CN100490967C - A preparation method of bismuth silicate powder photocatalyst - Google Patents
A preparation method of bismuth silicate powder photocatalyst Download PDFInfo
- Publication number
- CN100490967C CN100490967C CNB2007101662184A CN200710166218A CN100490967C CN 100490967 C CN100490967 C CN 100490967C CN B2007101662184 A CNB2007101662184 A CN B2007101662184A CN 200710166218 A CN200710166218 A CN 200710166218A CN 100490967 C CN100490967 C CN 100490967C
- Authority
- CN
- China
- Prior art keywords
- bismuth
- photocatalyst
- silicate powder
- preparation
- bismuth silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a preparation method for bismuth silicate powder photocatalyst. At first pentahydrate bismuth nitrate and active agent on the surface of a segmented copolymer are dissolved in acetic acid to form uniform clear solution, and then silicate ester is added into solution containing bismuth according that the mol ratio of bismuth to silicon is equal to 12:1, and is fully mixed to form uniform sol. After aging, the solution is moved into an autoclave to be hermetically crystallized, so as to obtain the composite oxide gel of the bismuth and the silicon, and after being filtered, cleaned, and dried, at last precursor powder is roasted in the air environment, namely, the bismuth silicate powder photocatalyst of the granularity with micron size is obtained. The invention can stably and uniformly obtain the bismuth silicate powder with good crystallinity under the lower temperature, and the granularity of the photocatalyst is larger, thereby being convenient for being separated from a water body to facilitate the recovery and the operation, the photocatalyst has highly effective photocatalytic activity, and is applicable for photocatalytic degrading organic pollutants.
Description
Technical field
The present invention relates to a kind of preparation method of bismuth silicate powder photocatalyst, belong to surround lighting catalysis water-treatment technology field.
Background technology
Bi silicate crystals is the non-ferroelectric cube semiconductor of a kind of broad-band gap, high resistivity.Multiple effects such as it has that electric light, photoconduction, light are sold off, piezoelectricity, acousto-optic, optically-active and faraday rotation are a kind of optical information materials that extensive future is arranged.Utilize the electric light and the photoconductive property of bi silicate crystals, at room temperature just can realize many kinds of nonlinear optics conversion with low power laser.Bi silicate crystals is one of several photorefractive materials that sensitivity is the highest, response speed is the fastest that obtained at present, thereby is widely used in technology such as optical information processing in real time and light operation calculating.
The research of bi silicate crystals material is existing two more than ten years so far, initial it be used as a kind of piezoelectric and photorefractive material is studied, as a kind of important photoelectric material, bi silicate crystals has caused material science and photocatalysis field scientist's very big attention but in recent years.The method of growth silicic acid bismuth single crystal all is to adopt from the fusion czochralski method both at home and abroad at present, and making bismuth silicate is the large volume crystal.Traditional solid phase reaction sintering process can be that raw material mixes with bismuth oxide and silicon oxide powder, makes bismuth silicate powder by solid phase reaction.The shortcoming of this method is that the mixing of two kinds of raw materials is difficult to reach complete and homogeneous, and grain growth at high temperature, reunion, is difficult to obtain the desirable amount powder granule.Simultaneously since bismuth oxide 800 ℃ of high temperature (〉) under boiling characteristics, after heat treatment, can cause departing from the appearance of the substandard product of desirable stoichiometric proportion.
Document " Journal of Materials Science Letters 1999,18:1871-1874 " is to adopt mechanical alloying to prepare bismuth silicate powder.This method is to be raw material with bismuth oxide and silicon oxide powder, directly prepare bismuth silicate nano powder through high-energy ball milling, this method has utilized the mechanical alloying that two kinds of powders take place in collision and crushing process repeatedly to react to synthesize target product, has saved high-temperature heat treatment process.But the mechanical alloying method required time is long, and production efficiency is low, is unsuitable for producing in batches bismuth silicate powder.
In addition, the method for synthetic silicic acid bismuth meal body also has sol-gal process and solvent evaporation method.Document " Bai Chaohui, Ba Xuewei, Jia Ru, Liu Bo, Xiao Zhiyi, Zhang Xiyan Chinese Journal of Inorganic Chemistry 2006; 22:1327-1329 " with Prepared by Sol Gel Method the bismuth silicate powder of nano-scale, and its optical excitation characteristic studied, but its light degradation property is not investigated; Document " preparation method of CN1821088A bismuth silicate nano powder and use to adopt solvent evaporation method to prepare nano level bismuth silicate powder; and Congo red performance in its photocatalytic degradation water estimated, think that bismuth silicate has bigger potentiality to be exploited as photochemical catalyst.
Above-mentioned work has successfully realized the artificial synthetic of bismuth silicate powder, and method is also comparatively ripe and stable, but gained bismuth silicate material is nano-powder, and granularity is less, still can't solve the problem that catalyst separates from water body; And the specific area of these materials is limited, can't adsorb a large amount of organic matters and carry out degradation reaction in water body, therefore need further improve its structure and form, makes it better to be the service of water body purification industry.
Summary of the invention
The objective of the invention is to propose a kind of bismuth silicate powder photocatalyst that is used for degradable organic pollutant and preparation method thereof with highlight catalytic active, bigger serface and bulky grain size.This photochemical catalyst specific area is bigger, and easier separation is reclaimed, and has kept the high catalytic activity of nanometer bismuth silicate powder, so have better industrial prospect.
The bismuth silicate powder photocatalyst of the micron particles degree that is used for degradable organic pollutant that the present invention proposes is that the crystal grain by 300～500 nanometer sizes gathers the diameter that forms at 10～30 microns bulky grain, have unique loose structure (seeing accompanying drawing 1), specific area is in 3～10 meters squared per gram.
This bismuth silicate powder photocatalyst adopts solvent-thermal method synthetic, wherein the source of silicon is an esters of silicon acis, the source of bismuth is five water bismuth nitrates, and the mol ratio of each component is an esters of silicon acis when synthetic: bismuth nitrate: acetate: block interpolymers surfactant=1:12:350:0.17～0.34.
The concrete preparation method of the bismuth silicate powder photocatalyst that is used for degradable organic pollutant that the present invention proposes is as follows: 1) five water bismuth nitrates are dissolved in the acetic acid solution of 0.008～0.016 mol block interpolymers surfactant, forming bismuth nitrate concentration is the bismuth-containing solution of 0.7 mol; 2) bismuth in molar ratio: silicon=12:1 meter, esters of silicon acis is joined in the bismuth-containing solution, fully stir, form uniform sol; 3) with colloidal sol ageing at room temperature after 3 hours, move in the autoclave of band polytetrafluoroethylene bushing, airtight crystallization is 24～48 hours under 120 ℃～160 ℃, takes out crystallization product bismuth Si composite oxide gel, filter, washing, 120～150 ℃ be dry down, obtains the presoma of bismuth silicate powder; 4) in air ambient, precursor powder, is promptly got aggregate and is of a size of 10～30 microns, the bismuth silicate powder photocatalyst of grain size between 300～500 nanometers after 3 hours in 380～550 ℃ of following high-temperature roastings.
Among the present invention, used esters of silicon acis is a kind of of ethyl orthosilicate, methyl silicate; Structure directing agent is a kind of of block interpolymers surfactant P123, F108, F127.Wherein the molecular formula of P123 is PEO20-PPO70-PEO20, and molecular weight is 5750 gram/moles; The molecular formula of F108 is PEO132-PPO50-PEO132, and molecular weight is 15500 gram/moles; The molecular formula of F127 is PEO106-PPO70-PEO106, and molecular weight is 14600 gram/moles.
The present invention before crystallization process with acetate as solvent, can complexing five water bismuth nitrates, hydrolysis is relaxed more, obtain uniform composite oxide sol easily.Activity to photochemical catalyst provided by the invention can be tested with the following method:
Accurately take by weighing 0.1～0.2 gram bismuth silicate powder photocatalyst, then it is joined in the organic aqueous solution that 100 ml concns are 15～20 mg/litre, under the ultrasonic wave effect, make suspension, under xenon lamp (simulated solar spectrum, 500 watts) irradiation, react.4 milliliters of samplings in per 20 minutes, catalyst is removed with high speed centrifugation.The ultraviolet-visible spectrum of surplus solution is analyzed on ultraviolet specrophotometer (Varian, Cary50 type).Degradation rate (%)=residual organic substances concentration/initial organic concentration) * 100.
Photochemical catalyst provided by the invention has following advantage:
1. have unique loose structure, aggregate is of a size of 10～30 microns, and crystal grain is big or small between 300～500 nanometers, the bismuth silicate particle of gamma oxidation bismuth crystal formation, and its specific area is 3～10 meters squared per gram.
2. be light source with the xenon lamp, need not oxidant applying and auxiliary agent, can a step degradable organic pollutant.
3. catalyst preparation process is simple, the catalytic activity height, and the reaction condition gentleness, low to the reaction unit requirement, be beneficial to industrialization promotion.
Description of drawings
Fig. 1 is the Large-angle X-ray diffraction spectrogram of bismuth silicate powder photocatalyst;
Fig. 2 is the scanning electron microscope image of bismuth silicate powder photocatalyst under different resolution;
Fig. 3 is the X-ray energy spectrum spectrogram of bismuth silicate powder photocatalyst;
Fig. 4 is that the uv-visible absorption spectroscopy of its aqueous solution is penetrated the variation of time with illumination in the process of using bismuth silicate powder photocatalyst photocatalytic degradation acridine orange of the present invention.
The specific embodiment
Embodiment 1
Take by weighing 4.6 gram P123 block interpolymers surfactants, at room temperature it is dissolved in 50 milliliters of acetate (CH
3COOH) forming concentration is the solution of 0.016 mol, constantly is stirred to dissolving, then adds 17 grams, five water bismuth nitrate (Bi (NO
3)
3) 5H
2O), after the dissolving fully, dropwise add 0.52 gram ethyl orthosilicate (Si (OC
2H
5)
4), this moment, the two mol ratio was 12:1.Vigorous stirring forms uniform and stable colloidal sol.Under stirring, with this colloidal sol ageing at room temperature 3 hours, a small amount of muddy particle occurs, be silicon bismuth composite oxide gel, then move in the autoclave, further descended airtight crystallization 24 hours at 150 ℃, take out the composite oxides gel precipitation, washing is filtered, 120 ℃ of evaporation oven dry down, obtain precursor powder.The gained precursor powder is roasting 3 hours in the air atmosphere under 550 ℃ temperature, promptly obtains bismuth silicate powder photocatalyst, is designated as the 1# sample.This sample is measured through nitrogen adsorption-desorption specific surface determination method, and its specific area is 3.3 meters squared per gram.
Embodiment 2
7.75 gram F108 block interpolymers surfactant dissolves is in 50 milliliters of acetate, forming concentration is the solution of 0.01 mol.Add 16.95 grams, five water bismuth nitrates to dissolving, dropwise add 0.34 gram methyl silicate (Si (OCH
3)
4), this moment, the two mol ratio was 12:1.Vigorous stirring forms uniform sol.Ageing moved to aforementioned colloidal sol in the autoclave after 3 hours, took out washing in 36 hours 140 ℃ of following crystallization, filtered, and 120 ℃ of evaporation oven dry down, roasting is 3 hours in 450 ℃ of following air atmospheres, promptly obtains bismuth silicate powder photocatalyst, is designated as the 2# sample.Its specific area is 4.6 meters squared per gram.
Embodiment 3
2.3 gram P123 block interpolymers surfactant dissolves is in 50 milliliters of acetate, forming concentration is the solution of 0.008 mol.Add 17.5 gram nitric hydrate bismuths to dissolving fully, dropwise add 0.52 gram ethyl orthosilicate then and form uniform sol.Ageing moved to this colloidal sol in the autoclave after 3 hours, took out after 48 hours 160 ℃ of following crystallization, and washing is filtered, and 130 ℃ of evaporation oven dry down, the gained precursor powder was 380 ℃ of following roastings 3 hours, and the gained bismuth silicate powder photocatalyst is designated as the 3# sample.Its specific area is 10.1 meters squared per gram.
Embodiment 4
6 gram F127 block interpolymers surfactant dissolves are in 50 milliliters of acetate, and forming concentration is the solution of 0.0082 mol.Add 17 grams, five water bismuth nitrates and be stirred to dissolving, dropwise add 0.52 gram ethyl orthosilicate, vigorous stirring forms even colloidal sol.Ageing moved to this colloidal sol in the autoclave after 3 hours, 120 ℃ of following crystallization 48 hours, took out precipitation, washing, drying is 130 ℃ of evaporation oven dry down, obtain precursor powder roasting 3 hours in 450 ℃ of following air atmospheres, the gained bismuth silicate powder photocatalyst is designated as the 4# sample.Its specific area is 5.3 meters squared per gram.
Embodiment 5
3.2 gram P123 block interpolymers surfactant dissolves is in 50 milliliters of acetate, forming concentration is the solution of 0.011 mol.Add 17 grams, five water bismuth nitrates, constantly be stirred to dissolving fully, dropwise add 0.34 gram methyl silicate then, vigorous stirring forms uniform sol.Ageing moved to aforementioned colloidal sol in the autoclave after 3 hours, 160 ℃ of following crystallization 24 hours, took out gel precipitation, washing, 140 ℃ of down oven dry, obtain precursor powder roasting 3 hours in 400 ℃ of following air atmospheres, the bismuth silicate powder photocatalyst that obtains is designated as the 5# sample.Its specific area is 6.9 meters squared per gram.
Choose the 1# sample application in different light-catalyzed reactions, active fructufy is for example following:
Reaction 1: take by weighing 0.1 gram 1# sample, it is joined in the methyl orange aqueous solution that 100 ml concns are 15 mg/litre, under ultrasonication, make suspension, magnetic agitation is reacted under xenon lamp (simulated solar spectrum, 500 watts) irradiation, 4 milliliters of samplings in per 20 minutes, high speed centrifugation separates, and (Varian analyzes on cary50) at ultraviolet-visible spectrometer to get supernatant liquor.One hour degradation rate of methyl orange is 53.6%.
Reaction 2: take by weighing 0.2 gram 1# sample, it is joined in the acridine orange aqueous solution that 100 ml concns are 20 mg/litre, under ultrasonic, make suspension, magnetic agitation, react under the xenon lamp irradiation, supernatant liquor analysis is got in sampling in per 20 minutes after the centrifugation.One hour degradation rate of acridine orange is 92.8%.
Claims (3)
1. the preparation method of a bismuth silicate powder photocatalyst, it is characterized in that may further comprise the steps: 1) five water bismuth nitrates are dissolved in the acetic acid solution of 0.008～0.016 mol polyoxyethylene-poly-oxypropylene polyoxyethylene block polyether, forming bismuth nitrate concentration is the bismuth-containing solution of 0.7 mol; 2) bismuth in molar ratio: silicon=12:1 meter, esters of silicon acis is joined in the bismuth-containing solution, fully stir, form uniform sol; 3) with colloidal sol ageing at room temperature after 3 hours, move in the autoclave of band polytetrafluoroethylene bushing, airtight crystallization is 24～48 hours under 120 ℃～160 ℃, take out crystallization product bismuth Si composite oxide gel, filter, washing, 120～150 ℃ be dry down, obtains the presoma of bismuth silicate powder photocatalyst; 4) in air ambient, precursor powder, is promptly got by aggregate crystal grain and piles up the bismuth silicate powder photocatalyst of forming after 3 hours in 380～550 ℃ of following high-temperature roastings.
2. the preparation method of photochemical catalyst as claimed in claim 1, wherein said polyoxyethylene-poly-oxypropylene polyoxyethylene block polyether is P123, F108 or F127.
3. the preparation method of photochemical catalyst as claimed in claim 1, wherein said esters of silicon acis is ethyl orthosilicate or methyl silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101662184A CN100490967C (en) | 2007-11-08 | 2007-11-08 | A preparation method of bismuth silicate powder photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101662184A CN100490967C (en) | 2007-11-08 | 2007-11-08 | A preparation method of bismuth silicate powder photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101157026A CN101157026A (en) | 2008-04-09 |
| CN100490967C true CN100490967C (en) | 2009-05-27 |
Family
ID=39305332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101662184A Expired - Fee Related CN100490967C (en) | 2007-11-08 | 2007-11-08 | A preparation method of bismuth silicate powder photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100490967C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575098B (en) * | 2009-05-26 | 2013-03-20 | 内蒙古华生高岭土有限责任公司 | Composite additive applied in coal hard kaolin wet milling technology |
| CN101670285B (en) * | 2009-09-16 | 2012-07-04 | 桂林理工大学 | Visible light responding Bi-system composite oxide photocatalyst Bi2-xRxO3 and preparation method |
| CN101709508B (en) * | 2009-11-10 | 2011-10-26 | 陕西科技大学 | Preparation method of bismuth-containing eulytite bismuth silicate crystals |
| CN101891274B (en) * | 2010-07-27 | 2011-08-03 | 北京师范大学 | Method for coprocessing crystal violet polluted sewage by outdoor natural light-hydrogen peroxide |
| CN102120665B (en) * | 2011-01-18 | 2012-08-29 | 北京师范大学 | Method for purifying pentachlorophenol in water through photocatalysis |
| CN102275944A (en) * | 2011-07-06 | 2011-12-14 | 陕西科技大学 | Preparation method of new scintillating bismuth silicate powder |
| CN102716701B (en) * | 2012-06-21 | 2014-07-23 | 华中师范大学 | Method for preparing nickel-doped bismuth silicon oxide microspheres by ultrasonic spray |
| CN103831094B (en) * | 2012-11-23 | 2016-08-10 | 北京师范大学 | A kind of with doped yttrium induced oxidation bismuth crystal conversion with the method improving its photocatalysis effect |
| CN103949655B (en) * | 2014-04-11 | 2016-04-20 | 西安建筑科技大学 | A kind of raw material of stoichiometric proportion and sol-gal process prepare the method for bismuth silicate powder |
| CN104192854B (en) * | 2014-07-07 | 2016-02-10 | 上海应用技术学院 | A kind of method preparing bismuth silicate powder |
| CN104607174B (en) * | 2014-12-31 | 2017-02-22 | 中国石油天然气股份有限公司 | Calcium-doped beta-Bi2O3 photocatalyst as well as preparation method and application thereof |
| CN105948118B (en) * | 2016-05-05 | 2017-10-27 | 陕西科技大学 | A kind of porous Bi4Si3O12The preparation method of bulk |
| CN111330588A (en) * | 2018-12-19 | 2020-06-26 | 福州大学 | High-activity propylene gas-phase epoxidation catalyst and preparation method thereof |
| CN110586067B (en) * | 2019-09-20 | 2022-08-05 | 太原理工大学 | Bi/Bi 2 SiO 5 Preparation method and application of photocatalyst |
| CN114471586A (en) * | 2022-03-28 | 2022-05-13 | 王美珍 | Composite photocatalyst for treating organic pollutants in wastewater and preparation method and application thereof |
-
2007
- 2007-11-08 CN CNB2007101662184A patent/CN100490967C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| Hydrothermal growth of bismuth silicate(BSO). John Larkin et al.Journal of Crystal Growth,Vol.128 . 1993 |
| Hydrothermal growth of bismuth silicate(BSO). John Larkin et al.Journal of Crystal Growth,Vol.128 . 1993 * |
| Low-defect colorless Bi12SiO20 grown by hydrothermaltechniques. Meckie T. et al.Appl. Phys. Lett.,Vol.60 No.17. 1992 |
| Low-defect colorless Bi12SiO20 grown by hydrothermaltechniques. Meckie T. et al.Appl. Phys. Lett.,Vol.60 No.17. 1992 * |
| 硅酸铋（BSO）纳米粉体的制备与表征. 柏朝晖等.无机化学学报，第22卷第7期. 2006 |
| 硅酸铋（BSO）纳米粉体的制备与表征. 柏朝晖等.无机化学学报，第22卷第7期. 2006 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101157026A (en) | 2008-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100490967C (en) | A preparation method of bismuth silicate powder photocatalyst | |
| Pattnaik et al. | Synthesis, photoelectrochemical properties and solar light-induced photocatalytic activity of bismuth ferrite nanoparticles | |
| Kallawar et al. | Bismuth titanate based photocatalysts for degradation of persistent organic compounds in wastewater: A comprehensive review on synthesis methods, performance as photocatalyst and challenges | |
| Morassaei et al. | Simple salt-assisted combustion synthesis of Nd 2 Sn 2 O 7–SnO 2 nanocomposites with different amino acids as fuel: an efficient photocatalyst for the degradation of methyl orange dye | |
| Zinatloo-Ajabshir et al. | Recent advances in nanostructured Sn− Ln mixed-metal oxides as sunlight-activated nanophotocatalyst for high-efficient removal of environmental pollutants | |
| Li et al. | Enhanced photocatalytic activity of gC 3 N 4–ZnO/HNT composite heterostructure photocatalysts for degradation of tetracycline under visible light irradiation | |
| CN101890354B (en) | Method for preparing bismuth ferrite photocatalyst | |
| Duan et al. | Synthesis and characterization of morphology-controllable BiFeO3 particles with efficient photocatalytic activity | |
| Sui et al. | Photocatalytically reducing CO 2 to methyl formate in methanol over Ag loaded SrTiO 3 nanocrystal catalysts | |
| CN105854863B (en) | A kind of C/ZnO/TiO2The preparation method of composite Nano catalysis material | |
| US20100062928A1 (en) | Method for production of doped titanium oxide, doped titanium oxide, and visible light-responsive photocatalyst comprising the doped titanium oxide | |
| CN102000584A (en) | Method for preparing cobalt-doped improved beta-bismuth oxide photocatalyst | |
| CN101147859A (en) | Method for preparing porous bismuth titanate photocatalyst | |
| Zhang et al. | The synergetic enhancement of piezo catalytic performance to remove tetracycline by K2Ti6O13/TiO2 composite | |
| CN100509146C (en) | Method for preparing porous barium titanate photocatalyst | |
| CN105879884A (en) | One-dimensional ZnS (zinc sulfide)/CdS-C nanocomposite material and preparation method thereof | |
| Zhang et al. | Uniform hollow TiO2: Sm3+ spheres: Solvothermal synthesis and luminescence properties | |
| Zhang et al. | UV-Vis-NIR-light-driven Ag2O/Ag2S/CuBi2O4 double Z-scheme configuration for enhanced photocatalytic applications | |
| CN101693552B (en) | Method for preparing tin dioxide nanostructure material with floriform appearance by hydrothermal synthesis | |
| CN114392734B (en) | Tungsten oxide composite material and preparation method and application thereof | |
| CN109382088B (en) | SnO2/α～Bi2O3/β～Bi2O3Composite material and preparation method thereof | |
| CN114618537A (en) | Red phosphorus/strontium titanate heterojunction photocatalyst and preparation method and application thereof | |
| Huan et al. | Enhanced ferro-photocatalytic performance for ANbO 3 (A= Na, K) nanoparticles | |
| CN113289646A (en) | Core-shell structured nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst and preparation method and application thereof | |
| CN102219263A (en) | Method for preparing Gamma-MnOOH nanometer rod |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090527 Termination date: 20091208 |