CN102794186A - Oxyhalide photo-catalytic material and preparation method thereof - Google Patents
Oxyhalide photo-catalytic material and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to an oxyhalide photo-catalytic material and a preparation method thereof, and belongs to the field of photo-catalytic materials. The oxyhalide photo-catalytic material is prepared by using a solid phase or liquid phase method. The photo-catalytic material is characterized in that the chemical composition of the material is BiOX, wherein X is Cl, Br or I; and [Bi2O2] and [X] structural layers are alternately and mutually stacked along the c axis to form a lamellar crystal structure. The prepared BiOX (X is Cl, Br or I) has excellent photo-catalytic performance, and can be used for degrading organic dyes, degrading harmful gases, sterilizing and photolyzing water to produce hydrogen. By supporting nano metal particles with high electron affinity such as Ag and Pt, the photo-catalytic performance of the material can be greatly improved.
Description
Technical field
The present invention relates to halogen-oxide photocatalytic material and preparation method thereof, belong to field of photocatalytic material, especially belong to fields such as dyestuff degraded, photodissociation aquatic products hydrogen, the degraded of organic pernicious gas, sterilization.
Background technology
Find at TiO from Fujishima in 1972 and Honda
2The electrode material surface photoresponse has been produced since the hydrogen phenomenon, and photocatalysis causes global concern as solving environmental pollution and a kind of potential technology of energy crisis.In the conductor photocatalysis process, illumination is penetrated the electron transition that excites in the valence band to conduction band, is promptly forming photohole forming on light induced electron and the valence band on the conduction band; Carrier mobility is behind powder particle surface, and complicated oxidation, reduction reaction take place abundant and environmental activity on every side.Mat utilizes the strong reduction characteristic of electronics and the oxidation in hole in this, can be with the H in the water
+And OH
-Reduce respectively and be oxidized to H
2And O
2In addition, move to photocatalyst surface electronics and hole can also with the O in the environment
2, H
+, OH
-Form O Deng effect
2 -, OH and HO
2 -The isoreactivity strong oxidizer is used for oxidative degradation and the organic pollution that purifies liquid phase, gas phase.
Except potential photodissociation aquatic products hydrogen energy source purposes, photocatalysis technology solves in the problem of environmental pollution in reality shows up prominently.At present, with TiO with low cost, that have high chemical stability
2For the photocatalysis technology of base material has obtained application in anti-Exposure to Sunlight cosmetics, sedan limousine metallochrome finish paint and electronics industry, duplicator industry, high voltage insulating materials, ic substrate, fluorescent tube and other more fields.It is introduced that this photocatalysis technology also can be widely used in household electrical appliance such as sanitary ceramics, glassware, burner, numeric keypad and air-conditioning, refrigerator, washing machine, will bring dramatic change to construction material, household electrical appliance and daily life.The relevant expert claims, if this technology large-scale promotion application will be expected to become the high-tech sharp weapon that solve problem of environmental pollution.
The research majority of photochemical catalyst rests on TiO both at home and abroad at present
2And relevant modifications,, noble metal compound and oxide carried etc. like the nanometerization of material and high-ratio surfaceization, doping, semiconductor.Although these work are fruitful, its quantum yield is not high, and is difficult to use in the purposes of photocatalysis cracking aquatic products hydrogen, and therefore, looking for new and effective photochemical catalyst has become one of most important problem in field up till now.According to the catalysis material of having found, its system is sorted out can be divided into oxide, sulfide, oxysulfide, nitride and oxynitride, and wherein oxide often has reasonable (light) chemical stability; Though sulfide and oxysulfide can show comparatively ideal visible light-responded characteristic, are easy to generate photochemical corrosion as catalysis material; Nitride and oxynitride also have visible light absorption preferably; The photocatalysis effect of its material own is desirable not to the utmost; But behind load electron affinity strong noble metal or its oxide, photocatalytic activity can be able to be increased sharply, like (GaN) of load Rh-Cr nano composite oxide
x(ZnO)
1-xSolid-solution powder visible light responsible photocatalytic splitting water hydrogen-producing speed can reach the mmol/h order of magnitude, and the active extreme difference of the powder photocatalytic of load not.
Seek new and effective photochemical catalyst and be always the long-term and difficult task in one in photocatalysis technology field, it is that photocatalysis technology can be able to the especially key issue in application place in the photolysis water hydrogen field of large-scale promotion application.
Summary of the invention
The object of the present invention is to provide a kind of novel halogen-oxide photocatalytic material and multiple preparation method.
BiOX (X=Cl, Br, I) in the crystal structure, [Bi
2O
2] alternately pile up each other along the c direction of principal axis with [X] structure sheaf, form the layered crystal configuration of this type uniqueness.(X=Cl, Br I) can be with calculating, and the result shows that conduction band mainly is made up of Bi 6p track, and valence band is mainly by Cl 3p (or Br 4p, I5p) composition to utilize Density functional (DFT) band theory computational methods to carry out BiOX; (I) semiconductor is a kind of indirect transition material to BiOX for X=Cl, Br, and Bi6p is comparatively disperse in conduction band, helps the transmission of electronics at material internal, improves electron conduction and corresponding light induced electron-hole separating power.Uv-visible absorption spectroscopy shows that (I) the absorbed limit corresponds to 358,426 respectively to BiOX for X=Cl, Br, and about 646nm, its optical energy gap is corresponding to 3.46,2.91, about 1.92eV.
We adopt several different methods such as multiple solid phase or liquid phase to come synthetic material, and material is carried out the photocatalysis performance test.
One, material preparation
Method one:
With Bi
2O
3Powder is dissolved in the dense hydracid (HCl, HBr, HI), is adjusted to pH=2～5 with ammoniacal liquor, and the process multiple times of filtration is until detecting less than X
-Behind the ion (checking with liquor argenti nitratis ophthalmicus), sediment is dried the photocatalytic powder that gets product.
The BiOX of load (I) detailed process of catalysis material can be for X=Cl, Br: (I) insert in the beaker that contains deionized water for X=Cl, Br, adds the methyl alcohol hole sacrifice agent of capacity and the AgNO of 0.05～5wt% to get BiOX by catalyst fines
3Or 0.05～5wt%H
2PtCl
66H
2O shines 5～10h under mercury lamp in the time of powerful the stirring, through the multiple times of filtration washing, be drying to obtain the catalysis material that load has nanometer Ag or Pt particle.
(I) the photocatalysis powder particle diameter is 5～120nm to the BiOX of gained for X=Cl, Br, and load has Ag or the Pt of 0.05～5wt%.
Method two:
Will be by the Bi of stoichiometric proportion
2O
3And BiX
3(I) powder placed quartz ampoule for X=Cl, Br, vacuumizes the back encapsulation, 400-750 ℃ of heating 2-24 hour.Cooling back open pipe grinds the photocatalytic powder that gets product.
Method three:
Remove ionized water in beaker;, then solution is heated less than 1 with corresponding hydracid regulator solution pH, when constantly stirring; Bismuth nitrate-hydracid the solution that slowly adds stoichiometric proportion, slowly adding concentration simultaneously is the HNO that 5～20%NaOH solution produces with neutralizing hydrolysis
3, keep the pH value 2～5, whole process continues about 0.5～5h.Temperature constant is about 50～90 ℃ therebetween, and continuation is stirred more than the 10min, cools off, filters, washs, dries the photocatalytic powder that gets product.
Method four:
The hydracid, the solid nitric acid bismuth that add stoichiometric proportion mix; Add then and account for mixture weight 0.5～5% anhydrous sodium sulfate and 0.5～5% neopelex solution; Add the hot water stirring again and obtain clear solution; Put into the micro-wave oven microwave irradiation then 2～3 minutes, and took out chilling, filter, wash, dry the photocatalytic powder that gets product.
Method five:
Get stoichiometric proportion bismuth nitrate-hydracid solution, add the alkali halide (corresponding with hydracid) of excessive ratio when constantly stirring, using weak aqua ammonia to regulate pH then is 2～5, stirs, and filters, washing, dries the photocatalytic powder that gets product.
Method six:
Bismuth nitrate is dissolved in the capacity glacial acetic acid; The mixed solution that adds sodium carbonate and alkali halide when stirring fast; The mol ratio of sodium carbonate and alkali halide is 1: (0.5～1.5), after the vigorous stirring, filter, wash, dry the photocatalytic powder that gets product.
Two, performance evaluation (photocatalysis performance)
Select P25-TiO for use
2The qualitative judge of photochemical catalyst BiOX (X=Cl, Br, photocatalytic activity I), the same BiOX of experimentation (X=Cl, Br, I).
(1) dyestuff degraded and photodissociation aquatic products hydrogen
Gained sample powder of the present invention is carried out the research of photocatalytically degradating organic dye (methyl orange) and photocatalysis Decomposition aquatic products hydrogen in homemade reactor.The irradiation light source is the high-pressure mercury light modulation of 500W.During the catalysis experiment, the concentration of dyestuff is: 10mg/L, the powder amount in dye solution or in the pure water is: 0.2g/100mL.
(2) pernicious gas degraded
Gained sample powder of the present invention is carried out the research of the representative pernicious gas formaldehyde of photocatalytic degradation in homemade reactor.Light-catalyzed reaction is carried out in homemade column type stainless steel photo catalysis reactor, and light source is 8W uviol lamp (a PHILIPS company).The photochemical catalyst water is coated on the square glass sheet of a 70mm * 70mm * 2mm equably, after the oven dry it is suspended between the uviol lamp and aerofoil fan in the reactor.Earlier reaction system is vacuumized, reactor is airtight container.After vacuumizing, feed dry air, until reaching atmospheric pressure.With after a certain amount of solid polyformaldehyde gasification, inject reaction vessel then.When beginning experiment closed ultraviolet source, opens uviol lamp when content of formaldehyde in the system no longer reduces when promptly having reached adsorption equilibrium, carries out the UV irradiation, every at a distance from 20min with the interior formaldehyde gas concentration of gas chromatograph detection system, press Δ C/C
0Calculate the degradation rate of photochemical catalytic oxidation decomposing formaldehyde.
(3) sterilization test
Choose Escherichia coli E.coli and staphylococcus aureus as test strain.With beef-protein medium bacterium is bred.Adopt blood cell counting plate institute's bacteria containing amount in microscopically direct count mensuration solution to measure the germicidal efficiency of powder.
See that from test result (I) ability of degradable organic pollutant is superior to nanometer P25-TiO to BiOX for X=Cl, Br
2, photodissociation aquatic products hydrogen speed reaches 10～100 μ mol/h orders of magnitude under ultraviolet light response, is superior to nanometer P25-TiO
2, the BiOX pernicious gas formaldehyde of also can degrading kills the effect of removing Escherichia coli and staphylococcus aureus and all is superior to nanometer P25-TiO
2
Description of drawings
Fig. 1 is the BiOX layered crystal structure;
Fig. 2 is the BiOCl band structure;
Fig. 3 is BiOCl partial density of states and total density of states;
Fig. 4 is BiOX (X=Cl, Br, I) uv-visible absorption spectra;
Fig. 5 be BiOX (X=Cl, Br, I) and P25-TiO
2The activity of photocatalytic degradation of dye methyl orange;
Fig. 6 is the field emission scanning electron microscope figure of the BiOCl of embodiment 1 preparation.
The specific embodiment
Introduce embodiments of the invention below, but the present invention is limited to embodiment absolutely not.
Embodiment 1:
With Bi
2O
3Powder dissolution is adjusted to pH=3 with weak aqua ammonia in corresponding dense hydracid, after detecting less than X-ion (checking with liquor argenti nitratis ophthalmicus), sediment is at 80 ℃ of oven dry nano-photo catalytic powder that gets product through multiple times of filtration.
The BiOX of load (I) detailed process of catalysis material can be for X=Cl, Br: (I) insert in the beaker that contains the 1OOml deionized water for X=Cl, Br, adds the methyl alcohol hole sacrifice agent of 10ml and an amount of AgNO to get 2g BiOX by catalyst fines
3Or H
2PtCl
66H
2O, in the time of powerful the stirring at 300W mercury lamp 85～10h, after through filtration washing repeatedly, be drying to obtain the catalysis material that load has nanometer Ag or Pt particle.
The experiment of photocatalysis to degrade organic matter methyl orange shows that (X=Cl, ultraviolet catalytic performance Br) is superior to P25-TiO to BiOX
2, (I) photocatalytic degradation methyl orange (MO) effect improves BiOX behind the loaded Ag nano particle for X=Cl, Br; And the effect of the Pt of load equal in quality mark is same as the situation of Ag load basically.
In photocatalysis cracking aquatic products hydrogen, hydrogen-producing speed all can reach the 10 μ mol/h orders of magnitude, and hydrogen output is in proper order under the same terms: BiOCl＞BiOBr＞BiOI.The effect of supporting Pt is superior to the situation of loaded Ag, and hydrogen-producing speed all rises, and reaches the 100 μ mol/h orders of magnitude, and the hydrogen output order still is: BiOCl＞BiOBr＞BiOI.And pure P25-TiO
2The ability that does not then have photocatalysis cracking aquatic products hydrogen.
In the experiment of the organic pernicious gas formaldehyde of degraded, behind the photocatalysis 2h, (degradation rate I) has all surpassed 90% to BiOX for X=Cl, Br.Degradation rate is BiOCl＞BiOBr＞BiOI in proper order, and pure P25-TiO
2Degradation rate is 81%.
In sterilization experiment, behind the photocatalysis 10h, BiOX (X=Cl, Br, sterilizing rate I) they are BiOCl＞BiOBr＞BiOI in proper order, sterilizing rate has all surpassed 70%.And pure P25-TiO
2Sterilizing rate is 55%.
Embodiment 2:
Bi with stoichiometric proportion
2O
3And BiX
3(X=Cl, Br I) placed quartz ampoule, vacuumize the back encapsulation, 550 ℃ of heating 12 hours.Cooling back open pipe grinds the photocatalytic powder that gets product.
Photocatalytic degradation of dye methyl orange, photodissociation aquatic products hydrogen, degraded harmful substance formaldehyde and sterilization test result are about about 40% in the embodiment 1, and this possibly be because less the causing of specific area of the sample that solid phase method makes.
Embodiment 3:
Get the 100ml deionized water in beaker;, then solution is heated to about 70 ℃ less than 1 with corresponding hydracid regulator solution pH, when constantly stirring; Slowly add 1mol bismuth nitrate-hydracid solution, slowly add the HNO that 15%NaOH solution produces with neutralizing hydrolysis simultaneously
3, keep the pH value about 2, whole process continues about 1h.Temperature constant is about 75 ℃ therebetween, continues to stir 10min, cooling, filter, washing, in 80 ℃ of oven dry photocatalytic powder that gets product.
The performance test results and embodiment 1 are basic identical.
Embodiment 4:
Add capacity 3mol hydracid, 1mol solid nitric acid bismuth, 2wt% anhydrous sodium sulfate and 1wt% neopelex solution; The hot water stirring that adds 75 ℃ again obtains transparent solution; Making cumulative volume is 200ml; Put into micro-wave oven irradiation then 2-3 minute, and took out chilling, filter, washing, in 80 ℃ of oven dry photocatalytic powder that gets product.
The performance test results is a little more than embodiment 1.
Embodiment 5:
Get the 1mol bismuth nitrate and be dissolved in capacity hydracid solution, add the corresponding sodium halide of 2mol when constantly stirring, using ammoniacal liquor to regulate pH then is 3, behind the vigorous stirring 30min, filter, washing, in 80 ℃ of oven dry photocatalytic powder that gets product.
The performance test results and embodiment 1 are basic identical.
Embodiment 6:
The 1mol bismuth nitrate is dissolved in the 5mol glacial acetic acid, adds fast the mixed solution of 3mol sodium carbonate and 2mol sodium halide in the time of stirring, behind the vigorous stirring 30min, filter, wash, in 80 ℃ of oven dry photocatalytic powder that gets product.
The performance test results and embodiment 1 are basic identical.
Claims (5)
1. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi
2O
2] alternately pile up each other along the c direction of principal axis with [X] structure sheaf, form the layered crystal configuration, it is characterized in that Bi by stoichiometric proportion
2O
3And BiX
3(I) powder places quartz ampoule for X=Cl, Br, vacuumizes the back encapsulation, and 400-750 ℃ of heating 2-24 hour, cooling back open pipe ground.
2. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi
2O
2] alternately pile up each other along the c direction of principal axis with [X] structure sheaf; Form the layered crystal configuration, it is characterized in that removing ionized water in beaker, with corresponding hydracid regulator solution pH less than 1; Then solution is heated; When constantly stirring, slowly add the bismuth nitrate-hydracid solution of stoichiometric proportion, slowly adding concentration simultaneously is the HNO that 5～20%NaOH solution produces with neutralizing hydrolysis
3, keep the pH value 2～5, whole process continues 0.5～5h, and temperature constant continues to stir more than the 10min cooling, filtration, washing, oven dry about 50～90 ℃ therebetween.
3. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi
2O
2] alternately pile up each other along the c direction of principal axis with [X] structure sheaf; Form the layered crystal configuration, the hydracid, the solid nitric acid bismuth that it is characterized in that adding stoichiometric proportion mix, and add then to account for mixture weight 0.5～5% anhydrous sodium sulfate and 0.5～5% neopelex solution; Add the hot water stirring again and obtain clear solution; Put into the micro-wave oven microwave irradiation then 2～3 minutes, and took out chilling, filter, wash, dry the photocatalytic powder that gets product.
4. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi
2O
2] alternately pile up each other along the c direction of principal axis with [X] structure sheaf; Form the layered crystal configuration; It is characterized in that getting stoichiometric proportion bismuth nitrate-hydracid solution, add the alkali halide (corresponding with hydracid) of excessive ratio when constantly stirring, using weak aqua ammonia to regulate pH then is 2～5; Stir, filter, wash, dry.
5. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi
2O
2] alternately pile up each other along the c direction of principal axis with [X] structure sheaf; Form the layered crystal configuration; It is characterized in that bismuth nitrate is dissolved in the capacity glacial acetic acid, add the mixed solution of sodium carbonate and alkali halide in the time of stirring fast, the mol ratio of sodium carbonate and alkali halide is 1: (0.5～1.5); After the vigorous stirring, filter, wash, dry the photocatalytic powder that gets product.
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| CN103130275A (en) * | 2013-03-25 | 2013-06-05 | 中国科学院新疆理化技术研究所 | Preparation method of laminar pearl bismuth oxychloride |
| CN105916812B (en) * | 2014-01-16 | 2017-09-08 | 默克专利股份有限公司 | Pigment based on bismuth compound |
| CN105916812A (en) * | 2014-01-16 | 2016-08-31 | 默克专利股份有限公司 | Pigments based on bismuth compounds |
| US9890287B2 (en) | 2014-01-16 | 2018-02-13 | Merck Patent Gmbh | Pigments |
| CN106807412A (en) * | 2017-03-16 | 2017-06-09 | 苏州德捷膜材料科技有限公司 | A kind of halogen-oxide photocatalytic agent, the preparation method and applications of Ag/AgCl loads |
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| CN107790159A (en) * | 2017-09-28 | 2018-03-13 | 浙江理工大学 | Photochemical catalyst and its preparation and application of a kind of high selectivity catalysis oxidation alcohol into aldehyde |
| CN107790159B (en) * | 2017-09-28 | 2020-05-01 | 浙江理工大学 | Photocatalyst for high-selectivity catalytic oxidation of alcohol into aldehyde and preparation and application thereof |
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