CN104174408A - Ferrochrome vanadate photocatalytic material with visible light response as well as preparation method and application thereof - Google Patents
Ferrochrome vanadate photocatalytic material with visible light response as well as preparation method and application thereof Download PDFInfo
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- CN104174408A CN104174408A CN201410339327.1A CN201410339327A CN104174408A CN 104174408 A CN104174408 A CN 104174408A CN 201410339327 A CN201410339327 A CN 201410339327A CN 104174408 A CN104174408 A CN 104174408A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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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 discloses a ferrochrome vanadate photocatalytic material CrFe(VO4)2 with visible light response as well as a preparation method and an application thereof. The sample of a photocatalytic material is prepared by using a high-temperature solid-phase reaction method, a chemical solution method and a co-precipitation method; the production cost and device requirement are low; the prepared material is good in dispersion performance, uniform in granularity, good in chemical stability and optic stability; and the prepared photocatalyst sample CrFe(VO4)2 has relatively small spectrum width, excellent photocatalytic performance and good photocatalytic stability and good application prospect and has the effect of decomposing toxic chemical substances under visible light response.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof with visible light-responded ferrochrome vanadate catalysis material, particularly for the photochemical catalyst CrFe (VO of degradable organic pollutant
4)
2and preparation method thereof, belong to inorganic field of photocatalytic material.
Background technology
Along with the continuous growth of world population, the fast development of industry, the consumption problem of energy becomes a problem of needing solution badly.At present, the main source of energy remains oil, the fuel such as natural gas and coal.Yet a large amount of consumption of fossil fuel, can discharge a large amount of toxic gases, relevant various problem of environmental pollutions also occur in succession with it.Therefore, developing continuable energy technology is brought into schedule.In all reproducible energy technologys, comprise water generating, solar energy, wind energy, geothermal energy and biological energy source, wherein, utilize photovoltaic technology that solar energy is transformed into electric energy, is to solve the most promising technology of energy sustainable supply problem.Because solar energy is totally clean, use and can not cause environmental pollution, in liberal supply, impinge upon ground solar energy every day and be the more than 10,000 times of required energy whole world every day, now, solar photoelectric is regarded the third-largest regenerative resource in the whole world, and to the end of the year 2012, the accumulation sunshine electric energy in the whole world has been broken through 100GW high point.Effectively directly utilizing of solar energy, develops efficient sunshine response type semiconductor catalyst, is to solve energy crisis and the dual the very corn of a subject means of environmental problem.
Along with developing rapidly of modern social economy, the energy and ecological environment more and more cause people's concern, solve the energy and problem of environmental pollution and be realize China's sustainable development, improve people's living standard and safeguard national security in the urgent need to.The organic matter of some difficult degradations, as dyestuff, agricultural chemicals etc. is often present in air, water body and soil with very low concentration, has a strong impact on people's Health and Living.So environment purification pollution is cost-effectively the significant problem facing now.The method of conventional process sewage mainly contains Physical, bioanalysis and chemical oxidization method, but these processing method ubiquity long processing period, degradation rate are low, the difficult degradation problem such as completely, and light-catalyzed reaction has mild condition, consersion unit is simple, operating cost is low, secondary pollution is few and the feature such as applied widely, therefore, photocatalysis technology becomes a kind of desirable environmental pollution treatment technology, becomes people's study hotspot.
Light-catalyzed reaction refers to that photochemical catalyst, after the photon having absorbed higher than its band-gap energy, has generated hole and electronics, and these holes and electronics carry out respectively oxidation reaction and reduction reaction, reaches the object of decomposing harmful chemical, organic-biological matter and sterilization.From phase late 1970s, people proposed to utilize in photochemical catalyst decomposition water and atmosphere in agricultural chemicals and the organic matter such as odorant, and application examples such as self-cleaning that scribble the surface of solids of photochemical catalyst.Photochemical catalyst has many kinds, and wherein most representative is titanium dioxide (TiO
2), utilize titanium dioxide to decompose organic matters such as the agricultural chemicals in water and in atmosphere and odorants, yet the band gap of titanium dioxide is 3.2eV, only under the ultraviolet irradiation shorter than 400nm, just can show activity, can only be indoor or have a local work of uviol lamp, almost can not utilize visible ray, this has limited the use of titanium dioxide optical catalyst greatly.In order to develop visible light-responded catalyst, generally have two kinds of modes, a kind of method is to TiO
2carry out modification, by carried noble metal, doped metal ion, make its absorbing wavelength red shift and reduce light induced electron and the recombination probability of photohole with metal oxide coupling etc., thereby improve catalytic activity.But from many results of study, the photocatalytic activity under solar light irradiation of the photochemical catalyst after modification is not high, and stability is bad.
Second method is development of new catalysis material, as oxynitride, titanate, tungstates, vanadate, niobates, chromate, also there is good visible photic photocatalytic activity and chemical stability, therefore work in this respect has more DEVELOPMENT PROSPECT, and the exploitation of the visible light-responded photochemical catalyst of non-oxide titanium is more and more subject to people's attention.The invention relates to a kind of preparation method and application thereof of novel ferrochrome vanadate photocatalyst material, it has the optical absorption in visible-range, has excellent visible light-responded photocatalysis performance, can be used as photocatalyst for degrading organic matter.
Summary of the invention
The present invention seeks to: a kind of visible light-responded catalysis material ferrochrome vanadate CrFe (VO that has is provided
4)
2and preparation method thereof.It prepares production cost and equipment requirement is low, and the material scatter for preparing is good, uniform granularity, chemical stability are good, the good stability of optical property, and it has less interband width, and Organic Hazardous Compounds is had to good Photocatalytic Degradation Property.
Technical scheme of the present invention is:
Have a visible light-responded ferrochrome vanadate catalysis material, its chemical formula is CrFe (VO
4)
2, its pattern is graininess, grain diameter is for being less than 10 microns.
The present invention provides the preparation method of above-mentioned ferrochrome vanadate catalysis material simultaneously, and described method is high-temperature solid phase reaction method, comprises the following steps:
(1) press chemical formula CrFe (VO
4)
2the stoichiometric proportion of middle respective element, takes respectively and contains chromium ion Cr
3+compound, contain iron ion Fe
3+compound, contain vanadium ion V
5+compound, grind and mix, obtain mixture;
(2) by mixture precalcining under air atmosphere in above-mentioned steps (1), calcining heat is 300～500 ℃, and calcination time is 3～15 hours, naturally cooling;
(3) mixture of precalcining grinds and mixes, and in air atmosphere, calcines, and calcining heat is 500～1000 ℃, and calcination time is 5～20 hours, obtains ferrochrome vanadate catalysis material after naturally cooling.
Further, preferred, described containing chromium ion Cr
3+compound be a kind of in chromium oxide, chromium carbonate, chromic nitrate, chromium sulfate or chromium hydroxide; Described containing iron ion Fe
3+compound be a kind of in iron oxide, ferric carbonate, iron hydroxide, ferric nitrate, ferric sulfate or iron chloride;
Further, preferred, the described vanadium ion V that contains
5+compound be a kind of in vanadic anhydride or ammonium metavanadate.
Further, preferred, the precalcining temperature described in step (2) is 350～500 ℃, and calcination time is 5～12 hours; Calcining heat described in step (3) is 500～900 ℃, and calcination time is 9～15 hours.
Above-mentioned a kind of preparation method with visible light-responded ferrochrome vanadate catalysis material, can also adopt chemical solution method, and the method comprises the following steps:
(1) according to chemical formula CrFe (VO
4)
2the stoichiometric proportion of middle respective element takes raw material: containing chromium ion Cr
3+compound, contain iron ion Fe
3+compound, contain vanadium ion V
5+compound, the raw material taking is dissolved in respectively in rare nitric acid;
(2) containing vanadium ion V
5+solution in, in whipping process, add vanadium ion V
5+the complexing agent that mole is 1.5～2 times, obtains vanadium ion V
5+complex liquid;
(3) by above-mentioned vanadium ion V
5+complex liquid in temperature, be to stir after 1～5 hour under the condition of 20～60 ℃, slowly add containing chromium ion Cr respectively
3+compound and contain iron ion Fe
3+the solution of compound, both add in no particular order order, are to stir 1～5 hour under the condition of 60～100 ℃ in temperature, standing, obtain fluffy presoma after drying;
(4) above-mentioned presoma is calcined for the first time in air atmosphere, calcining heat is 250～500 ℃, and calcination time is 1～15 hour; Naturally after cooling, grind and mix, in air atmosphere, calcine for the second time, calcining heat is 500～800 ℃, and calcination time is 3～20 hours, obtains ferrochrome vanadate catalysis material.
Further, preferably, described in step (1) is a kind of in chromium oxide, chromium carbonate, chromic nitrate, chromium sulfate or chromium hydroxide containing the compound of chromium ion, the described compound containing iron ion is a kind of in iron oxide, ferric carbonate, iron hydroxide, ferric nitrate, ferric sulfate or iron chloride, and the described compound that contains vanadium ion is a kind of in vanadic anhydride or ammonium metavanadate;
Further, preferred, the complexing agent described in chemical solution method step (2) is a kind of in citric acid, oxalic acid.
Further, preferred, described in chemical solution method step (4), calcining heat is 300～500 ℃ for the first time, and calcination time is 3～9 hours; Calcining heat is 500～650 ℃ for the second time, and calcination time is 5～15 hours.
Above-mentioned a kind of preparation method with visible light-responded ferrochrome vanadate catalysis material, can also adopt coprecipitation, and the method comprises the following steps:
(1) according to chemical formula CrFe (VO
4)
2the stoichiometric proportion of middle chromium, iron and v element, takes respectively and contains chromium ion Cr
3+compound, contain iron ion Fe
3+compound, contain vanadium ion V
5+compound;
(2) by the chromium ion Cr taking
3+compound, iron ion Fe
3+compound, vanadium ion V
5+compound be dissolved in respectively water or be dissolved in watery hydrochloric acid, the solution of various raw materials is mixed, the mixing of three kinds of raw materials is order in no particular order, obtain the mixed liquor of each raw material, be heated to 60～90 ℃, and keep a certain stationary temperature, under stirring condition, use alkaline solution to regulate the PH of mixed liquor between 6～10, finally obtain flocky precipitate;
(3), by sediment obtained above washing, isolated by filtration, is to dry under the condition of 50～100 ℃ in temperature;
(4) sediment of cleaning in above-mentioned steps (3), dry is calcined in air atmosphere, calcining heat is 500～900 ℃, and calcination time is 1～20 hour, obtains ferrochrome vanadate catalysis material after naturally cooling.
Further, preferably, described in step (1), containing the compound of chromium ion, be a kind of in chromium oxide, chromium carbonate, chromic nitrate, chromium sulfate or chromium hydroxide, the described compound containing iron ion is a kind of in iron oxide, ferric carbonate, iron hydroxide, ferric nitrate, ferric sulfate or iron chloride, and the described compound that contains vanadium ion is a kind of in vanadic anhydride or ammonium metavanadate;
Further, preferred, described in step (2), alkaline solution is NaOH solution, KOH solution, Ca (OH)
2solution, NaNH
2solution, NH
3h
2o solution, Na
2cO
3solution, NaHCO
3a kind of in solution;
Further, preferred, the calcining heat described in step (3) is 600～800 ℃, and calcination time is 5～10 hours.
The above-mentioned a kind of application of visible light-responded ferrochrome vanadate catalysis material in degradating organic dye pollutant that have.
Advantage of the present invention is:
(1) CrFe (VO
4)
2photocatalyst material be take inorganic salts as raw material, and this compound is without any toxicity, and handling safety, energy consumption is low, cost is low, and the powder particle obtaining is little and even.
(2) preparation method of the present invention is simple, without any need for special installation, does not need special atmosphere, and all reaction conditions are gentle, are easy to suitability for industrialized production.Compare with other sulfide, halide and the preparation of some nano material thereof, without waste water and gas discharge, environmentally friendly.
(3) prepared CrFe (VO
4)
2photochemical catalyst have narrower can band gap (2.11eV), be far smaller than TiO
23.2eV, CrFe (VO
4)
2photochemical catalyst all has absorption within the scope of very wide solar spectrum.
(4) under visible ray (λ>=420nm) irradiates, CrFe (VO
4)
2photochemical catalyst can high efficiency photocatalysis degradation of methylene blue, has good photocatalytic activity.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described:
Fig. 1 is the prepared CrFe (VO of the embodiment of the present invention 1
4)
2the X-ray powder diffraction collection of illustrative plates of sample;
Fig. 2 is the prepared CrFe (VO of the embodiment of the present invention 1
4)
2the SEM SEM photo of sample;
Fig. 3 is the prepared CrFe (VO of the embodiment of the present invention 1
4)
2sample UV-Vis DRS spectrum;
Fig. 4 is the prepared CrFe (VO of the embodiment of the present invention 1
4)
2sample is the degradation curve to organic dyestuff methylene blue under different visible light application times;
Fig. 5 is the prepared CrFe (VO of embodiment 4
4)
2the electron scanning micrograph of sample;
Fig. 6 is the prepared CrFe (VO of embodiment 4
4)
2sample is the degradation curve to organic dyestuff methylene blue under different visible light application times;
Fig. 7 is the prepared CrFe (VO of embodiment 7
4)
2the electron scanning micrograph of sample;
Fig. 8 is the prepared CrFe (VO of embodiment 7
4)
2sample is the degradation curve to organic dyestuff methylene blue under different visible light application times.
The specific embodiment
Embodiment 1: solid reaction process is prepared CrFe (VO
4)
2and degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO
4)
2the stoichiometric proportion of middle respective element, takes respectively chromium oxide Cr
2o
3: 0.95 gram, iron oxide Fe
2o
3: 1.00 grams, ammonium metavanadate NH
4vO
3: 2.925 grams, in agate mortar, grind and mix, obtain mixture;
(2) get the mixture in above-mentioned steps (1), select air atmosphere to carry out precalcining, calcining heat is 300 ℃, and calcination time 15 hours is naturally cooling;
(3) take out sample, by the mixture after precalcining, fully mixed grinding is even again, places it in Muffle furnace, under air atmosphere, calcines, and calcining heat is 1000 ℃, and calcination time is 5 hours, obtains ferrochrome vanadate CrFe (VO
4)
2powder.
To prepared ferrochrome vanadate CrFe (VO
4)
2material carries out dependence test, is illustrated in figure 1 the present embodiment CrFe (VO
4)
2the X-ray powder diffraction collection of illustrative plates of sample, XRD test result shows, prepared ferrochrome vanadate CrFe (VO
4)
2for monophase materials, without any other dephasign, exist, and degree of crystallinity is better;
Be illustrated in figure 2 the present embodiment CrFe (VO
4)
2the SEM electron scanning micrograph of sample, as can be seen from the figure sample crystallizes into irregular grain shape, and the size of particle is between 0.5-2 micron, and average grain diameter is approximately 1 micron.
Be illustrated in figure 3 the present embodiment CrFe (VO
4)
2the UV-Vis DRS spectrum of sample, as can be seen from the figure, this sample has good light absorption in ultraviolet to the range of wavelengths (200-700 nanometer) of visible ray, and the width between material conduction band and valence band is roughly 2.11eV;
Get the present embodiment CrFe (VO
4)
2sample carries out the experiment of photocatalytic degradation methylene blue:
Adopt self-control photocatalytic reaction device, illuminator is the cylindrical shape xenon lamp of 500W, the cylindrical light-catalyzed reaction instrument that reactive tank is used pyrex to make, illuminator is inserted in reactive tank, between illuminator and liquid level, place filter plate and filter ultraviolet light and infrared light, and pass into condensed water cooling, during reaction, temperature is room temperature.Catalyst amount 100mg, liquor capacity 250mL, the concentration of methylene blue is 10mg/L.Catalyst is placed in reactant liquor, and catalysis time is set as 120 minutes, starts illumination after opening condensed water, after illumination, every 15min gets sample one time, centrifugal, get its supernatant, with ultraviolet-visible spectrophotometer, at wavelength 664-666nm place, measure the absorbance of methylene blue solution.According to Lambert-Beer's law, the absorbance of solution is directly proportional to concentration, and therefore available absorbance replaces concentration to calculate clearance, as the clearance of methylene blue solution.Computing formula: degradation rate=(1-C/C
0) * 100%=(1-A/A
0) * 100%, wherein C
0, C is respectively the concentration before and after photocatalytic degradation, A
0, A be respectively degraded before and after absorbance.
Obtain sample CrFe (VO as shown in Figure 4
4)
2degradation curve to organic dyestuff methylene blue under different visible light application times.As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue reaches 90.81% in 240 minutes, and the pure phase CrFe (VO preparing is described
4)
2material has photocatalytic activity.
Embodiment 2: solid reaction process is prepared CrFe (VO
4)
2and degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO
4)
2the stoichiometric proportion of middle respective element, takes respectively chromium hydroxide Cr (OH)
3: 1.29 grams, iron oxide Fe
2o
3: 1.00 grams, ammonium metavanadate NH
4vO
3: 2.925 grams, in agate mortar, grind and mix, obtain mixture;
(2) get the mixture of above-mentioned steps (1), select air atmosphere to carry out precalcining, precalcining temperature is 500 ℃, and calcination time 3 hours is naturally cooling;
(3) take out sample, the mixture of precalcining is fully ground again, be placed in Muffle furnace, under air atmosphere, calcine, calcining heat is 500 ℃, and calcination time is 20 hours, obtains ferrochrome vanadate CrFe (VO
4)
2powder.
Get CrFe (VO prepared by the present embodiment
4)
2sample carries out the experiment of row photocatalytic degradation methylene blue, and its experimental procedure is with embodiment 1.
After measured, the crystal structure of photocatalysis sample that the present embodiment obtains is, the pattern of outward appearance, similar to embodiment 1 to the degradation rate of methylene blue.
Embodiment 3: solid reaction process is prepared CrFe (VO
4)
2and degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO
4)
2middle corresponding chemical element dose ratio, takes respectively chromium sulfate Cr
2(SO
4)
3: 1.96 grams, iron oxide Fe
2o
3: 0.80 gram, ammonium metavanadate NH
4vO
3: 2.34 grams, in agate mortar, grind and mix, obtain mixture;
(2) get the mixture of above-mentioned steps (1), select air atmosphere to carry out precalcining, precalcining temperature is 350 ℃, and calcination time 7 hours is naturally cooling;
(3) take out sample, after the raw material of precalcining is fully ground again, be placed in Muffle furnace, under air atmosphere, calcine, calcining heat is 900 ℃, and calcination time is 13 hours, obtains ferrochrome vanadate CrFe (VO
4)
2powder.
Get CrFe (VO prepared by the present embodiment
4)
2sample carries out the experiment of row photocatalytic degradation methylene blue, and its experimental procedure is with embodiment 1.
The crystal structure of photocatalysis sample that the present embodiment obtains is, the pattern of outward appearance, similar to embodiment 1 to the degradation rate of methylene blue.
Embodiment 4: chemical solution method is prepared CrFe (VO
4)
2and degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO
4)
2the chemical dosage ratio of middle respective element, takes respectively chromium oxide Cr
2o
3: 1.09 grams, iron oxide Fe
2o
3: 1.14 grams, ammonium metavanadate NH
4vO
3: 3.34 grams, be dissolved in respectively in rare nitric acid;
(2) take oxalic acid H
2c
2o
4-2H
2o:14.41 gram, adds under stirring and contains vanadium ion V
5+solution in, at 20 ℃, stir 5 hours, obtain oxalic acid complexing vanadium ion V
5+complex liquid;
(3) solution that contains chromium ion and iron ion is added respectively to this oxalic acid complexing vanadium ion V
5+complex liquid among, both add in no particular order; The mixed liquor obtaining is stirred 1 hour under the condition of 100 ℃, rest on subsequently in the baking oven of 50 ℃, until obtain fluffy presoma;
(4) presoma above-mentioned steps (3) being obtained is calcined in air atmosphere, calcining heat is 250 ℃, and calcination time is 15 hours, is then cooled to room temperature, take out sample, by the raw material of calcining for the first time, fully mixed grinding is even again, in air atmosphere, calcines for the second time, and calcining heat is 800 ℃, calcination time 3 hours, then be cooled to room temperature, take out sample, obtain ferrochrome vanadate CrFe (VO
4)
2powder.
Be illustrated in figure 5 CrFe (VO prepared by the present embodiment
4)
2the electron scanning micrograph of sample, as can be seen from the figure sample crystallizes into irregular grain shape, and the size of particle is between 200-500 nanometer, and average grain diameter is approximately 300 nanometers.
Get the present embodiment CrFe (VO
4)
2sample carries out the experiment of photocatalytic degradation methylene blue, and its experimental procedure is with embodiment 1.
Sample CrFe (VO as shown in Figure 6
4)
2degradation curve to organic dyestuff methylene blue under visible light application time.As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue reaches 90% in 180 minutes, and the pure phase CrFe (VO preparing is described
4)
2material has photocatalytic activity.
Embodiment 5: chemical solution method is prepared CrFe (VO
4)
2and degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO
4)
2the dose ratio of middle corresponding chemical element, takes respectively chromic nitrate Cr (NO
3)
39H
2o:2.00 gram, ferric nitrate Fe (NO
3)
39H
2o:2.02 gram, ammonium vanadate NH
4vO
3: 1.17 grams, be dissolved in respectively in rare nitric acid;
(2) take citric acid C
6h
8o
7: 2.882 grams, under stirring, add and contain vanadium ion V
5+solution in, at 60 ℃, stir 1 hour, obtain oxalic acid complexing vanadium ion V
5+complex liquid;
(3) solution that contains chromium ion and iron ion is added respectively to this oxalic acid complexing vanadium ion V
5+complex liquid among, both add in no particular order; The mixed liquor obtaining is stirred 1 hour under the condition of 60 ℃, rest on subsequently in the baking oven of 100 ℃, until obtain fluffy presoma;
(4) presoma above-mentioned steps (3) being obtained is calcined in air atmosphere, calcining heat is 500 ℃, and calcination time is 1 hour, is then cooled to room temperature, take out sample, by the raw material of calcining for the first time, fully mixed grinding is even again, in air atmosphere, calcines for the second time, and calcining heat is 500 ℃, calcination time 20 hours, then be cooled to room temperature, take out sample, obtain ferrochrome vanadate CrFe (VO
4)
2powder.
Get the present embodiment gained CrFe (VO
4)
2sample carries out SEM takes pictures, degradation of methylene blue experiment, and result shows its main structure and morphology, similar to embodiment 4 to the degradation rate of methylene blue.
Embodiment 6: chemical solution method is prepared CrFe (VO
4)
2and degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO
4)
2the dose ratio of middle corresponding chemical element, takes respectively chromium hydroxide Cr (OH)
3: 0.79 gram, ferric nitrate Fe (NO
3)
39H
2o:3.11 gram, ammonium vanadate NH
4vO
3: 1.80 grams, be dissolved in respectively in rare nitric acid;
(2) take oxalic acid H
2c
2o
4-2H
2o:11.64 gram, adds under stirring and contains vanadium ion V
5+solution in, at 50 ℃, stir 2 hours, obtain oxalic acid complexing vanadium ion V
5+complex liquid;
(3) solution that contains chromium ion and iron ion is added respectively to this oxalic acid complexing vanadium ion V
5+complex liquid among, both add in no particular order; The mixed liquor obtaining is stirred 3 hours under the condition of 80 ℃, rest on subsequently in the baking oven of 100 ℃, until obtain fluffy presoma;
(4) presoma above-mentioned steps (3) being obtained is calcined in air atmosphere, and calcining heat is 400 ℃, and calcination time is 5 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, in air atmosphere, calcines for the second time, and calcining heat is 750 ℃, and calcination time 10 hours, is then cooled to room temperature, takes out sample, obtains ferrochrome vanadate CrFe (VO
4)
2powder.
Get the present embodiment gained CrFe (VO
4)
2sample carries out SEM takes pictures, degradation of methylene blue experiment, and result shows its main structure and morphology, similar to embodiment 4 to the degradation rate of methylene blue.
Embodiment 7: coprecipitation is prepared CrFe (VO
4)
2and degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO
4)
2the dose ratio of middle corresponding chemical element, takes respectively chromic nitrate Cr (NO
3)
39H
2o:5.72 gram, ferric nitrate Fe (NO
3)
39H
2o:5.77 gram, vanadic anhydride V
2o
5: 2.60 grams;
(2) above-mentioned three kinds of compounds are dissolved in respectively in watery hydrochloric acid, are configured to the chromium salt solution that concentration is 1mol/L, iron salt solutions, vanadic salts solution; Mix three kinds of salting liquids and stir, 90 ℃ of heating water baths also keep constant temperature, and the ammonia spirit that is 40% to mixed solution and dripping volume fraction is about at 6 o'clock to PH and stops, and stirs, and obtains gradually cotton-shaped sediment;
(3) by the sediment washing obtaining for several times, isolated by filtration is placed in porcelain crucible, is to dry under the condition of 50 ℃ in temperature, obtains powder;
(4) by above-mentioned steps (3), clean to dry powder in air atmosphere, calcine, calcining heat is 500 ℃, calcination time is 20 hours, obtains ferrochrome vanadate catalysis material after naturally cooling.
Be illustrated in figure 7 the prepared sample CrFe of the present embodiment (VO
4)
2scanning electron microscope diagram, as can be seen from the figure sample crystallizes into irregular long plate shape and grain shape, granule size 0.5-1 micron.
Get CrFe (VO prepared by the present embodiment
4)
2sample carries out methylene blue degradation experiment, and step, with embodiment 1, obtains sample CrFe (VO as shown in Figure 8
4)
2degradation curve to organic dyestuff methylene blue under different visible light application times.As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue reaches 95% in 180 minutes, and the pure phase CrFe (VO preparing is described
4)
2material has photocatalytic activity.
Result shows CrFe (VO in the present embodiment
4)
2sample primary structure pattern, similar to embodiment 1 to the kinetic curve of the degradation rate of methylene blue and degradation of methylene blue.
Embodiment 8: coprecipitation is prepared CrFe (VO
4)
2and degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO
4)
2the dose ratio of middle corresponding chemical element, takes respectively chromium sulfate Cr
2(SO
4)
3: 4.90 grams, ferric sulfate Fe
2(SO
4)
3: 5.00 grams, ammonium vanadate NH
4vO
3: 5.85 grams;
(2) above-mentioned three kinds of compounds are dissolved in respectively in watery hydrochloric acid, are configured to the chromium salt solution that concentration is 1mol/L, iron salt solutions, vanadic salts solution; Mix three kinds of dissolved salt liquid and constantly stir, the ammonia spirit that is 40% to mixed solution and dripping volume fraction, is about at 10 o'clock to PH and stops, and heating water bath to 60 ℃ also keeps constant temperature, stirs, and obtains gradually cotton-shaped sediment;
(3) by the sediment washing obtaining for several times, isolated by filtration is placed in porcelain crucible, is to dry under the condition of 100 ℃ in temperature, obtains powder;
(4) by above-mentioned steps (3), clean to dry powder in air atmosphere, calcine, calcining heat is 900 ℃, calcination time is 1 hour, must ferrochrome vanadate catalysis material after naturally cooling.
The structure and morphology of the ferrochrome vanadate catalysis material that after measured, the present embodiment obtains, similar to embodiment 7 to the degradation rate of methylene blue.
By above-described embodiment, can find out the novel ferrochrome vanadate CrFe (VO in the present invention
4)
2catalysis material, can prepare by high-temperature solid phase reaction method, chemical solution method and coprecipitation several method, its production cost and equipment requirement are low, the material scatter for preparing is good, uniform granularity, chemical stability are good, the good stability of optical property, and it has less interband width, has excellent photocatalysis performance, under visible light-responded, there is the effect of decomposing harmful chemical, light-catalysed good stability, has a good application prospect.
Claims (10)
1. have a visible light-responded ferrochrome vanadate catalysis material, it is characterized in that, its chemical formula is CrFe (VO
4)
2, its pattern is graininess, grain diameter is for being less than 10 microns.
2. a kind of preparation method with visible light-responded ferrochrome vanadate catalysis material as claimed in claim 1, is characterized in that, described method is high-temperature solid phase reaction method, comprises the following steps:
(1) press chemical formula CrFe (VO
4)
2the stoichiometric proportion of middle respective element, takes respectively and contains chromium ion Cr
3+compound, contain iron ion Fe
3+compound, contain vanadium ion V
5+compound, grind and mix, obtain mixture;
(2) by mixture precalcining under air atmosphere in above-mentioned steps (1), calcining heat is 300～500 ℃, and calcination time is 3～15 hours, naturally cooling;
(3) mixture of precalcining is ground and mixed, in air atmosphere, calcine, calcining heat is 500～1000 ℃, and calcination time is 5～20 hours, obtains ferrochrome vanadate catalysis material after naturally cooling.
3. preparation method according to claim 2, is characterized in that, described containing chromium ion Cr
3+compound be a kind of in chromium oxide, chromium carbonate, chromic nitrate, chromium sulfate or chromium hydroxide; Described containing iron ion Fe
3+compound be a kind of in iron oxide, ferric carbonate, iron hydroxide, ferric nitrate, ferric sulfate or iron chloride; The described vanadium ion V that contains
5+compound be a kind of in vanadic anhydride or ammonium metavanadate.
4. preparation method according to claim 2, is characterized in that, the calcining heat described in step (2) is 350～500 ℃, and calcination time is 5～12 hours; Calcining heat described in step (3) is 500～900 ℃, and calcination time is 9～15 hours.
5. a kind of preparation method with visible light-responded ferrochrome vanadate catalysis material as claimed in claim 1, is characterized in that, described method is chemical solution method, comprises the following steps:
(1) according to chemical formula CrFe (VO
4)
2the stoichiometric proportion of middle respective element takes raw material: containing chromium ion Cr
3+compound, contain iron ion Fe
3+compound, contain vanadium ion V
5+compound, the raw material taking is dissolved in respectively in rare nitric acid;
(2) containing vanadium ion V
5+solution in, in whipping process, add vanadium ion V
5+the complexing agent that mole is 1.5～2 times, obtains complexing vanadium ion V
5+complex liquid;
(3) by above-mentioned vanadium ion V
5+complex liquid in temperature, be to stir after 1～5 hour under the condition of 20～60 ℃, slowly add containing chromium ion Cr respectively
3+compound and contain iron ion Fe
3+the solution of compound, both add in no particular order order, are to stir 1～5 hour under the condition of 60～100 ℃ in temperature, standing, obtain fluffy presoma after drying;
(4) above-mentioned presoma is calcined for the first time in air atmosphere, calcining heat is 250～500 ℃, calcination time is 1～15 hour, naturally after cooling, grind and mix, in air atmosphere, calcine for the second time, calcining heat is 500～800 ℃, calcination time is 3～20 hours, obtains ferrochrome vanadate catalysis material.
6. preparation method according to claim 5, it is characterized in that, described in step (1) is a kind of in chromium oxide, chromium carbonate, chromic nitrate, chromium sulfate or chromium hydroxide containing the compound of chromium ion, the described compound containing iron ion is a kind of in iron oxide, ferric carbonate, iron hydroxide, ferric nitrate, ferric sulfate or iron chloride, and the described compound that contains vanadium ion is a kind of in vanadic anhydride or ammonium metavanadate; Complexing agent described in step (2) is a kind of in citric acid, oxalic acid.
7. preparation method according to claim 5, is characterized in that, calcining for the first time described in step (4), calcining heat is 300～500 ℃, and calcination time is 3～9 hours, described calcining for the second time, calcining heat is 500～650 ℃, and calcination time is 5～15 hours.
8. a kind of preparation method with visible light-responded ferrochrome vanadate catalysis material as claimed in claim 1, is characterized in that, described method is coprecipitation, comprises the following steps:
(1) according to chemical formula CrFe (VO
4)
2the stoichiometric proportion of middle chromium, iron and v element, takes respectively and contains chromium ion Cr
3+compound, contain iron ion Fe
3+compound, contain vanadium ion V
5+compound;
(2) by the chromium ion Cr taking
3+compound, iron ion Fe
3+compound, vanadium ion V
5+compound be dissolved in respectively water or be dissolved in watery hydrochloric acid, the solution of various raw materials is mixed, the mixing of three kinds of raw materials is order in no particular order, obtain the mixed liquor of each raw material, be heated to 60～90 ℃, and keep a certain stationary temperature, under stirring condition, use alkaline solution to regulate the PH of mixed liquor between 6～10, finally obtain flocky precipitate;
(3), by sediment obtained above washing, isolated by filtration, is to dry under the condition of 50～100 ℃ in temperature;
(4) sediment of cleaning in above-mentioned steps (3), dry is calcined in air atmosphere, calcining heat is 500～900 ℃, and calcination time is 1～20 hour, obtains ferrochrome vanadate catalysis material after naturally cooling.
9. preparation method according to claim 8, it is characterized in that, described in step (1), containing the compound of chromium ion, be a kind of in chromium oxide, chromium carbonate, chromic nitrate, chromium sulfate or chromium hydroxide, the described compound containing iron ion is a kind of in iron oxide, ferric carbonate, iron hydroxide, ferric nitrate, ferric sulfate or iron chloride, and the described compound that contains vanadium ion is a kind of in vanadic anhydride or ammonium metavanadate; Described in step (2), alkaline solution is NaOH solution, KOH solution, Ca (OH)
2solution, NaNH
2solution, NH
3h
2o solution, Na
2cO
3solution, NaHCO
3a kind of in solution; Calcining heat described in step (3) is 600～800 ℃, and calcination time is 5～10 hours.
10. a kind of application of visible light-responded ferrochrome vanadate catalysis material in degradating organic dye pollutant that have as claimed in claim 1.
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