CN101444744A - Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof - Google Patents
Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof Download PDFInfo
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- CN101444744A CN101444744A CNA2008101366594A CN200810136659A CN101444744A CN 101444744 A CN101444744 A CN 101444744A CN A2008101366594 A CNA2008101366594 A CN A2008101366594A CN 200810136659 A CN200810136659 A CN 200810136659A CN 101444744 A CN101444744 A CN 101444744A
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Abstract
The invention relates to a zeolite-based nano bismuth molybdate visible light catalytic material. With a zeolite molecule sieve as a carrier, bismuth molybdate nano-particles are loaded on the surface of the zeolite molecular sieve, the zeolite molecular sieve is provided with an 8-oxygen ring and pore canal structure, or a 10-oxygen ring and pore canal structure or a 12-oxygen ring and pore canal structure, and the zeolite molecular sieve is a natural or synthetic sieve with the silica alumina ratio less than or equal to 30. The invention provides a simple and poison-and-pollution-free preparation method with low cost, the method is used for producing the bismuth molybdate nano-particles on the surface of the zeolite molecular sieve with low silica alumina ratio, thus obtaining a novel photocatalytic composite material. The bismuth molybdate is loaded on the zeolite molecular sieve, thus improving the stability of the bismuth molybdate nano particles. After the catalytic reaction of the zeolite-based nano bismuth molybdate visible light catalytic material, the catalytic material can be separated from the compound for recycle and reuse by the method of stewing, centrifuging or filtering.
Description
Technical field
The present invention relates to a kind of Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof, belong to the new function material field.The present invention is substrate with the zeolite molecular sieve, generates the nano bismuth molybdate particle on the zeolite molecular sieve surface, thereby constitutes a kind of new material with visible light catalytic performance.
Background technology
In recent years; the conductor photocatalysis technology has become one of research focus in photochemistry field and the field of environment protection; the oxide semiconductor photocatalysis technology is as a class in the semiconductor catalysis technique; owing to multiple organic matter is had tangible degradation effect, thereby more wide application prospect is arranged.
1972, Fujishima etc. reported in photocell, light radiation titanium dioxide (TiO
2) time sustainable generation water redox reaction, this characteristic has caused the very big interest of environmental protection field researcher, the new era of from then on having started the conductor photocatalysis technology.TiO
2Though have advantages such as photocatalytic activity height, oxidability is strong, nontoxic, chemical stability is good, inexpensive, still, it must be under the irradiation of ultraviolet light, and well therefore the performance photo-catalysis function has limited its range of application.Current TiO
2The research of photochemical catalyst mainly concentrates on TiO
2Doping vario-property on.
At present, under visible light, have the existing report of novel photocatalysis material bismuth molybdate of catalytic performance, as the low-temperature molten salt synthetic method that is seen in report (Materials Chemistry and Physics, 2008,110 (2-3), 197-200); The microwave hydrothermal synthetic method (Materials Chemistry and Physics, 2008,110 (2-3), 332-336); Backflow synthetic method (J.Phys.Chem.B, 2006,110 (36), 17790-17797) and pre-ultrasonic-hydrothermal synthesis method (Chinese invention patent CN200810023411.7) etc.But, no matter which kind of synthetic method, all wish to obtain the littler bismuth molybdate particle of particle, to increase its surface area, improve photocatalysis efficiency, but after the bismuth molybdate particle is reduced to nano-scale, stability decreases, reunite easily between the nanometer, also exist the bismuth molybdate nano particle to be difficult to problems such as recycling simultaneously.
Summary of the invention
The invention provides a kind of Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof, purpose be solve that the synthetic catalysis material bismuth molybdate particle of prior art is big, specific area is little, poor stability and the problem that is difficult to recycling.
For achieving the above object, the technical solution used in the present invention is: a kind of Zeolite-based nano bismuth molybdate visible light catalytic material is a carrier with the zeolite molecular sieve, and the bismuth molybdate nanometer particle load is on the surface of described zeolite molecular sieve; Described zeolite molecular sieve is selected 8 oxygen membered ring channel structures, 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, and silica alumina ratio is less than or equal to 30 natural or synthesis zeolite.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of Zeolite-based nano bismuth molybdate visible light catalytic material, made by following raw materials according and operating procedure:
(1), raw material
1., zeolite molecular sieve: select 8 oxygen membered ring channel structures, 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, and silica alumina ratio is less than or equal to 30 natural or synthesis zeolite;
2., bismuth salting liquid: soluble bismuth salt is dissolved in the deionized water, and being made into concentration is the bismuth salting liquid of 1～5mol/L; Described soluble bismuth salt selects to fluoridize a kind of in bismuth, bismuth chloride, bismuth bromide, bismuth iodide, bismuth nitrate and the bismuth sulfate;
3., molybdate solution: the soluble molybdenum hydrochlorate is dissolved in is made into molybdate solution in the deionized water; Described soluble molybdenum hydrochlorate is selected a kind of in molybdenum acid ammonia, sodium molybdate and the potassium molybdate;
(2), operating procedure
Step 1, according to 0.1～1: 1 mass ratio between soluble bismuth salt and the zeolite molecular sieve, described zeolite molecular sieve is immersed in the described bismuth salting liquid, make the zeolite molecular sieve liquid that obtains bismuth-containing after soluble bismuth salt and the zeolite molecular sieve generation ion-exchange reactions;
Step 2, according to bismuth element and molybdenum element 2: 1 mol ratio between the two, in step 1, add described molybdate solution in the zeolite molecular sieve liquid of bismuth-containing, regulate pH value to 4～7 with ammoniacal liquor, simultaneously it is heated and stir, molybdenum acid ion and bismuth ion are fully reacted generate bismuth molybdate to obtain product;
Step 3, the product that step 2 is obtained carry out centrifugation, obtain sediment;
Step 4, spend the sediment that the deionised water step 3 obtains, remove the soluble-salt of participating in reaction, obtain the wet basis Zeolite-based nano bismuth molybdate visible light catalytic material;
Step 5, the wet basis Zeolite-based nano bismuth molybdate visible light catalytic material that step 4 is obtained are under 120 ℃～400 ℃ the condition after the oven dry at bake out temperature, finally obtain Zeolite-based nano bismuth molybdate visible light catalytic material.
Related content in the technique scheme is explained as follows:
1, in the such scheme, the silica alumina ratio of described zeolite molecular sieve is less than or equal to 15.
2, in the such scheme, the silica alumina ratio of described zeolite molecular sieve is less than or equal to 10.
3, in the such scheme, the zeolite molecular sieve of described 8 oxygen membered ring channel structures adopts A type zeolite; The zeolite molecular sieve of described 10 oxygen membered ring channel structures is selected a kind of in MFI, TON, FER and the STI zeolite for use;
International code name commercial disignation source
MFI ZSM-5 is synthetic
TON ZSM-22 is synthetic
FER ZSM-35 is synthetic
The STI foresite is natural
The zeolite molecular sieve of described 12 oxygen membered ring channel structures is selected a kind of in FAU, LAL, MTN, BEA and the MOR zeolite for use;
International code name commercial disignation source
FAU Y type, the X type is synthetic
LAL L type is synthetic
MTN ZSM-12 is synthetic
BEA β type is synthetic
The MOR modenite is natural or synthetic.
4, in the such scheme, described bake out temperature is 200 ℃～300 ℃.
5, state in the scheme, in order to make the bismuth molybdate nanometer particle load on zeolite molecular sieve, the silica alumina ratio of described zeolite molecular sieve≤15, the best is≤10, can make bismuth ion or bismuth oxygen cation exchange like this to zeolite molecular sieve, the molybdate anion in conjunction with getting on, has formed the bismuth molybdate particle more then.So-called silica alumina ratio is meant the ratio of silicon and aluminium atomicity in the zeolite molecular sieve, and it is an index of zeolite molecular sieve character, and what the present invention adopted is the low silica-alumina ratio zeolite molecular sieve, has only the low silica-alumina ratio zeolite molecular sieve just to have ion exchanging function.
6, in the such scheme, regulate pH value to 4～7, heat stirring reaction half an hour with ammoniacal liquor.Purpose is the protection zeolite molecular sieve, and in stronger acid solution, the zeolite molecular sieve skeleton of low silica-alumina ratio is destroyed easily.
7, in the such scheme, the soluble-salt in the step 3 is meant soluble bismuth salt and/or the soluble molybdenum hydrochlorate of not participating in reaction.
Operation principle of the present invention is: with the zeolite molecular sieve of low silica-alumina ratio as matrix, make zeolite molecular sieve have certain ion-exchange capacity, to zeolite molecular sieve, the molybdate anion is again in conjunction with getting on to form the bismuth molybdate particle then with bismuth ion or bismuth oxygen cation exchange.The mechanism of visible light catalytic material catalytic degradation organic wastewater is: when energy in the visible light is mapped to the bismuth molybdate nano particle greater than the illumination of the energy gap of bismuth molybdate, the separation of charge of bismuth molybdate nano particle produces electron-hole pair, the hole that is positioned at valence band has strong oxidability, can rapid oxidation Decomposition be CO with whole organic matters almost
2, H
2Innocuous substances such as O.
Because the technique scheme utilization, the present invention compared with prior art has following advantage and effect:
The invention provides a kind of low cost, oversimplify, the method for nontoxic pollution-free is used for the superficial growth nano bismuth molybdate particle at the low silica-alumina ratio zeolite molecular sieve, makes a kind of novel photocatalysis composite.The bismuth molybdate appendix on zeolite molecular sieve, has been increased the stability of nano bismuth molybdate particle.After Zeolite-based nano bismuth molybdate visible light catalytic material carries out catalytic reaction, can by leave standstill, method centrifugal or that filter separates catalysis material recycling from mixture.
Description of drawings
Accompanying drawing 1 is the X-ray diffraction spectrogram of NaY zeolite molecular sieve and nano bismuth molybdate composite;
Accompanying drawing 2 is the transmission electron microscope photo of nano bismuth molybdate on the NaY zeolite.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: a kind of Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof
Employing silica alumina ratio (Si/Al) is 2.3 NaY (FAU) zeolite molecular sieve, and sintering temperature is 400 ℃.
Take by weighing 0.4851g bismuth nitrate (Bi (NO
3)
35H
2O) in small beaker, add 10mL distilled water, the 1.0000gNaY zeolite molecular sieve is added wherein, at 50 ℃ of heating, stirring 15min, with 0.0882g ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) adding wherein, is 5 with the pH value of ammoniacal liquor regulator solution, and in 50 ℃ of heating, stirring reaction half an hour, centrifugation is washed three times with distilled water, puts into 120 ℃ of oven dry of baking oven, promptly gets product in 2 hours in 400 ℃ of roastings of Muffle furnace then.As shown in Figures 1 and 2, wherein, the weak peak with "+" expression broadening among the figure belongs to diffraction maximum into nano bismuth molybdate, and the broadening from the diffraction maximum of bismuth molybdate illustrate the nano particle formation of bismuth molybdate.The result of transmission electron microscope has confirmed that further nano bismuth molybdate forms on zeolite surface, from transmission electron microscope photo, the size of nano bismuth molybdate particle is about the 10-60 nanometer.This product characterizes proof through X-ray diffraction, transmission electron microscope: nano bismuth molybdate forms on the NaY zeolite surface, and it is of a size of 10～60 nanometers, and prove through the performance test of visible light degraded methyl orange: this material has degradation to methyl orange.
The new material feature that the present invention obtains can be tested with the following method:
(1), X-ray diffraction: material of the present invention is the composite that zeolite molecular sieve and nano bismuth molybdate are formed, can provide the strong diffraction maximum of zeolite molecular sieve and the broadening characteristic diffraction peak of bismuth molybdate in the x-ray diffraction pattern, judge with this whether nano bismuth molybdate forms.
(2), transmission electron microscope: can be clear that the existence and the size of nano bismuth molybdate at the zeolite molecular sieve grain surface by transmission electron microscope.
(3), photocatalytic activity: with the methyl orange solution is research system, detailed process is as follows: injecting the 100mL mass concentration in the 250mL beaker is the methyl orange solution of 10mg/L, the 0.1g Zeolite-based nano bismuth molybdate is put into methyl orange aqueous solution, use magnetic stirrer, make air enter reactant liquor, give the reactant liquor oxygen supply.Use visible lamp as light source, the irradiation reaction system.In the course of reaction, the solution quality change in concentration is calculated its percent of decolourization by the light absorption value of ultraviolet-visible spectrophotometer in 463nm place mensuration methyl orange.
Embodiment two: a kind of Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof
Employing silica alumina ratio (Si/Al) is 7 FER zeolite molecular sieve, and bake out temperature is 120 ℃.
Take by weighing the 0.4851g bismuth sulfate in small beaker, add 10mL distilled water, the 1.0000gFER zeolite molecular sieve is added wherein,, the 0.0882g sodium molybdate is added wherein at 50 ℃ of heating, stirring 15min, pH with the ammoniacal liquor regulator solution is 5, in 50 ℃ of heating, stirring reaction half an hour, centrifugation is with distilled water washing three times, put into 120 ℃ of oven dry of baking oven, promptly get product.This product characterizes proof through X-ray diffraction, transmission electron microscope: nano bismuth molybdate forms on the EFR zeolite surface, and it is of a size of the 10-60 nanometer, and prove through the performance test of visible light degraded methyl orange: this material has degradation to methyl orange.
Embodiment three: a kind of Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof
Employing silica alumina ratio (Si/Al) is 10 TON zeolite molecular sieve, and bake out temperature is 120 ℃.
Take by weighing 2.25g bismuth bromide (BiBr
3) in small beaker, add 10mL distilled water, the 5.0gTON zeolite molecular sieve is added wherein,, the 0.44g ammonium molybdate is added wherein at 50 ℃ of heating, stirring 15min, pH with the ammoniacal liquor regulator solution is 5, in 50 ℃ of heating, stirring reaction half an hour, centrifugation is with distilled water washing three times, put into 120 ℃ of oven dry of baking oven, promptly get product.This product characterizes proof through X-ray diffraction, transmission electron microscope: nano bismuth molybdate forms on the TON zeolite surface, and it is of a size of the 15-60 nanometer, and prove through the performance test of visible light degraded methyl orange: this material has degradation to methyl orange.
Embodiment four: a kind of Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof
Employing silica alumina ratio (Si/Al) is 10 BEA zeolite molecular sieve, and bake out temperature is 120 ℃.
Take by weighing 1.58g bismuth chloride (BiCl
3) in small beaker, add 10mL distilled water, the 5.0gBEA zeolite molecular sieve is added wherein,, the 0.44g ammonium molybdate is added wherein at 50 ℃ of heating, stirring 15min, pH with the ammoniacal liquor regulator solution is 5, in 50 ℃ of heating, stirring reaction half an hour, centrifugation is with distilled water washing three times, put into 120 ℃ of oven dry of baking oven, promptly get product.This product characterizes proof through X-ray diffraction, transmission electron microscope: nano bismuth molybdate forms on the BEA zeolite surface, and it is of a size of the 15-70 nanometer, and prove through the performance test of visible light degraded methyl orange: this material has degradation to methyl orange.
Embodiment five: a kind of Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof
Employing silica alumina ratio (Si/Al) is 10 MFI (ZSM-5) zeolite molecular sieve, and bake out temperature is 120 ℃.
Take by weighing the 1.58g bismuth chloride in small beaker, add 10mL distilled water, the 5.0gMFI zeolite molecular sieve is added wherein,, the 0.44g potassium molybdate is added wherein at 50 ℃ of heating, stirring 15min, pH with the ammoniacal liquor regulator solution is 5, in 50 ℃ of heating, stirring reaction half an hour, centrifugation is with distilled water washing three times, put into 120 ℃ of oven dry of baking oven, promptly get product.This product characterizes proof through X-ray diffraction, transmission electron microscope: nano bismuth molybdate forms on the MFI zeolite surface, and it is of a size of the 10-60 nanometer, and prove through the performance test of visible light degraded methyl orange: this material has degradation to methyl orange.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit essence is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (9)
1, a kind of Zeolite-based nano bismuth molybdate visible light catalytic material is characterized in that: be carrier with the zeolite molecular sieve, the bismuth molybdate nanometer particle load is on the surface of described zeolite molecular sieve; Described zeolite molecular sieve is selected 8 oxygen membered ring channel structures, 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, and silica alumina ratio is less than or equal to 30 natural or synthesis zeolite.
2, Zeolite-based nano bismuth molybdate visible light catalytic material according to claim 1 is characterized in that: the silica alumina ratio of described zeolite molecular sieve is less than or equal to 15.
3, Zeolite-based nano bismuth molybdate visible light catalytic material according to claim 1 is characterized in that: the silica alumina ratio of described zeolite molecular sieve is less than or equal to 10.
4, Zeolite-based nano bismuth molybdate visible light catalytic material according to claim 1 is characterized in that:
The zeolite molecular sieve of described 8 oxygen membered ring channel structures adopts A type zeolite;
The zeolite molecular sieve of described 10 oxygen membered ring channel structures is selected a kind of in MFI, TON, FER and the STI zeolite for use;
The zeolite molecular sieve of described 12 oxygen membered ring channel structures is selected a kind of in FAU, LAL, MTN, BEA and the MOR zeolite for use.
5, a kind of preparation method of Zeolite-based nano bismuth molybdate visible light catalytic material is characterized in that: made by following raw materials according and operating procedure:
(1), raw material
1., zeolite molecular sieve: select 8 oxygen membered ring channel structures, 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, and silica alumina ratio is less than or equal to 30 natural or synthesis zeolite;
2., bismuth salting liquid: soluble bismuth salt is dissolved in the deionized water, and being made into concentration is the bismuth salting liquid of 1～5mol/L; Described soluble bismuth salt selects to fluoridize a kind of in bismuth, bismuth chloride, bismuth bromide, bismuth iodide, bismuth nitrate and the bismuth sulfate;
3., molybdate solution: the soluble molybdenum hydrochlorate is dissolved in is made into molybdate solution in the deionized water; Described soluble molybdenum hydrochlorate is selected a kind of in molybdenum acid ammonia, sodium molybdate and the potassium molybdate;
(2), operating procedure
Step 1, according to 0.1～1: 1 mass ratio between soluble bismuth salt and the zeolite molecular sieve, described zeolite molecular sieve is immersed in the described bismuth salting liquid, make the zeolite molecular sieve liquid that obtains bismuth-containing after soluble bismuth salt and the zeolite molecular sieve generation ion-exchange reactions;
Step 2, according to bismuth element and molybdenum element 2: 1 mol ratio between the two, in step 1, add described molybdate solution in the zeolite molecular sieve liquid of bismuth-containing, regulate pH value to 4～7 with ammoniacal liquor, simultaneously it is heated and stir, molybdenum acid ion and bismuth ion are fully reacted generate bismuth molybdate to obtain product;
Step 3, the product that step 2 is obtained carry out centrifugation, obtain sediment;
Step 4, spend the sediment that the deionised water step 3 obtains, remove the soluble-salt of participating in reaction, obtain the wet basis Zeolite-based nano bismuth molybdate visible light catalytic material;
Step 5, the wet basis Zeolite-based nano bismuth molybdate visible light catalytic material that step 4 is obtained are under 120 ℃～400 ℃ the condition after the oven dry at bake out temperature, finally obtain Zeolite-based nano bismuth molybdate visible light catalytic material.
6, the preparation method of Zeolite-based nano bismuth molybdate visible light catalytic material according to claim 5 is characterized in that: the silica alumina ratio of described zeolite molecular sieve is less than or equal to 15.
7, the preparation method of Zeolite-based nano bismuth molybdate visible light catalytic material according to claim 5 is characterized in that: the silica alumina ratio of described zeolite molecular sieve is less than or equal to 10.
8, the preparation method of Zeolite-based nano bismuth molybdate visible light catalytic material according to claim 5 is characterized in that:
The zeolite molecular sieve of described 8 oxygen membered ring channel structures adopts A type zeolite;
The zeolite molecular sieve of described 10 oxygen membered ring channel structures adopts a kind of in MFI, TON, FER, the STI zeolite;
The zeolite molecular sieve of described 12 oxygen membered ring channel structures adopts a kind of in FAU, LAL, MTN, BEA, the MOR zeolite.
9, the preparation method of Zeolite-based nano bismuth molybdate visible light catalytic material according to claim 5 is characterized in that: described bake out temperature is 120 ℃～300 ℃.
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| CN109529919A (en) * | 2018-12-26 | 2019-03-29 | 桂林理工大学 | A kind of preparation method of the dedicated modified molecular sieve of ceramic ink |
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