CN102266783A - Iron-doped tungsten trioxide photocatalyst and preparation method thereof - Google Patents
Iron-doped tungsten trioxide photocatalyst and preparation method thereof Download PDFInfo
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- CN102266783A CN102266783A CN 201110170439 CN201110170439A CN102266783A CN 102266783 A CN102266783 A CN 102266783A CN 201110170439 CN201110170439 CN 201110170439 CN 201110170439 A CN201110170439 A CN 201110170439A CN 102266783 A CN102266783 A CN 102266783A
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Abstract
The invention provides an iron-doped tungsten trioxide photocatalyst. The photocatalyst comprises tungsten trioxide powder particles, and the tungsten trioxide powder particles comprise iron oxide with different contents and states. The photocatalyst of the invention has a significantly increased photocatalytic rate. The invention also provides a preparation method of the iron-doped tungsten trioxide photocatalyst; tungsten-containing and iron-containing compounds are used as precursors; the raw materials are finally transformed into forms of WO3 and iron oxide by processes of mixing the two compounds, grinding, high-temperature calcining and the like; and the iron oxide is distributed in WO3 in different forms so as to obtain the iron-doped tungsten trioxide photocatalyst. The raw materials used by the invention have low cost, and the equipment is simple and easy to operate; when the obtained photocatalyst is compared with simple tungsten trioxide and iron oxide, the photocatalytic activity in ultraviolet light and visible light is increased by several times.
Description
Technical field
The present invention relates to a kind of iron doping tungstic acid photochemical catalyst and preparation method thereof, belong to catalysis technical field, more concrete is the invention provides a kind of iron doping tungstic acid photochemical catalyst and preparation method thereof and optimal light reaction condition that dyestuff and phenol is all had higher catalytic activity under ultraviolet and visible light.
Background technology
Along with the continuous progress of human civilization, energy shortage and environmental pollution are serious day by day, and therefore, exploitation is efficient, low energy consumption, applied widely and the clean treatment technology of pollutant of deep oxidation ability is arranged is the target that the environmental protection researcher is pursued always.The conductor photocatalysis technology be owing to can at room temperature directly utilize the light source of the various approach that comprise sunshine, with all kinds of organic pollution permineralizations, and non-secondary pollution, therefore receive great concern.This technology have energy consumption low, easy to operate, remove characteristics such as cleanliness height, especially to some special pollutants, photocatalysis technology has more the incomparable advantage of other technologies.At present, photocatalysis technology has become a focus in various countries' high-tech competition, is with a wide range of applications.
In the conductor photocatalysis field, study and use the semiconductor more, that efficient is higher that TiO is arranged
2, SnO
2, WO
3, CdS, ZnO etc.TiO wherein
2Be studied and use at most, but its band gap is big, can only be by ultraviolet excitation, and that sunshine medium ultraviolet light only accounts for is about 4%, so it is very low to the utilization rate of sunshine.WO comparatively speaking
3Band gap is little, energy absorption portion visible light, and dispersiveness is also fine in water, is very potential visible light catalyst.But WO
3Photocatalytic activity lower, therefore how to WO
3The semi-conducting material modification is the important techniques focus to improve its photocatalytic activity.
In order to improve WO
3Photocatalytic activity, doping is important means.R. people such as Abe is deposited on WO with nanometer Pt
3On, make its multiple organic matter of can under visible light, degrading, activity even the TiO that mixes above N
2In addition, Pd, the doping of noble metals such as Ag also can make its activity improve a lot, but this doping method cost is too high, is unfavorable for large-scale promotion application.Also report at Ag
+, Cu
2+, Fe
3+And Ce
4+Plasma exists down, WO
3Activity raising is also arranged, also run counter to the original intention of environmental protection but in water body, introduce these ions.In present technique, we are with another kind of semiconductor oxide iron and WO
3Mix, make both activities that the raising of several times be arranged.
Iron oxide is one of the most common compound of occurring in nature, and it is with multi-form each corner that is present in the earth widely, so raw material is cheap and easy to get.Foremost about Fe is exactly Fenton reaction, i.e. H
2O
2In the presence of iron ion, can generate the very strong hydroxyl radical free radical of oxidability, can oxidative degradation overwhelming majority toxic organic pollutants, or thoroughly mineralising be CO
2, H
2O and corresponding organic matter, the green method that therefore becomes pollutant control and cut down.Studies show that the Fenton reaction speed is faster under the illumination, and hydrogen peroxide utilization ratio height, i.e. UV/Vis-Fenton reaction.Thereby iron mixed in the tungstic acid, Fenton reaction and conductor photocatalysis can be combined, make its photocatalysis efficiency that greatly raising be arranged.
Reference that the present invention adopts:
Gr tzel,?M.?A.?
Energy?Resources?through?Photochemistry?and?Catalysis;?Academic?Press:?New?York,?1983.
Tachikawa,?T.;?Majima,?T.?
Langmuir?2009,?25,?7791 7802.
Hoffmann,?M.?R.;?Martin,?S.?T.;?Choi,?W.;?Bahnemann,?D.?W.?
Chem.?Rev.?1995,?95,?69 96.
Carp,?O.;?Huisman,?C.?L.;?Reller,?A.?Prog.?
Solid.?State?Chem.?2004,?32,?33 177.
Abe,?R.;?Takami,?H.;?Murakami,?N.;?Ohtani,?B.?
J.?Am.?Chem.?Soc.?2008,?130,?7780 7781.
Arai,?T.;?Horiguchi,?M.;?Yanagida,?M.;?Gunji,?T.;?Sugihara,?H.;?Sayama,?K.?
Chem.?Commun.?2008,?43,?5565-5567.
Erbs,?W.;?Desilvestro,?J.;?Borgarello,?E.;?Gr tzel,?M.?
J.?Phys.?Chem.?1984,?88,?4001 4006.
Arai,?T.;?Yanagida,?M.;?Konishi,?Y.;?Iwasaki,?Y.;?Sugihara,?H.;?Sayama,?K.?
Catal.?Commun.?2008,?9,?1254 1258.
Wang,?C.?
Acc.?Chem.?Res.?1975,?8,?125 131.
Plgnatello,?J.?J.?
Environ.?Sci.?Technol.?1992,?26,?944 951.
Summary of the invention
The object of the present invention is to provide a kind of iron doping tungstic acid photochemical catalyst with high catalytic activity.Purpose of the present invention realizes by following technical measures:
It comprises tungstic acid powder particle, comprises the iron oxide of different content and state in the described tungstic acid powder particle.
By above technical scheme, photocatalytic speed of the present invention significantly improves.
The present invention also aims to provide the preparation method of iron doping tungstic acid photochemical catalyst, purpose of the present invention realizes by following technical measures:
The present invention is a precursor with the compound of tungstenic and iron content, and by both are mixed, processes such as grinding, high-temperature calcination make raw material finally be converted into WO
3With the form of iron oxide, and make iron oxide be distributed in WO with different shape
3In, make the tungstic acid photochemical catalyst that iron mixes.
The cost of material that the present invention uses is cheap, and equipment is simple, easy operating; The gained photochemical catalyst is than simple tungstic acid and iron oxide, and its ultraviolet light and visible light catalysis activity all have several times to improve.
Description of drawings
Fig. 1 is the structural representation of iron doping tungstic acid photochemical catalyst.
Fig. 2 is that the X ray diffracting spectrum of embodiment 2 is (with pure Fe
2O
3And WO
3Relatively);
Fig. 3 is that the ultraviolet degradation phenol curve of embodiment 1,2,3 is (with pure Fe
2O
3And WO
3Relatively).
The specific embodiment
With reference to accompanying drawing 1.The present invention is the tungstic acid photochemical catalyst that a kind of iron mixes, and it comprises tungstic acid powder particle, is doped with iron oxide in the described tungstic acid powder particle, and institute's doped ferric oxide has different content and different conditions.
In the iron oxide doping hour, this composite catalyst has the crystal structure similar with the tungstic acid raw material, crystalline phase is formed and average grain diameter, but it has ultraviolet and the visible light photocatalysis active that is several times as much as pure tungstic acid.When the iron oxide doping was higher, this composite catalyst then has the crystal structure and the crystalline phase of tungstic acid and iron oxide simultaneously to be formed, and also has ultraviolet and the visible light catalysis activity higher than pure iron oxide.The present invention direct doped ferric oxide in the tungstic acid powder particle of commodity that are easy to get or artificial preparation has been realized ferro element immobilized in the tungstic acid photocatalyst particles, makes conductor photocatalysis and light to Fenton reaction synergy; The gained catalyst has very high photocatalytic activity, and heterogeneous reaction, and catalyst can reuse, and greatly saves cost; At organic catalysis and Environmental Science and Engineering field very big application potential is arranged.
The invention also discloses a kind of preparation method with iron doping tungstic acid photochemical catalyst of highlight catalytic active.It is a precursor with the compound of tungstenic and iron content, by methods such as mechanical mixture and high-temperature calcinations, makes the iron doping tungstic acid photochemical catalyst of different iron dopings and different temperatures activation.Preparation method's difference, the crystalline phase of gained catalyst is formed, existence and the photocatalytic activity of iron in tungstic acid is all inequality, but all has ultraviolet and the visible light photocatalysis active higher than raw material.
The inventive method can be in the tungstic acid powder particle of commodity that are easy to get or artificial preparation direct doping iron, realized ferro element immobilized in the tungstic acid photochemical catalyst; The gained catalyst has very high ultraviolet and can be with the light photocatalytic activity; At organic catalysis and Environmental Science and Engineering field very big application potential is arranged.Technology of the present invention is simple, and lower to the equipment requirement, raw material is cheap and easy to get, has improved the photocatalytic activity of tungstic acid and iron oxide simultaneously.
Described preparation method is specific as follows:
The preparation method one of 1 one kinds of iron doping of method tungstic acid photochemical catalyst, i.e. solid phase mixing method may further comprise the steps:
1) at normal temperatures, the pressed powder of tungstenic and iron content is scattered under vigorous stirring forms suspension in the aqueous solution, tungsten and iron are scaled WO in the raw material
3And Fe
2O
3Calculate Fe
2O
3Doping is 0.1 ~ 90 %(quality percentage composition, WO
3%+Fe
2O
3%=100%);
2) this suspension stirring and ultrasonic making it mix.
3) step 2 gained suspension is on Rotary Evaporators 50 ~ 95
0The C evaporate to dryness.
4) step 3 gained evaporate to dryness powder grinds, in Muffle furnace 200 ~ 950
0The C calcining and activating promptly gets the tungstic acid photochemical catalyst that iron mixes.
The preparation method two of 2 one kinds of iron doping of method tungstic acid photochemical catalyst, i.e. infusion process may further comprise the steps:
1) at normal temperatures, presoma is contained in the aqueous solution that tungsten powder is scattered in ferric nitrate, tungsten and iron are scaled WO in the raw material
3And Fe
2O
3Calculate Fe
2O
3Doping is 0.1 ~ 90 %(quality percentage composition, WO
3%+Fe
2O
3%=100%);
2) above-mentioned suspension stirring and ultrasonic making it mix.
3) under the step 2 gained suspension vigorous stirring 50 ~ 95
0Evaporate to dryness in the C water-bath.
4) step 3 gained powder grinds, in Muffle furnace 400 ~ 950
0The C calcining and activating promptly gets the tungstic acid photochemical catalyst that iron mixes.
The preparation method three of 3 one kinds of iron doping of method tungstic acid photochemical catalyst, i.e. the precipitation method may further comprise the steps:
1) at normal temperatures, the molysite with stoichiometric proportion is added drop-wise in the soluble tungstate salt generation Fe
2(WO
4)
3Precipitation;
2) sedimentation and filtration, water washing, 60 ℃ ~ 120 ℃ oven dry of step 1 generation, grind into powder;
3) step 2 gained powder is in Muffle furnace 200 ~ 950
0The C calcining and activating promptly gets the tungstic acid photochemical catalyst that iron mixes.
The preparation method four of 4 one kinds of iron doping of method tungstic acid photochemical catalyst, i.e. decomposition method may further comprise the steps:
1) adds acid in the deionized water, make H in the solution
+Ion concentration is 1 molL
-1, a certain amount of tungstates is dissolved in this solution solution, get settled solution;
2) iron salt solutions that will be added with the saturated acetic acid sodium solution is added drop-wise in step 1 gained clear liquid, mixed solution;
3) step 2 gained mixed liquor 120 ~ 200
0The C oil bath refluxed 16 hours, got turbid solution;
4) step 3 gained turbid solution cooled and filtered, filtrate adds diethyl ether and acid extraction, and the gained etherate adds water, and 20 ~ 60
0C steams ether, keeps lower aqueous solution;
5) step 4 obtained aqueous solution evaporate to dryness on boiling water bath gets buff powder;
6) gained buff powder washing, 60 ℃ ~ 120 ℃ dryings are in the Muffle furnace 200 ~ 950
0The C calcining and activating promptly gets the tungstic acid photochemical catalyst that iron mixes.
In the above preparation process, selected tungstenic raw material can be WO
3, H
2WO
4, through the WO of high-temperature calcination
3, H
2WO
4, (NH
4)
6W
7O
246H
2Any one or its mixing of any two or three in O, the ammonium paratungstate.
Iron-bearing material can be α-Fe
2O
3, γ-Fe
2O
3, Fe
3O
4, any one or its any two or three the mixing in alpha-feooh, γ-FeOOH, δ-FeOOH, these iron oxide amorphous or the crystal habit that different temperatures activated.
Soluble tungstate salt can be any one or its any two or three the mixing in sodium tungstate, ammonium tungstate, para-tungstic acid, sodium paratungstate, the ammonium paratungstate.
Molysite can be an iron chloride, ferric nitrate, any one in the ferrous sulfate or its mixing of any two or three.
H is provided
+The acid of ion and extraction usefulness can be any one or its any two or three the mixing in hydrochloric acid, nitric acid, the sulfuric acid.
The evaluation method of photocatalytic activity is: is outer irradiation source with radiation dominant wavelength at the high-pressure sodium lamp (375 W) of 365 nm, and the anti-device of light is made with Pyrex glass, and the cool cycles water leg is arranged, and makes reaction temperature remain on 25 ± 2 ℃.Catalyst amount is 50 mg, is that the phenol solution of 40 ppm is mixed with 50 mL concentration before the reaction, the lucifuge balance of vibrating.Add certain amount of H before the illumination
2O
2After the beginning illumination, get 1.5 mL reactant liquors at regular intervals, filter, measure phenol concentration in the filtrate with HPLC through miillpore filter (0.22 μ m)
C tAccording to
C tWith the variation relation of light application time, weigh the relative photocatalytic activity of different catalysts.
Embodiment one
With the amorphous oxidation iron of 0.002 g (Fe
2O
3) and 1.998 g tungstic acids be scattered in the 30 mL water, stir the back ultrasonic 30 min, use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 400
0C calcines 3h, and 0.1 wt% Fe obtains mixing
2O
3Tungstic acid photochemical catalyst A(see A line in Fig. 1 ~ 3).With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, under ultraviolet light, shine after 3 hours Fe
2O
3, tungstic acid and catalyst A Pyrogentisinic Acid degradation rate be respectively 7.15%, 28.4 % and 50.96 %.Obviously, under the same conditions, catalyst A compares Fe
2O
3Has stronger ultraviolet catalytic activity with tungstic acid.
Embodiment two
With the amorphous oxidation iron of 0.02 g (Fe
2O
3) and 1.98 g tungstic acids be scattered in the 30 mL water, stir the back ultrasonic 30 min, use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 400
0C calcines 3h, and 1wt% Fe obtains mixing
2O
3Tungstic acid photochemical catalyst B(see B line in Fig. 1 ~ 3).With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, under ultraviolet light, shine after 3 hours Fe
2O
3, tungstic acid and catalyst B Pyrogentisinic Acid degradation rate be respectively 7.15%, 28.4 % and 60.07 %.Obviously, under the same conditions, the ultraviolet catalytic specific activity tungstic acid and the Fe of catalyst B
2O
3The raising of several times is arranged.
Embodiment three
With the amorphous oxidation iron of 0.02 g (Fe
2O
3) and 1.98 g tungstic acids be scattered in the 25 mL water, stir the back ultrasonic 30 min, use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 200
0C calcines 3h, and 1 wt% Fe obtains mixing
2O
3Tungstic acid photochemical catalyst C(see C line in Fig. 1 ~ 3).With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, irradiation is after 3 hours under ultraviolet light, and catalyst C Pyrogentisinic Acid's degradation rate is 59.98%.
Embodiment four
With the amorphous oxidation iron of 0.4 g (Fe
2O
3) and 1.6 g tungstic acids be scattered in the 25 mL water, stir the back ultrasonic 30 min, use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 400
0C calcines 3h, and 20 wt% Fe obtain mixing
2O
3The tungstic acid photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, irradiation is after 3 hours under ultraviolet light, and the degradation rate of phenol is 30.58%.
Embodiment five
With the amorphous oxidation iron of 0.02 g (Fe
2O
3) and 1.98 g tungstic acids be scattered in the 30 mL water, stir the back ultrasonic 30 min, use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 600
0C calcines 3h, and 1 wt% Fe obtains mixing
2O
3The tungstic acid photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, irradiation is after 3 hours under ultraviolet light, and the degradation rate of phenol is 41.11%.
Embodiment six
0.02 g 400 is spent the α-Fe that activated
2O
3Be scattered in the 30 mL water with 1.98 g tungstic acids, ultrasonic 30 min in back that stir use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 400
0C calcines 3h, and 1 wt% Fe obtains mixing
2O
3The tungstic acid photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, irradiation is after 3 hours under ultraviolet light, and the degradation rate of phenol is 50.94%.
Embodiment seven
With the amorphous oxidation iron of 0.02 g (Fe
2O
3) and the yellow wolframic acid of 2.13 g be scattered in the 25 mL water, ultrasonic 30 min in back that stir use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 400
0C calcines 3h, and 1wt% Fe obtains mixing
2O
3The tungstic acid photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, irradiation is after 3 hours under ultraviolet light, and the degradation rate of phenol is 35.19 %.
Embodiment eight
With the amorphous oxidation iron of 0.02 g (Fe
2O
3) and the yellow wolframic acid that activate of 1.98 g 400 degree be scattered in the 20 mL water, ultrasonic 30 min afterwards that stir use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 400
0C calcines 3h, and 1wt% Fe obtains mixing
2O
3The tungstic acid photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, irradiation is after 3 hours under ultraviolet light, and the degradation rate of phenol is 46.16%.
Embodiment nine
With the amorphous oxidation iron of 0.02 g (Fe
2O
3) and the tungstic acid that activate of 1.98 g 700 degree be scattered in the 20 mL water, ultrasonic 30 min afterwards that stir use Rotary Evaporators 60 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 400
0C calcines 3h, and 1wt% Fe obtains mixing
2O
3The tungstic acid photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, irradiation is after 3 hours under ultraviolet light, and the degradation rate of phenol is 55.89%.
Embodiment ten
0.02 g 700 is spent the α-Fe that activated
2O
3Be scattered in the 30 mL water with 1.98 g tungstic acids, ultrasonic 30 min in back that stir use Rotary Evaporators 70 afterwards
0The C evaporate to dryness.Powder behind the evaporate to dryness is in Muffle furnace 400
0C calcines 3h, and 1 wt% Fe obtains mixing
2O
3The tungstic acid photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, irradiation is after 3 hours under ultraviolet light, and the degradation rate of phenol is 54.29%.
Embodiment 11
8.6 g nitric hydrate iron is dissolved in the 100 mL water, adds 15 mL saturated acetic acid sodium solutions.Above-mentioned drips of solution is added to (H in the salpeter solution of 250 mL sodium tungstates
+=3 molL
-1).Mixed liquor is in oil bath 140
0C refluxed 16 hours.Cooled solution adds sulfuric acid and extracted with diethyl ether.Etherate adds water, steams the upper strata ether, and water layer decomposes to dried on boiling water bath.Powder is through water washing, and 60
0C oven dry is in Muffle furnace 400
0C calcines 3h, and 0.3 wt% Fe obtains mixing
2O
3The tungstic acid photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, add the H of 10 mM
2O
2, pH=1, irradiation is after 3 hours down for ultraviolet light, and the degradation rate of phenol is 56.85%.
?
The above-mentioned specific embodiment is used for the present invention that explains; only be the preferred embodiments of the present invention; rather than limit the invention; in the protection domain of spirit of the present invention and claim; any modification that the present invention is made, be equal to replacement, improvement etc., all fall into protection scope of the present invention.
Claims (10)
1. iron doping tungstic acid photochemical catalyst, it is characterized in that: it comprises tungstic acid powder particle, contains iron oxide in the described tungstic acid powder particle, the iron in the described iron oxide is trivalent and/or divalence.
2. the preparation method one of a kind of iron doping tungstic acid photochemical catalyst as claimed in claim 1 is characterized in that it may further comprise the steps:
1) at normal temperatures, the pressed powder of tungstenic and iron content is scattered under vigorous stirring forms suspension in the aqueous solution, tungsten and iron are scaled WO in the raw material
3And Fe
2O
3Calculate Fe
2O
3Doping is 0.1 ~ 90 % mass percent, described WO
3And Fe
2O
3The quality sum be absolutely;
2) stirring also to this suspension, ultrasonic making it mixes;
3) with step 2) the gained suspension is on Rotary Evaporators 50 ~ 95
0The C evaporate to dryness;
4) step 3) gained evaporate to dryness powder is ground, in Muffle furnace 200 ~ 950
0The C calcining and activating promptly gets the tungstic acid photochemical catalyst that iron mixes.
3. the preparation method two of a kind of iron doping tungstic acid photochemical catalyst as claimed in claim 1 is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma is contained in the aqueous solution that tungsten powder is scattered in ferric nitrate, tungsten and iron are scaled WO in the raw material
3And Fe
2O
3Calculate Fe
2O
3Doping is 0.1 ~ 90 % mass percent, described WO
3And Fe
2O
3The quality sum be absolutely;
2) stirring also to this suspension, ultrasonic making it mixes;
3) with step 2) under the gained suspension vigorous stirring, 50 ~ 95
0Evaporate to dryness in the C water-bath;
4) step 3) gained powder is ground, in Muffle furnace 400 ~ 950
0The C calcining and activating promptly gets the tungstic acid photochemical catalyst that iron mixes.
4. the preparation method three of a kind of iron doping tungstic acid photochemical catalyst as claimed in claim 1 is characterized in that it may further comprise the steps:
1) at normal temperatures, the molysite with stoichiometric proportion is added drop-wise in the soluble tungstate salt generation Fe
2(WO
4)
3Precipitation;
2) sedimentation and filtration, water washing, 60 ℃ ~ 120 ℃ oven dry that step 1) is generated, grind into powder;
3) with step 2) the gained powder is in Muffle furnace 200 ~ 950
0The C calcining and activating promptly gets the tungstic acid photochemical catalyst that iron mixes.
5. the preparation method four of a kind of iron doping tungstic acid photochemical catalyst as claimed in claim 1 is characterized in that it may further comprise the steps:
1) adds acid in the deionized water, make H in the solution
+Ion concentration is 0.5 ~ 8 molL
-1, a certain amount of tungstates is dissolved in this solution, get settled solution;
2) iron salt solutions that will be added with the saturated acetic acid sodium solution is added drop-wise in step 1) gained clear liquid, mixed solution;
3) with step 2) gained mixed liquor 120 ~ 200
0The C oil bath refluxed 16 hours, got turbid solution;
4) to step 3) gained turbid solution cooled and filtered, filtrate adds diethyl ether and acid extraction, and the gained etherate adds water, and 20 ~ 60
0C steams ether, keeps lower aqueous solution;
5), get buff powder with step 4) obtained aqueous solution evaporate to dryness on boiling water bath;
6) with gained buff powder washing, 60 ℃ ~ 120 ℃ dryings are in the Muffle furnace 200 ~ 950
0The C calcining and activating promptly gets the tungstic acid photochemical catalyst that iron mixes.
According to claim 2 and or the preparation method of the described iron doping of claim 3 tungstic acid photochemical catalyst, the pressed powder that it is characterized in that described tungstenic can be WO
3, H
2WO
4, H
2WO
4, (NH
4)
6W
7O
246H
2The mixture of one or both in O, the ammonium paratungstate or three kinds.
7. the preparation method of iron doping tungstic acid photochemical catalyst according to claim 2, the pressed powder that it is characterized in that iron content can be α-Fe
2O
3, γ-Fe
2O
3, Fe
3O
4, any one or its any two or three the mixing in alpha-feooh, γ-FeOOH, δ-FeOOH, these iron oxide amorphous or the crystal habit that different temperatures activated.
8. the preparation method of iron doping tungstic acid photochemical catalyst according to claim 4 is characterized in that described soluble tungstate salt can be sodium tungstate, ammonium tungstate, para-tungstic acid, sodium paratungstate and ammonium paratungstate.
9. the preparation method of iron doping tungstic acid photochemical catalyst according to claim 4 is characterized in that described molysite can be an iron chloride, ferric nitrate, any one in the ferrous sulfate or its mixing of any two or three.
10. the described H of providing is provided the preparation method of iron doping tungstic acid photochemical catalyst according to claim 5
+The acid of ion and extraction usefulness can be any one or its any two or three the mixing in hydrochloric acid, nitric acid, the sulfuric acid.
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| CN116328794A (en) * | 2023-04-19 | 2023-06-27 | 苏州科技大学 | Preparation method and application of high-efficiency catalytic oxidation heterojunction material |
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