CN104801302A - Visible-light-response vanadate photocatalytic material as well as preparation method and application thereof - Google Patents
Visible-light-response vanadate photocatalytic material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a visible-light-response vanadate photocatalytic material as well as a preparation method and application thereof. The chemical formula of the vanadate photocatalytic material is Ag2CaV4O12; the vanadate photocatalytic material can be prepared from a high-temperature solid-phase method, a chemical solution method or a coprecipitation method. The prepared visible-light-response vanadate photocatalytic material is good in dispersity, uniform in particle degree, good in chemical stability, and low in preparation cost and equipment requirements; besides, Ag2CaV4O12 has excellent photocatalytic performance, and can efficiently photoactivate and degrade methylene blue under near ultraviolet radiation, so that the visible-light-response vanadate photocatalytic material has the function of decomposing harmful chemical substances under visible light response; the vanadate photocatalytic material is good in photocatalytic stability, and has favorable application prospect.
Description
Technical field
The present invention relates to a kind of visible light-responded vanadate photocatalytic material and its preparation method and application, particularly for the photochemical catalyst Ag of degradable organic pollutant
2caV
4o
12preparation method and application, belong to inorganic field of photocatalytic material.
Background technology
At present, along with developing rapidly of industry, the energy and ecological environment problem are more and more worth people's duplicate removal to be looked, and the contradiction how solving energy shortage and environmental pollution realizes sustainable development, raising people's living standard and faced a great problem of safeguarding national security.Even to this day, be usually difficult to the organic matter of degraded in the environment of our existence containing some, at every moment endangering our healthy, how cost-effectively environment purification pollutes the focus having become catalytic science research.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, so the environmental treatment technology of developing green is the active demand under existing situation.In this context, light-catalyzed reaction by feat of mild condition, consersion unit is simple, operating cost is low, secondary pollution is few and the feature such as applied widely is more and more subject to people's attention in environmental pollution improvement.
The principle of light-catalyzed reaction is that photochemical catalyst is after absorbing the photon higher than its band-gap energy, generate hole and electronics, these holes and electronics carry out oxidation reaction and reduction reaction respectively, reach the object of decomposing harmful chemical, organic-biological matter and sterilization.In numerous photochemical catalyst, most is representational is titanium dioxide (TiO
2), nowadays titanium dioxide has been utilized to decompose organic matters such as the agricultural chemicals in water and in air and odorants, but the band gap of titanium dioxide is 3.2eV, known only under the ultraviolet irradiation shorter than 400nm titanium dioxide just can carry out light-catalyzed reaction, that is titanium dioxide can only at indoor or the local work having uviol lamp, almost cannot utilize visible ray, and visible ray has occupied very large ratio in sunshine, low to the utilization rate of sunshine, limit its extensive use in photocatalysis technology field.Therefore development of new catalysis material, as oxynitride, titanate, tungstates, vanadate, niobates, chromate etc., is more and more subject to people's attention.
Although for light-catalysed research from phase late 1970s, but at present report to have visible light-responded photochemical catalyst kind still very limited, still also exist that light conversion efficiency is low, poor stability and the problems such as spectrum respective range is narrow, be very important so research and develop the new visible light-responded high efficiency photocatalyst that has.Vanadium system compound is paid close attention to by people, particularly BiVO owing to having good photocatalytic activity
4, Ag
3vO
4, lnVO
4deng the design and development of photochemical catalyst.Although publication number 103611550A has reported a kind of preparation method of molybdenum disulfide-silver metavanadate composite nano photocatalyst, publication number 103846096A has reported a kind of silver/silver bromide/silver metavanadate plasma composite photo-catalyst and preparation method thereof, but for Ag
2caV
4o
12photocatalytic Performance Study also have not seen reported, therefore we are to Ag
2caV
4o
12photocatalysis performance study, find this compound excellence near visible response photocatalysis performance.
Summary of the invention
For above-mentioned existing technical problem, the invention provides a kind of visible light-responded vanadate photocatalytic material and its preparation method and application, with the obtained visible-light photocatalyst to the black light catalytic degradation function admirable of many organic pollutions, and its preparation method simple, there is stronger application prospect.
For achieving the above object, the invention provides a kind of visible light-responded vanadate photocatalytic material, chemical formula is Ag
2caV
4o
12, pattern is graininess, and grain diameter is less than 2 microns, and particle easily disperses, and chemical stability is good.
Invention also provides a kind of preparation method of above-mentioned visible light-responded vanadate photocatalytic material, namely adopt high temperature solid-state method, comprise following concrete steps:
(1) by chemical formula Ag
2caV
4o
12in the stoichiometric proportion of each element, take respectively containing silver ion Ag
+compound, containing calcium ion Ca
2+compound, containing vanadium ion V
5+compound, then grind respectively and mix, obtaining mixture.
(2) by said mixture precalcining 1 ~ 2 time in air atmosphere, calcining heat is 300 ~ 500 DEG C, and calcination time is 4 ~ 12 hours; Preferably, calcining heat is 350 ~ 500 DEG C, and calcination time is 5 ~ 10 hours.
(3) after said mixture cools naturally, carry out grinding and mixing, calcine in air atmosphere, calcining heat is 500 ~ 850 DEG C, and calcination time is 8 ~ 16 hours, after it cools naturally, obtain Ag
2caV
4o
12photochemical catalyst.Preferably, calcining heat is 500 ~ 800 DEG C, and calcination time is 9 ~ 15 hours.
Further, described silver ion Ag
+compound be one in silver oxide, silver carbonate, silver bicarbonate, silver nitrate, silver sulfate.Described calcium ions Ca
2+compound be one in calcium carbonate, calcium hydroxide, calcium nitrate, calcium sulfate.Described contains vanadium ion V
5+compound be one in vanadic anhydride, ammonium metavanadate.
The present invention separately provides a kind of preparation method of above-mentioned visible light-responded vanadate photocatalytic material, namely adopts chemical solution method, comprises following concrete steps:
(A) according to the stoichiometric proportion of corresponding element in chemical formula Ag2CaV4O12, silver ion Ag is taken respectively
+compound, containing calcium ion Ca
2+compound, containing vanadium ion V
5+compound, be then dissolved in deionized water respectively or be dissolved in nitric acid with deionized water dilution, obtain each material solution;
(B) vanadium ion V is contained above-mentioned
5+material solution in, add vanadium ion V while stirring
5+the complexing agent of mole 1.5 doubly to 2 times, obtains vanadium ion V
5+mixed liquor; Further, described complexing agent is the one in citric acid, oxalic acid.
(C) by above-mentioned vanadium ion V
5+mixed liquor be under the condition of 20 ~ 60 DEG C in temperature, stir 1 ~ 2 hour, become after blueness until it, slowly add other material solutions, obtain raw material mixed liquor;
(D) be, under the condition of 50 ~ 100 DEG C, stir 1 ~ 2 hour in temperature by above-mentioned raw materials mixed liquor, leave standstill, dry after obtain fluffy presoma;
(E) calcined in air atmosphere by above-mentioned presoma, calcining heat is 200 ~ 400 DEG C, and calcination time is 2 ~ 12 hours, repeats this step twice; Preferably, calcining heat is 300 ~ 400 DEG C, and calcination time is 3 ~ 10 hours.
(F) after said mixture cools naturally, carry out grinding and mixing, calcine in air atmosphere, calcining heat is 500 ~ 750 DEG C, and calcination time is 5 ~ 16 hours, after it cools naturally, obtain Ag
2caV
4o
12photochemical catalyst.Preferably, calcining heat is 500 ~ 700 DEG C, and calcination time is 5 ~ 15 hours.
Further, described silver ion Ag
+compound be one in silver oxide, silver carbonate, silver bicarbonate, silver nitrate, silver sulfate.Described calcium ions Ca
2+compound be one in calcium carbonate, calcium hydroxide, calcium nitrate, calcium sulfate.Described contains vanadium ion V
5+compound be one in vanadic anhydride, ammonium metavanadate.
The present invention has reoffered a kind of preparation method of above-mentioned visible light-responded vanadate photocatalytic material, namely adopts coprecipitation, comprises following concrete steps:
(I) according to the stoichiometric proportion of corresponding element in chemical formula Ag2CaV4O12, silver ion Ag is taken respectively
+compound, containing calcium ion Ca
2+compound, containing vanadium ion V
5+compound, and be dissolved in deionized water respectively or be dissolved in nitric acid, obtaining each material solution;
(II) be heated in 70 ~ 80 DEG C of thermostat water baths, by above-mentioned each material solution mixing, and slowly dripping ammoniacal liquor while stirring, and regulate pH value between 6 ~ 8, then leave standstill and be precipitated thing;
(III) by after above-mentioned sediment washing, isolated by filtration, being placed in porcelain crucible, is dry under the condition of 50 ~ 100 DEG C in temperature;
(IV) above-mentioned drying object calcined in air atmosphere, calcining heat is 200 ~ 850 DEG C, and calcination time is 2 ~ 15 hours, repeats this step two to three times, after it cools naturally, obtain Ag
2caV
4o
12photochemical catalyst.Preferably, calcining heat is 300 ~ 800 DEG C, and calcination time is 5 ~ 15 hours.
Further, described silver ion Ag
+compound be one in silver oxide, silver carbonate, silver bicarbonate, silver nitrate, silver sulfate.Described calcium ions Ca
2+compound be one in calcium carbonate, calcium hydroxide, calcium nitrate, calcium sulfate.Described contains vanadium ion V
5+compound be one in vanadic anhydride, ammonium metavanadate.
In addition, above-mentioned visible light-responded Ag
2caV
4o
12the application of photochemical catalyst is can degradating organic dye pollutant under the irradiation of visible ray, especially can degradation of methylene blue under the irradiation of visible ray.
Compared with prior art, photochemical catalyst Ag of the present invention
2caV
4o
12can band gap (2.06eV) narrower, under near ultraviolet is irradiated, can high efficiency photocatalysis degradation of methylene blue, there is good photocatalytic activity.Secondly, Ag
2caV
4o
12preparation take inorganic salts as raw material, handling safety, energy consumption are low, cost is low, and the powder particle obtained is little and evenly.Further, its preparation method is simple, mild condition, and consume energy low, the reaction time is short, is easy to suitability for industrialized production, without waste water and gas discharge, environmentally friendly.
Accompanying drawing explanation
The Ag of Fig. 1 obtained by the embodiment of the present invention 1
2caV
4o
12the X-ray powder diffraction figure of sample;
The Ag of Fig. 2 obtained by the embodiment of the present invention 1
2caV
4o
12the SEM(SEM of sample) figure;
The Ag of Fig. 3 obtained by the embodiment of the present invention 1
2caV
4o
12sample UV-Vis diffuse reflection spectroscopy figure;
The Ag of Fig. 4 obtained by the embodiment of the present invention 1
2caV
4o
12sample under different visible light application times to the degradation curve figure of organic dyestuff methylene blue;
The Ag of Fig. 5 obtained by the embodiment of the present invention 4
2caV
4o
12the X-ray powder diffraction figure of sample test;
The Ag of Fig. 6 obtained by the embodiment of the present invention 4
2caV
4o
12sample SEM schemes;
The Ag of Fig. 7 obtained by the embodiment of the present invention 4
2caV
4o
12the UV-Vis diffuse reflection spectroscopy figure of sample;
The Ag of Fig. 8 obtained by the embodiment of the present invention 4
2caV
4o
12sample under different visible light application times to the degradation curve figure of organic dyestuff methylene blue.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
The invention discloses a kind of visible light-responded vanadate photocatalyst, chemical formula is A g
2caV
4o
12, prepare by high temperature solid-state method, chemical solution method or coprecipitation.
Embodiment 1: in order to obtain the composite oxides Ag used in the present invention
2caV
4o
12, adopt high temperature solid-state method preparation, namely using as the various oxide of raw material or carbonate according to the metering of target constitutional chemistry than mixing, then to synthesize in air atmosphere at ambient pressure.In addition, in order to effectively light can be utilized, the size of the photochemical catalyst in the present invention is preferably in micron level, or even nano particle, and specific area is comparatively large, and with oxide powder prepared by solid-phase synthesis, its particle is comparatively large and surface area is less, but particle diameter can be made to diminish by pulverizing means such as ball mills, concrete steps are as follows.
First, according to chemical formula Ag
2caV
4o
12, take silver carbonate Ag respectively
2cO
3: 2.758 grams, calcium carbonate CaCO
3: 1.001 grams, ammonium metavanadate NH
4vO
3: 4.679 grams, grind and mix in agate mortar, select air atmosphere to carry out precalcining, precalcining temperature is 350 DEG C, and calcination time 5 hours, is cooled to room temperature, taking-up.
Then, by the mixture of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 400 DEG C, calcination time 10 hours, is then chilled to room temperature, taking-up.
Finally, be placed in Muffle furnace after again fully being ground by mixture, calcine in air atmosphere, calcining heat is 800 DEG C, and calcination time is 9 hours, namely obtains vanadate Ag
2caV
4o
12powder.
See accompanying drawing 1, Ag prepared by the present embodiment
2caV
4o
12x-ray powder diffraction figure, according to XRD test result display, prepared vanadate Ag
2caV
4o
12for monophase materials, exist without any other dephasign, diffraction maximum is sharp-pointed, and degree of crystallinity is better.
See accompanying drawing 2, the Ag prepared by the present embodiment
2caV
4o
12sEM(SEM) figure, as can be seen from the figure, Ag
2caV
4o
12grain size number is all at 1-2 micron, and particle contacts is loose, easily disperses.
See accompanying drawing 3, the Ag prepared by the present embodiment
2caV
4o
12uV-Vis diffuse reflection spectroscopy figure, as can be seen from the figure, this Ag
2caV
4o
12absorption shear wavelength near 550 nm, show effectively to absorb ultraviolet-visible light;
Get the Ag of the present embodiment 1
2caV
4o
12sample carries out the experiment of photocatalytic degradation methylene blue: photocatalytic degradation methylene blue activity rating adopts self-control photocatalytic reaction device, illuminator is the cylindrical xenon lamp of 500W, the cylindrical light catalytic reaction instrument that reactive tank uses pyrex to make, 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 240 minutes, starts illumination after opening condensed water, after illumination, every 15min gets a sample, centrifugal, get 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, as the clearance of methylene blue solution by absorbance.Computing formula: degradation rate=(1-C/C
0) × 100%=(1-A/A
0) × 100%, wherein C
0, C is respectively concentration before and after photocatalytic degradation, A
0, A be respectively degraded before and after absorbance.Thus, the Ag as Fig. 4 is obtained
2caV
4o
12degradation curve to organic dyestuff methylene blue under different visible light application times, as can be seen from the figure, this Ag
2caV
4o
12the degradation rate 300min of photocatalytic degradation methylene blue reaches 77%, and the Ag prepared is described
2caV
4o
12material has photocatalytic activity.
Embodiment 2: adopt high temperature solid-state method to prepare Ag
2caV
4o
12, concrete steps are as follows.
First, according to chemical formula Ag
2caV
4o
12, take silver carbonate Ag respectively
2cO
3: 2.758 grams, calcium hydroxide Ca (OH)
2: 0.741 gram, vanadic anhydride V
2o
5: 3.640 grams, to grind in agate mortar and after mixing, select air atmosphere to carry out precalcining, precalcining temperature is 400 DEG C, and calcination time 6 hours, is then cooled to room temperature, takes out.
Then, by the mixture of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 500 DEG C, calcination time 7 hours, is then chilled to room temperature, takes out.
Finally, be placed in Muffle furnace after again fully being ground by said mixture, calcine in air atmosphere, calcining heat is 800 DEG C, and calcination time is 9 hours, namely obtains vanadate Ag
2caV
4o
12powder.
Thus, obtained Ag
2caV
4o
12primary structure pattern, similar to the accompanying drawing in embodiment 1 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 3: adopt high temperature solid-state method to prepare Ag
2caV
4o
12, concrete steps are as follows.
First, according to chemical formula Ag
2caV
4o
12, take silver carbonate Ag respectively
2cO
3: 2.758 grams, calcium sulfate CaSO
4: 1.641 grams, ammonium metavanadate NH
4vO
3: 4.679 grams, to grind in agate mortar and after mixing, select air atmosphere to carry out precalcining, precalcining temperature is 350 DEG C, and calcination time 7 hours, is then cooled to room temperature, takes out.
Then, by the mixture of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 450 DEG C, calcination time 8 hours, is then chilled to room temperature, takes out.
Finally, be placed in Muffle furnace after again fully being ground by said mixture, calcine in air atmosphere, calcining heat is 750 DEG C, and calcination time is 15 hours, namely obtains vanadate Ag
2caV
4o
12powder.
Thus, obtained Ag
2caV
4o
12primary structure pattern, to the degradation rate of methylene blue and the kinetic curve of degradation of methylene blue also similar to the accompanying drawing in embodiment 1.
Embodiment 4: adopt chemical solution method to prepare Ag
2caV
4o
12, concrete steps are as follows.
First, according to chemical formula Ag
2caV
4o
12, take silver carbonate Ag respectively
2cO
3: 2.758 grams, calcium nitrate Ca (NO
3)
2: 1.641 grams, ammonium metavanadate NH
4vO
3: 4.679 grams, oxalic acid H
2c
2o
4-2H
2o:8.037 gram.Silver carbonate is dissolved in dust technology; Calcium nitrate is dissolved in deionized water; By ammonium metavanadate and dissolving oxalic acid in certain deionized water.
Secondly, by the vanadium ion V obtained
5+mixed liquor be stir to clarify blue solution under the condition of 50 DEG C in temperature, more slowly add other material solution, and be stir 2 hours under the condition of 60 DEG C in temperature.
Then, the mixed liquor obtained is placed in 50 DEG C of baking ovens dry 2 hours, leave standstill, naturally cool obtain fluffy presoma.
Then, presoma to be ground in agate mortar and after mixing, select air atmosphere to calcine, calcining heat is 300 DEG C, and calcination time is 3 hours, is then cooled to room temperature, takes out; By the mixture of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 400 DEG C, calcination time 10 hours, is then chilled to room temperature, takes out.
Finally, be placed in Muffle furnace after again fully being ground by gains, calcine in air atmosphere, calcining heat is 700 DEG C, and calcination time is 15 hours, namely obtains vanadate Ag
2caV
4o
12powder, its main structure and morphology is similar to the accompanying drawing of embodiment 1.
Seeing accompanying drawing 5, is Ag prepared by the present embodiment
2caV
4o
12x-ray powder diffraction figure, result display prepared by Ag
2caV
4o
12for monophase materials, do not have other dephasign, diffraction maximum is sharp-pointed, better crystallinity degree.
See accompanying drawing 6, Ag prepared by the present embodiment
2caV
4o
12sEM(SEM) figure, as can be seen from the figure, Ag
2caV
4o
12grain size number be all less than 1 micron, good dispersion.
See accompanying drawing 7, sample Ag prepared by the present embodiment
2caV
4o
12uV-Vis diffuse reflection spectroscopy figure, as can be seen from the figure, Ag
2caV
4o
12effectively absorbing wavelength can be less than the ultraviolet-visible light of 500 nm.
See accompanying drawing 8, the Ag prepared by the present embodiment
2caV
4o
12degradation curve to organic dyestuff methylene blue under different visible light application times.Can find out, this Ag
2caV
4o
12the degradation rate 300min of photocatalytic degradation methylene blue reaches nearly 90%, and the Ag prepared is described
2caV
4o
12material has photocatalytic activity.
Embodiment 5: adopt chemical solution method to prepare Ag
2caV
4o
12, concrete steps are as follows.
First, according to chemical formula Ag
2caV
4o
12, take silver nitrate AgNO respectively
3: 3.397 grams, calcium nitrate Ca (NO
3)
2: 1.641 grams, ammonium metavanadate NH
4vO
3: 4.679 grams, oxalic acid H
2c
2o
4-2H
2o:6.028 gram.Silver nitrate, calcium nitrate are dissolved in deionized water respectively; By ammonium metavanadate and dissolving oxalic acid in certain deionized water, obtain vanadium ion V
5+mixed liquor,
Secondly, by vanadium ion V
5+mixed liquor be that under the condition of 60 DEG C, heating stirs to clarify blue solution in temperature, and add silver nitrate, calcium nitrate solution, continue to stir a period of time, obtain raw material mixed liquor.
Then, the mixed liquor obtained is placed in 50 DEG C of baking ovens and dries 12 hours, after taking out nature cooling, obtain fluffy presoma.
Then, presoma to be ground in agate mortar and after mixing, select air atmosphere to calcine, calcining heat is 300 DEG C, and calcination time is 3 hours, is then cooled to room temperature, takes out.By first time calcining mixture fully mixed grinding is even again, in air atmosphere, carry out second time calcining, calcining heat is 350 DEG C, and calcination time 5 hours, is then cooled to room temperature, taking-up.
Finally, be placed in Muffle furnace after again fully being ground by said mixture, calcine in air atmosphere, calcining heat is 500 DEG C, and calcination time is 5 hours, namely obtains vanadate Ag
2caV
4o
12powder, its main structure and morphology is similar to the accompanying drawing of embodiment 1, similar to the accompanying drawing of embodiment 4 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 6: adopt chemical solution method to prepare Ag
2caV
4o
12, concrete steps are as follows.
First, according to chemical formula Ag
2caV
4o
12,take silver bicarbonate AgHCO respectively
3: 3.380 grams, calcium carbonate CaCO
3: 1.001 grams, vanadic anhydride V
2o
5: 3.640 grams, oxalic acid 7.233 grams, the silver bicarbonate AgHCO will taken respectively
3, calcium carbonate CaCO
3, vanadic anhydride V
2o
5be dissolved in dust technology and dilute by deionized water.Containing vanadium ion V
5+solution in, stir one hour, become after blueness until solution, add 2 times of vanadium ion V
5+the oxalic acid of mole, obtains vanadium ion V
5+mixed liquor.
Then, by vanadium ion V
5+mixed liquor be stir after 1 hour under the condition of 50 DEG C in temperature, slowly add the solution of other raw materials.
Then, be under the condition of 60 DEG C in temperature, above-mentioned raw materials mixed liquor stirred 2 hours, leave standstill, dry after obtain fluffy presoma.
Moreover calcined in air atmosphere by presoma, calcining heat is 300 DEG C, and calcination time is 3 hours, is then cooled to room temperature, take out.By the raw material of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 400 DEG C, calcination time 8 hours, is then chilled to room temperature, takes out.
Finally, be placed in Muffle furnace after it again fully being ground, calcine in air atmosphere, calcining heat is 650 DEG C, and calcination time is 12 hours, namely obtains vanadate Ag
2caV
4o
12powder, its main structure and morphology is similar to the accompanying drawing of embodiment 1, and it is similar to the accompanying drawing of embodiment 4 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 7: preparation Ag
2caV
4o
12, adopt coprecipitation, comprise following concrete steps.
First, according to chemical formula Ag
2caV
4o
12, take silver nitrate AgNO respectively
3: 3.397 grams, calcium carbonate CaCO
3: 1.001 grams, ammonium metavanadate NH
4vO
3: 4.679 grams, the raw material taken is dissolved in the compound of 2+, the compound containing vanadium ion V5+ respectively, is then dissolved in deionized water respectively or is dissolved in nitric acid, and mixing.Also can under water-bath be heated to 70 ~ 80 DEG C of constant temperatures, at raw material ammonium metavanadate NH
4vO
3slowly add the solution of other raw material when being dissolved in deionized water, and slowly drip ammoniacal liquor under constant agitation, regulate pH value between 6 ~ 8, leave standstill and be precipitated thing.
Then, by the sediment washing several obtained, isolated by filtration is placed in porcelain crucible, is to dry under the condition of 80 DEG C in temperature.Calcined in air atmosphere by the product obtained after oven dry, calcining heat is 300 DEG C, and calcination time 5 hours, is then cooled to room temperature, takes out.
Moreover fully mixed grinding is even again by the material of first time calcining, in air atmosphere, carry out second time calcining, calcining heat 400 DEG C, calcination time 8 hours, is then chilled to room temperature, takes out.
Finally, be placed in Muffle furnace after again fully being ground by the material of second time calcining, calcine in air atmosphere, calcining heat 800 DEG C, calcination time is 15 hours, namely obtains vanadate Ag
2caV
4o
12powder, its main structure and morphology, similar to the accompanying drawing of embodiment 4 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 8: preparation Ag
2caV
4o
12, adopt coprecipitation, comprise following concrete steps.
First, according to chemical formula Ag
2caV
4o
12, take silver oxide Ag respectively
2o:2.317 gram, calcium carbonate CaCO
3: 1.001 grams, ammonium metavanadate NH
4vO
3: 4.679 grams, the raw material taken is dissolved in the compound of 2+, the compound containing vanadium ion V5+ respectively, is then dissolved in deionized water respectively or is dissolved in nitric acid.
Secondly, under water-bath being heated to 70 ~ 80 DEG C of constant temperatures, by above-mentioned each material solution mixing, and slowly dripping ammoniacal liquor under constant agitation, regulate pH value between 6 ~ 8, leave standstill and be precipitated thing.
Moreover by the sediment washing several obtained, isolated by filtration is placed in porcelain crucible, is to dry under the condition of 80 DEG C in temperature.Calcined in air atmosphere by the product obtained after oven dry, calcining heat is 350 DEG C, and calcination time 5 hours, is then cooled to room temperature, takes out.By the material of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 600 DEG C, calcination time 10 hours, is then chilled to room temperature, takes out; Finally by 2 materials of second time calcining, it is placed in Muffle furnace after again fully grinding, and calcine in air atmosphere, calcining heat is 750 DEG C, and calcination time is 12 hours, namely obtains vanadate Ag
2caV
4o
12powder, its main structure and morphology, similar to the accompanying drawing of embodiment 1 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
In sum, by the catalysis material Ag obtained by each embodiment
2caV
4o
12pattern is graininess, and particle easily disperses, and has less interband width, have the effect of decomposing harmful chemical, and photocatalysis performance is excellent, has a good application prospect under visible light-responded.And material scatter is good, uniform granularity, chemical stability are good, and production cost and equipment requirement are also low, are convenient to application.
Claims (11)
1. a visible light-responded vanadate photocatalytic material, is characterized in that, chemical formula is Ag
2caV
4o
12, pattern is graininess, and grain diameter is less than 2 microns.
2. a preparation method for a kind of visible light-responded vanadate photocatalytic material as claimed in claim 1, is characterized in that, adopts high temperature solid-state method, comprises following concrete steps:
(1) by chemical formula Ag
2caV
4o
12in the stoichiometric proportion of each element, take respectively containing silver ion Ag
+compound, containing calcium ion Ca
2+compound, containing vanadium ion V
5+compound, then grind respectively and mix, obtaining mixture;
(2) by said mixture precalcining 1 ~ 2 time in air atmosphere, calcining heat is 300 ~ 500 DEG C, and calcination time is 4 ~ 12 hours;
(3) after said mixture cools naturally, carry out grinding and mixing, calcine in air atmosphere, calcining heat is 500 ~ 850 DEG C, and calcination time is 8 ~ 16 hours, after it cools naturally, obtain Ag
2caV
4o
12photochemical catalyst.
3. the preparation method of a kind of visible light-responded vanadate photocatalytic material according to claim 2, is characterized in that, described silver ion Ag
+compound be one in silver oxide, silver carbonate, silver bicarbonate, silver nitrate, silver sulfate; Described calcium ions Ca
2+compound be one in calcium carbonate, calcium hydroxide, calcium nitrate, calcium sulfate; Described contains vanadium ion V
5+compound be one in vanadic anhydride, ammonium metavanadate.
4. the preparation method of a kind of visible light-responded vanadate photocatalytic material according to Claims 2 or 3, it is characterized in that, the calcining heat described in step (2) is 350 ~ 500 DEG C, calcination time is 5 ~ 10 hours; Calcining heat described in step (3) is 500 ~ 800 DEG C, and calcination time is 9 ~ 15 hours.
5. a preparation method for a kind of visible light-responded vanadate photocatalytic material as claimed in claim 1, is characterized in that, adopts chemical solution method, comprises following concrete steps:
(A) according to the stoichiometric proportion of corresponding element in chemical formula Ag2CaV4O12, silver ion Ag is taken respectively
+compound, containing calcium ion Ca
2+compound, containing vanadium ion V
5+compound, be then dissolved in deionized water respectively or be dissolved in nitric acid with deionized water dilution, obtain each material solution;
(B) vanadium ion V is contained above-mentioned
5+material solution in, add vanadium ion V while stirring
5+the complexing agent of mole 1.5 doubly to 2 times, obtains vanadium ion V
5+mixed liquor;
(C) by above-mentioned vanadium ion V
5+mixed liquor be under the condition of 20 ~ 60 DEG C in temperature, stir 1 ~ 2 hour, become after blueness until it, slowly add other material solutions, obtain raw material mixed liquor;
(D) be, under the condition of 50 ~ 100 DEG C, stir 1 ~ 2 hour in temperature by above-mentioned raw materials mixed liquor, leave standstill, dry after obtain fluffy presoma;
(E) calcined in air atmosphere by above-mentioned presoma, calcining heat is 200 ~ 400 DEG C, and calcination time is 2 ~ 12 hours, repeats this step twice;
(F) after said mixture cools naturally, carry out grinding and mixing, calcine in air atmosphere, calcining heat is 500 ~ 750 DEG C, and calcination time is 5 ~ 16 hours, after it cools naturally, obtain Ag
2caV
4o
12photochemical catalyst.
6. the preparation method of a kind of visible light-responded vanadate photocatalytic material according to claim 5, is characterized in that, the complexing agent described in step (B) is the one in citric acid, oxalic acid; Described silver ion Ag
+compound be one in silver oxide, silver carbonate, silver bicarbonate, silver nitrate, silver sulfate; Described calcium ions Ca
2+compound be one in calcium carbonate, calcium hydroxide, calcium nitrate, calcium sulfate; Described contains vanadium ion V
5+compound be one in vanadic anhydride, ammonium metavanadate.
7. the preparation method of a kind of visible light-responded vanadate photocatalytic material according to claim 5 or 6, it is characterized in that, the calcining heat described in step (E) is 300 ~ 400 DEG C, calcination time is 3 ~ 10 hours; Calcining heat described in step (F) is 500 ~ 700 DEG C, and calcination time is 5 ~ 15 hours.
8. a preparation method for a kind of visible light-responded vanadate photocatalytic material as claimed in claim 1, is characterized in that, adopts coprecipitation, comprises following concrete steps:
(I) according to the stoichiometric proportion of corresponding element in chemical formula Ag2CaV4O12, silver ion Ag is taken respectively
+compound, containing calcium ion Ca
2+compound, containing vanadium ion V
5+compound, and be dissolved in deionized water respectively or be dissolved in nitric acid, obtaining each material solution;
(II) be heated in 70 ~ 80 DEG C of thermostat water baths, by above-mentioned each material solution mixing, and slowly dripping ammoniacal liquor while stirring, and regulate pH value between 6 ~ 8, then leave standstill and be precipitated thing;
(III) by after above-mentioned sediment washing, isolated by filtration, being placed in porcelain crucible, is dry under the condition of 50 ~ 100 DEG C in temperature;
(IV) above-mentioned drying object calcined in air atmosphere, calcining heat is 200 ~ 850 DEG C, and calcination time is 2 ~ 15 hours, repeats this step two to three times, after it cools naturally, obtain Ag
2caV
4o
12photochemical catalyst.
9. the preparation method of a kind of visible light-responded vanadate photocatalytic material according to claim 8, is characterized in that, described silver ion Ag
+compound be one in silver oxide, silver carbonate, silver bicarbonate, silver nitrate, silver sulfate; Described calcium ions Ca
2+compound be one in calcium carbonate, calcium hydroxide, calcium nitrate, calcium sulfate; Described contains vanadium ion V
5+compound be one in vanadic anhydride, ammonium metavanadate.
10. the preparation method of a kind of visible light-responded vanadate photocatalytic material according to claim 8 or claim 9, it is characterized in that, the calcining heat described in step (IV) is 300 ~ 800 DEG C, and calcination time is 5 ~ 15 hours.
11. 1 kinds as claim 1,2,5,8 arbitrary as described in a kind of visible light-responded vanadate photocatalytic material as the application of visible light-responded photochemical catalyst.
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