml concentration is 20mg/L, under similarity condition respectively with equivalent TiO 2For the TiO that embodiment nine obtains is got in reference 2Photochemical catalyst and P 25Do the photocatalysis experiment.Comparative test result as shown in Figure 3.The result is presented under the solar light irradiation, by the TiO of example one preparation 2-CoFe 2O 4Composite visible light urges agent to have higher visible light catalysis activity, photocatalysis 2 hours, and methyl orange degradation can reach 92%, and P under the same terms 25With embodiment nine TiO 2The methyl orange degradation rate of sample only is 7% and 12%.

Claims (4)

1. but the preparation method of magnetic separation titanium dioxide visible light catalyst, it is characterized in that being is primary raw material with titanium tetrachloride, solubility trivalent iron salt, solubility divalent cobalt, regulate the pH value with ammoniacal liquor, obtain solid product under mechanical agitation and the ultrasonic dispersion acting in conjunction, then by washing, ethanol washes, oven dry, roasting, one-step method makes TiO 2-CoFe 2O 4Composite visible light catalyst;
Concrete steps are as follows: under ice-water bath and mechanical agitation condition, the titanium tetrachloride adding is dissolved with in the deionized water of hydrolysis inhibitor, obtains flaxen titanium tetrachloride aqueous solution; In the above-mentioned titanium tetrachloride aqueous solution with mol ratio nTi 4+: nFe 3+: nCo 2+=1～5: add solubility trivalent iron salt, solubility divalent cobalt at 2: 1, continuing mechanical agitation mixes reaction system, system temperature is risen to 68-80 ℃, start ultrasonic wave and carry out ultrasonic dispersion, in 8～10 scopes, mechanical agitation and ultrasonic dispersion acting in conjunction reaction down obtained solid sample in 0.8-1 hour with ammoniacal liquor regulation system pH value; With above-mentioned solid sample through washing, ethanol washes, oven dry, roasting, promptly is able to TiO 2And CoFe 2O 4Composite visible light catalyst for main component;
Described sintering temperature scope is 300-500 ℃.
2. but the preparation method of magnetic separation titanium dioxide visible light catalyst described in claims 1 is characterized in that described hydrolysis inhibitor is a kind of in hydrochloric acid, nitric acid, the acetic acid.
3. but the preparation method of magnetic separation titanium dioxide visible light catalyst described in claims 1 is characterized in that described solubility trivalent iron salt is FeCl 36H 2O, Fe 2(SO 4) 3XH 2O, Fe (NO 3) 39H 2A kind of among the O.
4. but the preparation method of magnetic separation titanium dioxide visible light catalyst described in claims 1 is characterized in that described solubility divalent cobalt is CoCl 26H 2O, Co (NO 3) 26H 2A kind of among the O.
CN2010102030499A 2010-06-10 2010-06-10 Preparation method of magnetic separation titanium dioxide visible light catalyst Expired - Fee Related CN101850251B (en)

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CN102794164A (en) * 2012-07-19 2012-11-28 湖南先科环保有限公司 Preparation method of magnetic doped nano titanium dioxide
CN102784662B (en) * 2012-08-13 2013-12-18 天津城市建设学院 Preparation method for micro magnet-carried TiO2 catalyst
CN104128184B (en) * 2014-06-24 2016-05-11 安徽理工大学 A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof
CN105855539B (en) * 2016-04-13 2020-09-01 安徽大学 CoFe for photocatalysis field2Core CoFe2O4Construction method of shell layer nano structure
CN106268819B (en) * 2016-08-04 2018-11-30 苏州科技学院 Active carbon-ferrous acid cobalt composite material, preparation method and photocatalysis denitrogenation purposes
CN106540717A (en) * 2016-10-21 2017-03-29 江苏大学 A kind of hydro-thermal method synthesizes recyclable CdS/CoFe2O4The preparation method and its usage of/rGO composite photo-catalysts
CN110479293A (en) * 2017-07-06 2019-11-22 于清花 A kind of photochemical catalyst preparation method
CN108928881A (en) * 2018-08-02 2018-12-04 四川大学 Magnetic agglomerates photo catalysis reactor and photocatalysis sewage treatment equipment and method

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JP2005138008A (en) * 2003-11-05 2005-06-02 National Institute For Materials Science Visible light responding type titanium oxide composite photocatalyst and its manufacturing method
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