CN104174408B - A kind of have visible light-responded ferrochrome vanadate photocatalytic material and its preparation method and application - Google Patents

A kind of have visible light-responded ferrochrome vanadate photocatalytic material and its preparation method and application Download PDF

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CN104174408B
CN104174408B CN201410339327.1A CN201410339327A CN104174408B CN 104174408 B CN104174408 B CN 104174408B CN 201410339327 A CN201410339327 A CN 201410339327A CN 104174408 B CN104174408 B CN 104174408B
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马忠
谢洪德
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Suzhou Dejie Membrane Material Technology Co Ltd
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Abstract

The invention discloses and a kind of there is visible light-responded ferrochrome vanadate photocatalytic material CrFe (VO4)2And its preparation method and application.Inventive samples is to adopt high-temperature solid phase reaction method, chemical solution method, coprecipitation to prepare, and production cost and equipment requirements are low, and the material scatter of preparation is good, uniform granularity, chemical stability are good, the good stability of optical property.The photocatalyst sample CrFe (VO of preparation4)2There is less interband width, there is the photocatalysis performance of excellence, under visible light-responded, there is the effect decomposing harmful chemical, light-catalysed good stability, have a good application prospect.

Description

A kind of have visible light-responded ferrochrome vanadate photocatalytic material and its preparation method and application
Technical field
The present invention relates to a kind of preparation method with visible light-responded ferrochrome vanadate photocatalytic material and application thereof, particularly to the photocatalyst CrFe (VO for degradable organic pollutant4)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 needing solution badly.At present, the main source of energy remains oil, the fuel such as natural gas and coal.But, a large amount of consumption of Fossil fuel, a large amount of toxic gas can be discharged, various problem of environmental pollutions relevant with it also occur in succession.Therefore, develop continuable energy technology to be brought into schedule.In all reproducible energy technologys, including water generating, solar energy, wind energy, geothermal energy and bioenergy, wherein, utilize photovoltaic technology to convert solar energy into electric energy, be solve the energy sustainable supply the most promising technology of problem.Owing to solar energy totally cleans, use will not cause environmental pollution, in liberal supply, impinging upon ground solar energy every day is more than 10,000 times of the energy needed for whole world every day, now, solar photoelectric has been taken as the third-largest regenerative resource in the whole world, and to the end of the year 2012, the accumulation sunlight electric energy in the whole world has broken through 100GW high point.Effectively directly utilizing of solar energy, develops efficient sunlight response type semiconductor catalyst, is the core means solving energy crisis and environmental problem two fold problem.
Along with developing rapidly of modern social economy, the energy and ecological environment increasingly cause the concern of people, solve the energy and problem of environmental pollution be realize China's sustainable development, improve people's living standard and safeguard national security in the urgent need to.The Organic substance of some difficult degradations such as dyestuff, pesticide etc. are often present in air, water body and soil with very low concentration, have a strong impact on the Health and Living of people.So, environment purification pollutes cost-effectively is the significant problem faced now.The method of conventional process sewage mainly has 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 desirably environmental pollution treatment technology, becomes the study hotspot of people.
Light-catalyzed reaction refers to that photocatalyst is absorbing after higher than the photon of its band-gap energy, generates hole and electronics, and these holes and electronics carry out oxidation reaction and reduction reaction respectively, reaches to decompose the purpose of harmful chemical, organic-biological matter and sterilization.From phase late 1970s, there has been proposed and utilize in photocatalyst decomposition water and the Organic substance such as pesticide in air and odorant, and scribble the application example such as self-cleaning of the surface of solids of photocatalyst.Photocatalyst has many kinds, and wherein most representative is titanium dioxide (TiO2), utilize titanium dioxide that the Organic substances such as the pesticide in water and in air and odorant are decomposed, but the band gap of titanium dioxide is 3.2eV, under the ultraviolet irradiation shorter than 400nm, only just can show activity, can only at indoor or the local work having uviol lamp, being little to utilize visible ray, this greatly limits the use of titanium dioxide optical catalyst.Generally having two ways to develop visible light-responded catalyst, a kind of method is to TiO2It is modified, is coupled with metal-oxide by carried noble metal, doped metal ion etc. and to make its absorbing wavelength red shift and to reduce the recombination probability of light induced electron and photohole, thus carrying high catalytic activity.But from many results of study, modified photocatalyst photocatalytic activity under sunlight is not high, and stability is bad.
Second method is development of new catalysis material, such as oxynitride, titanate, tungstates, vanadate, niobates, chromate, also there is good visible photic photocatalytic activity and chemical stability, work in this respect has more DEVELOPMENT PROSPECT, and therefore the exploitation of the photocatalyst that non-oxide titanium is visible light-responded is increasingly subject to people's attention.The present invention is the preparation method about a kind of novel ferrochrome vanadate photocatalyst material and application thereof, and it has the optical absorption in visible-range, has the visible light-responded photocatalysis performance of excellence, it is possible to as photocatalyst for degrading Organic substance.
Summary of the invention
The present invention seeks to: provide a kind of and there is visible light-responded catalysis material ferrochrome vanadate CrFe (VO4)2And preparation method thereof.It prepares production cost and equipment requirements is low, and the material scatter prepared is good, uniform granularity, chemical stability are good, the good stability of optical property, and it has less interband width, and Organic Hazardous Compounds has excellent Photocatalytic Degradation Property.
The technical scheme is that
A kind of have visible light-responded ferrochrome vanadate photocatalytic material, and its chemical formula is CrFe (VO4)2, its pattern is graininess, and grain diameter is less than 10 microns.
The preparation method that invention also provides above-mentioned ferrochrome vanadate photocatalytic material, described method is high-temperature solid phase reaction method, comprises the following steps:
(1) by chemical formula CrFe (VO4)2The stoichiometric proportion of middle respective element, weighs respectively containing chromium ion Cr3+Compound, containing iron ion Fe3+Compound, containing vanadium ion V5+Compound, grind and mix homogeneously, obtain mixture;
(2) by mixture precalcining in air atmosphere in above-mentioned steps (1), calcining heat is 300~500 DEG C, and calcination time is 3~15 hours, natural cooling;
(3) mixture of precalcining grinds and mix homogeneously, calcines in air atmosphere, and calcining heat is 500~1000 DEG C, and calcination time is 5~20 hours, obtains ferrochrome vanadate photocatalytic material after natural cooling.
Further, it is preferred that described containing chromium ion Cr3+Compound be the one in chromium oxide, chromium carbonate, chromic nitrate, chromic sulfate or chromic oxide gel;Described containing iron ion Fe3+Compound be the one in ferrum oxide, ferric carbonate, hydrated ferric oxide., ferric nitrate, iron sulfate or iron chloride;
Further, it is preferred that described contains vanadium ion V5+Compound be the one in vanadic anhydride or ammonium metavanadate.
Further, it is preferred that the precalcining temperature described in step (2) is 350~500 DEG C, calcination time is 5~12 hours;Calcining heat described in step (3) is 500~900 DEG C, and calcination time is 9~15 hours.
Above-mentioned a kind of preparation method with visible light-responded ferrochrome vanadate photocatalytic material, it is also possible to adopting chemical solution method, the method comprises the following steps:
(1) according to chemical formula CrFe (VO4)2The stoichiometric proportion of middle respective element weighs raw material: containing chromium ion Cr3+Compound, containing iron ion Fe3+Compound, containing vanadium ion V5+Compound, the raw material weighed is dissolved separately in dust technology;
(2) containing vanadium ion V5+Solution in, in whipping process add vanadium ion V5+The chelating agent that mole is 1.5~2 times, obtains vanadium ion V5+Complex liquid;
(3) by above-mentioned vanadium ion V5+Complex liquid stir 1~5 hour when temperature is 20~60 DEG C after, be respectively added slowly to containing chromium ion Cr3+Compound and containing iron ion Fe3+The solution of compound, both additions are order in no particular order, stirs 1~5 hour when temperature is 60~100 DEG C, obtains fluffy presoma after standing, drying;
(4) above-mentioned presoma carries out first time calcining in air atmosphere, and calcining heat is 250~500 DEG C, and calcination time is 1~15 hour;After natural cooling, grinding and mix homogeneously, carry out second time calcining in air atmosphere, calcining heat is 500~800 DEG C, and calcination time is 3~20 hours, obtains ferrochrome vanadate photocatalytic material.
Further, preferably, the compound containing chromium ion described in step (1) is the one in chromium oxide, chromium carbonate, chromic nitrate, chromic sulfate or chromic oxide gel, the described compound containing iron ion is the one in ferrum oxide, ferric carbonate, hydrated ferric oxide., ferric nitrate, iron sulfate or iron chloride, and the described compound containing vanadium ion is the one in vanadic anhydride or ammonium metavanadate;
Further, it is preferred that the chelating agent described in chemical solution method step (2) is the one in citric acid, oxalic acid.
Further, it is preferred that first time calcining heat described in chemical solution method step (4) is 300~500 DEG C, and calcination time is 3~9 hours;Second time calcining heat is 500~650 DEG C, and calcination time is 5~15 hours.
Above-mentioned a kind of preparation method with visible light-responded ferrochrome vanadate photocatalytic material, it is also possible to adopting coprecipitation, the method comprises the following steps:
(1) according to chemical formula CrFe (VO4)2The stoichiometric proportion of middle chromium, ferrum and v element, weighs respectively containing chromium ion Cr3+Compound, containing iron ion Fe3+Compound, containing vanadium ion V5+Compound;
(2) the chromium ion Cr that will weigh3+Compound, iron ion Fe3+Compound, vanadium ion V5+Compound be dissolved separately in water or be dissolved in dilute 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, heating is to 60~90 DEG C, and keeps 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) precipitate obtained above is washed, isolated by filtration, dry when temperature is 50~100 DEG C;
(4) being calcined in air atmosphere by the precipitate cleaned in above-mentioned steps (3), dry, calcining heat is 500~900 DEG C, and calcination time is 1~20 hour, obtains ferrochrome vanadate photocatalytic material after natural cooling.
Further, preferably, described in step (1), the compound containing chromium ion is the one in chromium oxide, chromium carbonate, chromic nitrate, chromic sulfate or chromic oxide gel, the described compound containing iron ion is the one in ferrum oxide, ferric carbonate, hydrated ferric oxide., ferric nitrate, iron sulfate or iron chloride, and the described compound containing vanadium ion is the one in vanadic anhydride or ammonium metavanadate;
Further, it is preferred that alkaline solution described in step (2) is NaOH solution, KOH solution, Ca (OH)2Solution, NaNH2Solution, NH3·H2O solution, Na2CO3Solution, NaHCO3One in solution;
Further, it is preferred that the calcining heat described in step (3) is 600~800 DEG C, calcination time is 5~10 hours.
Above-mentioned a kind of have the application in degradating organic dye pollutant of the visible light-responded ferrochrome vanadate photocatalytic material.
The invention have the advantage that
(1)CrFe(VO4)2Photocatalyst material is with inorganic salt for raw material, and this compound does not have any toxicity, and operation safety, energy consumption is low, cost is low, and the powder particle obtained is little and uniform.
(2) preparation method of the present invention is simple, it is not necessary to any special installation, it is not necessary to special atmosphere, and all reaction conditions are gentle, it is easy to industrialized production.Compared with preparing with other sulfide, halogenide and some nano material thereof, discharge without waste water and gas, environmentally friendly.
(3) CrFe (VO prepared by4)2Photocatalyst has narrower energy band band gap (2.11eV), is far smaller than TiO23.2eV, CrFe (VO4)2Photocatalyst all has absorption within the scope of very wide solar spectrum.
(4) under visible ray (λ >=420nm) irradiates, CrFe (VO4)2Photocatalyst can high efficiency photocatalysis degradation of methylene blue, there is good photocatalytic activity.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described:
Fig. 1 is the CrFe (VO prepared by the embodiment of the present invention 14)2The X-ray powder diffraction pattern of sample;
Fig. 2 is the CrFe (VO prepared by the embodiment of the present invention 14)2The scanning electron microscope SEM photograph of sample;
Fig. 3 is the CrFe (VO prepared by the embodiment of the present invention 14)2Sample UV-Vis DRS spectrum;
Fig. 4 is the CrFe (VO prepared by the embodiment of the present invention 14)2Sample degradation curve to organic dyestuff methylene blue under different visible light application times;
Fig. 5 is the CrFe (VO prepared by embodiment 44)2The electron scanning micrograph of sample;
Fig. 6 is the CrFe (VO prepared by embodiment 44)2Sample degradation curve to organic dyestuff methylene blue under different visible light application times;
Fig. 7 is the CrFe (VO prepared by embodiment 74)2The electron scanning micrograph of sample;
Fig. 8 is the CrFe (VO prepared by embodiment 74)2Sample degradation curve to organic dyestuff methylene blue under different visible light application times.
Detailed description of the invention
Embodiment 1: solid reaction process prepares CrFe (VO4)2And degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO4)2The stoichiometric proportion of middle respective element, weighs chromium oxide Cr respectively2O3: 0.95 gram, ferrum oxide Fe2O3: 1.00 grams, ammonium metavanadate NH4VO3: 2.925 grams, grind and mix homogeneously in agate mortar, obtain mixture;
(2) taking the mixture in above-mentioned steps (1), select air atmosphere to carry out precalcining, calcining heat is 300 DEG C, calcination time 15 hours, natural cooling;
(3) taking out sample, the mixture after precalcining is sufficiently mixed grinding again uniformly, places it in Muffle furnace, calcine in air atmosphere, calcining heat is 1000 DEG C, and calcination time is 5 hours, namely obtains ferrochrome vanadate CrFe (VO4)2Powder.
To prepared ferrochrome vanadate CrFe (VO4)2Material carries out dependence test, is illustrated in figure 1 the present embodiment CrFe (VO4)2The X-ray powder diffraction pattern of sample, XRD test result shows, prepared ferrochrome vanadate CrFe (VO4)2For monophase materials, it does not have other dephasign any exists, and degree of crystallinity is better;
It is illustrated in figure 2 the present embodiment CrFe (VO4)2The SEM electron scanning micrograph of sample, as can be seen from the figure sample crystallizes into irregular grain shape, and the size of granule is between 0.5-2 micron, and mean diameter is about 1 micron.
It is illustrated in figure 3 the present embodiment CrFe (VO4)2The UV-Vis DRS spectrum of sample, it can be seen that this sample has good light to absorb at the range of wavelengths (200-700 nanometer) of ultraviolet to visible ray, the substantially 2.11eV of the width between material conduction band and valence band;
Take the present embodiment CrFe (VO4)2Sample carries out photocatalytic degradation methylene blue experiment:
Adopt self-control photocatalytic reaction device, illuminator is 500W cylinder shape xenon lamp, reactive tank uses the cylindrical light catalytic reaction instrument that pyrex is made, illuminator is inserted in reactive tank, place filter plate between illuminator and liquid level and filter ultraviolet light and infrared light, and passing 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 takes a sample, centrifugal, take its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer at wavelength 664-666nm place.According to Lambert-Beer's law, the absorbance of solution is directly proportional to concentration, therefore concentration can be replaced to calculate clearance with absorbance, as the clearance of methylene blue solution.Computing formula: degradation rate=(1-C/C0) × 100%=(1-A/A0) × 100%, wherein C0, concentration before and after C respectively photocatalytic degradation, A0, A respectively be degraded before and after absorbance.
Obtain sample CrFe (VO as shown in Figure 44)2Degradation curve to organic dyestuff methylene blue under different visible light application times.It can be seen that the degradation rate of this sample photocatalytic degradation methylene blue reaches 90.81% in 240 minutes, the pure phase CrFe (VO prepared is described4)2Material has photocatalytic activity.
Embodiment 2: solid reaction process prepares CrFe (VO4)2And degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO4)2The stoichiometric proportion of middle respective element, weighs chromic oxide gel Cr (OH) respectively3: 1.29 grams, ferrum oxide Fe2O3: 1.00 grams, ammonium metavanadate NH4VO3: 2.925 grams, grind and mix homogeneously in agate mortar, obtain mixture;
(2) taking the mixture of above-mentioned steps (1), select air atmosphere to carry out precalcining, precalcining temperature is 500 DEG C, calcination time 3 hours, natural cooling;
(3) taking out sample, be again fully ground by the mixture of precalcining, be placed in Muffle furnace, calcine in air atmosphere, calcining heat is 500 DEG C, and calcination time is 20 hours, namely obtains ferrochrome vanadate CrFe (VO4)2Powder.
Take CrFe (VO prepared by the present embodiment4)2Sample carries out the experiment of row photocatalytic degradation methylene blue, and its experimental procedure is with embodiment 1.
After measured, the present embodiment obtains the crystal structure of photocatalysis sample, the pattern of outward appearance, the degradation rate of methylene blue is similar to embodiment 1.
Embodiment 3: solid reaction process prepares CrFe (VO4)2And degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO4)2Middle corresponding chemical element dose ratio, weighs chromic sulfate Cr respectively2(SO4)3: 1.96 grams, ferrum oxide Fe2O3: 0.80 gram, ammonium metavanadate NH4VO3: 2.34 grams, grind and mix homogeneously in agate mortar, obtain mixture;
(2) taking the mixture of above-mentioned steps (1), select air atmosphere to carry out precalcining, precalcining temperature is 350 DEG C, calcination time 7 hours, natural cooling;
(3) taking out sample, be placed in Muffle furnace, calcine in air atmosphere after being again fully ground by the raw material of precalcining, calcining heat is 900 DEG C, and calcination time is 13 hours, namely obtains ferrochrome vanadate CrFe (VO4)2Powder.
Take CrFe (VO prepared by the present embodiment4)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, the pattern of outward appearance, the degradation rate of methylene blue is similar to embodiment 1.
Embodiment 4: chemical solution method prepares CrFe (VO4)2And degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO4)2The chemical dosage ratio of middle respective element, weighs chromium oxide Cr respectively2O3: 1.09 grams, ferrum oxide Fe2O3: 1.14 grams, ammonium metavanadate NH4VO3: 3.34 grams, it is dissolved separately in dust technology;
(2) oxalic acid H is weighed2C2O4-2H2O:14.41 gram, stirring is lower to add containing vanadium ion V5+Solution in, at 20 DEG C stir 5 hours, obtain oxalic acid complexation vanadium ion V5+Complex liquid;
(3) solution containing chromium ion and iron ion is separately added into this oxalic acid complexation vanadium ion V5+Complex liquid among, both additions are in no particular order;By the mixed liquor that obtains stirring 1 hour when 100 DEG C, rest on subsequently in the baking oven of 50 DEG C, until obtaining fluffy presoma;
(4) presoma that above-mentioned steps (3) obtains is calcined in air atmosphere, calcining heat is 250 DEG C, and calcination time is 15 hours, is subsequently cooled to room temperature, take out sample, the raw material of first time calcining being sufficiently mixed grinding again uniformly, carries out second time calcining in air atmosphere, calcining heat is 800 DEG C, calcination time 3 hours, it is subsequently cooled to room temperature, takes out sample, namely obtain ferrochrome vanadate CrFe (VO4)2Powder.
It is illustrated in figure 5 CrFe (VO prepared by the present embodiment4)2The electron scanning micrograph of sample, as can be seen from the figure sample crystallizes into irregular grain shape, and the size of granule is between 200-500 nanometer, and mean diameter is about 300 nanometers.
Take the present embodiment CrFe (VO4)2Sample carries out photocatalytic degradation methylene blue experiment, and its experimental procedure is with embodiment 1.
Sample CrFe (VO as shown in Figure 64)2Degradation curve to organic dyestuff methylene blue under visible light application time.It can be seen that the degradation rate of this sample photocatalytic degradation methylene blue reaches 90% in 180 minutes, the pure phase CrFe (VO prepared is described4)2Material has photocatalytic activity.
Embodiment 5: chemical solution method prepares CrFe (VO4)2And degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO4)2The dose ratio of middle corresponding chemical element, weighs chromic nitrate Cr (NO respectively3)3·9H2O:2.00 gram, ferric nitrate Fe (NO3)3·9H2O:2.02 gram, ammonium vanadate NH4VO3: 1.17 grams, it is dissolved separately in dust technology;
(2) citric acid C is weighed6H8O7: 2.882 grams, stirring is lower to add containing vanadium ion V5+Solution in, at 60 DEG C stir 1 hour, obtain oxalic acid complexation vanadium ion V5+Complex liquid;
(3) solution containing chromium ion and iron ion is separately added into this oxalic acid complexation vanadium ion V5+Complex liquid among, both additions are in no particular order;By the mixed liquor that obtains stirring 1 hour when 60 DEG C, rest on subsequently in the baking oven of 100 DEG C, until obtaining fluffy presoma;
(4) presoma that above-mentioned steps (3) obtains is calcined in air atmosphere, calcining heat is 500 DEG C, and calcination time is 1 hour, is subsequently cooled to room temperature, take out sample, the raw material of first time calcining being sufficiently mixed grinding again uniformly, carries out second time calcining in air atmosphere, calcining heat is 500 DEG C, calcination time 20 hours, it is subsequently cooled to room temperature, takes out sample, namely obtain ferrochrome vanadate CrFe (VO4)2Powder.
Take the present embodiment gained CrFe (VO4)2Sample is scanned ultramicroscope and takes pictures, and degradation of methylene blue is tested, and result shows its main structure and morphology, the degradation rate of methylene blue is similar to embodiment 4.
Embodiment 6: chemical solution method prepares CrFe (VO4)2And degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO4)2The dose ratio of middle corresponding chemical element, weighs chromic oxide gel Cr (OH) respectively3: 0.79 gram, ferric nitrate Fe (NO3)3·9H2O:3.11 gram, ammonium vanadate NH4VO3: 1.80 grams, it is dissolved separately in dust technology;
(2) oxalic acid H is weighed2C2O4-2H2O:11.64 gram, stirring is lower to add containing vanadium ion V5+Solution in, at 50 DEG C stir 2 hours, obtain oxalic acid complexation vanadium ion V5+Complex liquid;
(3) solution containing chromium ion and iron ion is separately added into this oxalic acid complexation vanadium ion V5+Complex liquid among, both additions are in no particular order;By the mixed liquor that obtains stirring 3 hours when 80 DEG C, rest on subsequently in the baking oven of 100 DEG C, until obtaining fluffy presoma;
(4) being calcined in air atmosphere by the presoma that above-mentioned steps (3) obtains, calcining heat is 400 DEG C, and calcination time is 5 hours, is subsequently cooled to room temperature, takes out sample;The raw material of first time calcining being sufficiently mixed grinding again uniformly, carries out second time calcining in air atmosphere, calcining heat is 750 DEG C, calcination time 10 hours, is subsequently cooled to room temperature, takes out sample, namely obtains ferrochrome vanadate CrFe (VO4)2Powder.
Take the present embodiment gained CrFe (VO4)2Sample is scanned ultramicroscope and takes pictures, and degradation of methylene blue is tested, and result shows its main structure and morphology, the degradation rate of methylene blue is similar to embodiment 4.
Embodiment 7: coprecipitation prepares CrFe (VO4)2And degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO4)2The dose ratio of middle corresponding chemical element, weighs chromic nitrate Cr (NO respectively3)3·9H2O:5.72 gram, ferric nitrate Fe (NO3)3·9H2O:5.77 gram, vanadic anhydride V2O5: 2.60 grams;
(2) above-mentioned three kinds of compounds are dissolved in dilute hydrochloric acid respectively, are configured to the chromium salt solution that concentration is 1mol/L, iron salt solutions, vanadic salts solution;Mixing three kinds of saline solution and stir, heating in water bath 90 DEG C also keeps constant temperature, is the ammonia spirit of 40% to mixed solution and dripping volume fraction, stops, stirring, obtain cotton-shaped precipitate gradually when being about 6 to PH;
(3) being washed for several times by the precipitate obtained, isolated by filtration is placed in porcelain crucible, dries when temperature is 50 DEG C, obtains powder;
(4) by above-mentioned steps (3) clean dry powder calcine in air atmosphere, calcining heat is 500 DEG C, and calcination time is 20 hours, obtains ferrochrome vanadate photocatalytic material after natural cooling.
It is illustrated in figure 7 sample CrFe (VO prepared by the present embodiment4)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.
Take CrFe (VO prepared by the present embodiment4)2Sample carries out methylene blue degradation experiment, and step, with embodiment 1, obtains sample CrFe (VO as shown in Figure 84)2Degradation curve to organic dyestuff methylene blue under different visible light application times.It can be seen that the degradation rate of this sample photocatalytic degradation methylene blue reaches 95% in 180 minutes, the pure phase CrFe (VO prepared is described4)2Material has photocatalytic activity.
Result shows CrFe (VO in the present embodiment4)2Sample primary structure pattern, the degradation rate of methylene blue is similar to embodiment 1 with the kinetic curve of degradation of methylene blue.
Embodiment 8: coprecipitation prepares CrFe (VO4)2And degradation of methylene blue experiment
Its preparation process is as follows:
(1) according to chemical formula CrFe (VO4)2The dose ratio of middle corresponding chemical element, weighs chromic sulfate Cr respectively2(SO4)3: 4.90 grams, iron sulfate Fe2(SO4)3: 5.00 grams, ammonium vanadate NH4VO3: 5.85 grams;
(2) above-mentioned three kinds of compounds are dissolved in dilute hydrochloric acid respectively, are configured to the chromium salt solution that concentration is 1mol/L, iron salt solutions, vanadic salts solution;Mixing three kinds of dissolved salt liquid and be stirred continuously, being the ammonia spirit of 40% to mixed solution and dripping volume fraction, stopping when being about 10 to PH, heating in water bath is to 60 DEG C and keeps constant temperature, stirs, and obtains cotton-shaped precipitate gradually;
(3) being washed for several times by the precipitate obtained, isolated by filtration is placed in porcelain crucible, dries when temperature is 100 DEG C, obtains powder;
(4) by above-mentioned steps (3) clean dry powder calcine in air atmosphere, calcining heat is 900 DEG C, and calcination time is 1 hour, after natural cooling obtain ferrochrome vanadate photocatalytic material.
After measured, the structure and morphology of the ferrochrome vanadate photocatalytic material that the present embodiment obtains, the degradation rate of methylene blue is similar to embodiment 7.
By above-described embodiment it can be seen that novel ferrochrome vanadate CrFe (VO in the present invention4)2Catalysis material, can be prepared by high-temperature solid phase reaction method, chemical solution method and coprecipitation several method, its production cost and equipment requirements are low, the material scatter prepared is good, uniform granularity, chemical stability are good, the good stability of optical property, and it has less interband width, there is the photocatalysis performance of excellence, under visible light-responded, there is the effect decomposing harmful chemical, light-catalysed good stability, has a good application prospect.

Claims (9)

1. having the application in degradating organic dye pollutant of the visible light-responded ferrochrome vanadate photocatalytic material, the chemical formula of described catalysis material is CrFe (VO4)2, its pattern is graininess, and grain diameter is less than 10 microns.
2. application according to claim 1, it is characterised in that wherein said CrFe (VO4)2Prepared by employing high-temperature solid phase reaction method, comprise the following steps:
(1) by chemical formula CrFe (VO4)2The stoichiometric proportion of middle respective element, weighs respectively containing chromium ion Cr3+Compound, containing iron ion Fe3+Compound, containing vanadium ion V5+Compound, grind and mix homogeneously, obtain mixture;
(2) by mixture precalcining in air atmosphere in above-mentioned steps (1), calcining heat is 300~500 DEG C, and calcination time is 3~15 hours, natural cooling;
(3) being ground and mix homogeneously by the mixture of precalcining, calcine in air atmosphere, calcining heat is 500~1000 DEG C, and calcination time is 5~20 hours, obtains ferrochrome vanadate photocatalytic material after natural cooling.
3. application according to claim 2, it is characterised in that described containing chromium ion Cr3+Compound be the one in chromium oxide, chromium carbonate, chromic nitrate, chromic sulfate or chromic oxide gel;Described containing iron ion Fe3+Compound be the one in ferrum oxide, ferric carbonate, hydrated ferric oxide., ferric nitrate, iron sulfate or iron chloride;Described contains vanadium ion V5+Compound be the one in vanadic anhydride or ammonium metavanadate.
4. application according to claim 2, it is characterised in that the calcining heat described in step (2) is 350~500 DEG C, calcination time is 5~12 hours;Calcining heat described in step (3) is 500~900 DEG C, and calcination time is 9~15 hours.
5. application according to claim 1, it is characterised in that wherein said CrFe (VO4)2Prepared by employing chemical solution method, comprise the following steps:
(1) according to chemical formula CrFe (VO4)2The stoichiometric proportion of middle respective element weighs raw material: containing chromium ion Cr3+Compound, containing iron ion Fe3+Compound, containing vanadium ion V5+Compound, the raw material weighed is dissolved separately in dust technology;
(2) containing vanadium ion V5+Solution in, in whipping process add vanadium ion V5+The chelating agent that mole is 1.5~2 times, obtains complexation vanadium ion V5+Complex liquid;
(3) by above-mentioned vanadium ion V5+Complex liquid stir 1~5 hour when temperature is 20~60 DEG C after, be respectively added slowly to containing chromium ion Cr3+Compound and containing iron ion Fe3+The solution of compound, both additions are order in no particular order, stirs 1~5 hour when temperature is 60~100 DEG C, obtains fluffy presoma after standing, drying;
(4) above-mentioned presoma is carried out in air atmosphere first time calcining, calcining heat is 250~500 DEG C, calcination time is 1~15 hour, after natural cooling, grinding and mix homogeneously, carry out second time calcining in air atmosphere, calcining heat is 500~800 DEG C, calcination time is 3~20 hours, obtains ferrochrome vanadate photocatalytic material.
6. application according to claim 5, it is characterized in that, the compound containing chromium ion described in step (1) is the one in chromium oxide, chromium carbonate, chromic nitrate, chromic sulfate or chromic oxide gel, the described compound containing iron ion is the one in ferrum oxide, ferric carbonate, hydrated ferric oxide., ferric nitrate, iron sulfate or iron chloride, and the described compound containing vanadium ion is the one in vanadic anhydride or ammonium metavanadate;Chelating agent described in step (2) is the one in citric acid, oxalic acid.
7. application according to claim 5, it is characterised in that first time calcining described in step (4), calcining heat is 300~500 DEG C, and calcination time is 3~9 hours, and described second time is calcined, calcining heat is 500~650 DEG C, and calcination time is 5~15 hours.
8. application according to claim 1, it is characterised in that wherein said CrFe (VO4)2Prepared by employing coprecipitation, comprise the following steps:
(1) according to chemical formula CrFe (VO4)2The stoichiometric proportion of middle chromium, ferrum and v element, weighs respectively containing chromium ion Cr3+Compound, containing iron ion Fe3+Compound, containing vanadium ion V5+Compound;
(2) the chromium ion Cr that will weigh3+Compound, iron ion Fe3+Compound, vanadium ion V5+Compound be dissolved separately in water or be dissolved in dilute 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, heating is to 60~90 DEG C, and keeps 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) precipitate obtained above is washed, isolated by filtration, dry when temperature is 50~100 DEG C;
(4) being calcined in air atmosphere by the precipitate cleaned in above-mentioned steps (3), dry, calcining heat is 500~900 DEG C, and calcination time is 1~20 hour, obtains ferrochrome vanadate photocatalytic material after natural cooling.
9. application according to claim 8, it is characterized in that, described in step (1), the compound containing chromium ion is the one in chromium oxide, chromium carbonate, chromic nitrate, chromic sulfate or chromic oxide gel, the described compound containing iron ion is the one in ferrum oxide, ferric carbonate, hydrated ferric oxide., ferric nitrate, iron sulfate or iron chloride, and the described compound containing vanadium ion is the one in vanadic anhydride or ammonium metavanadate;Alkaline solution described in step (2) is NaOH solution, KOH solution, Ca (OH)2Solution, NaNH2Solution, NH3·H2O solution, Na2CO3Solution, NaHCO3One in solution;Calcining heat described in step (3) is 600~800 DEG C, and calcination time is 5~10 hours.
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