CN101264930A - Method for preparing metallic ion doping nano bismuth oxide - Google Patents
Method for preparing metallic ion doping nano bismuth oxide Download PDFInfo
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- CN101264930A CN101264930A CNA2008100310229A CN200810031022A CN101264930A CN 101264930 A CN101264930 A CN 101264930A CN A2008100310229 A CNA2008100310229 A CN A2008100310229A CN 200810031022 A CN200810031022 A CN 200810031022A CN 101264930 A CN101264930 A CN 101264930A
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- metal ion
- bismuth oxide
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- doped metal
- nano bismuth
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Abstract
The invention provides a method for preparing bismuth oxide doped with a metal ion, which is characterized in that the easy-made bismuth compound and an alcohol compound are acted as the reaction raw material, the transitional metal ion Fe <SUP> 3+</SUP> and Ni <SUP>2+</SUP> are doped, and then the metal ion doped bismuth oxide is prepared by means of an ultrasonic radiation. The preparation method for preparing bismuth oxide doped with the metal ion has the advantages of no environmental pollution, simple process, low production cost, and relatively narrow particle size distribution, strong oxidation capability, high catalysis activity, nontoxicity, good chemical stability of the produced product, which is applicable to the fields such as wastewater treatment, sewage treatment, waste gas disposal, and energy material, and also promoted to be used in the disposal of waste gas exhausted from the domestic rubbish burning industry and steel enterprises.
Description
Technical field
The present invention relates to a kind of preparation doped metal ion nano bismuth oxide (Bi
2O
3) method.
Background technology
Bi
2O
3Be a kind of important functional material, mainly exist with α (monoclinic form), β (square crystal formation), γ (cubic) and three kinds of crystal formations of δ (cubic).β-Bi wherein
2O
3And γ-Bi
2O
3It is the steady state crystal formation that is situated between.Application at present mainly concentrates on α and δ crystal formation.δ-Bi
2O
3Having very high oxide ion conduction performance, is a kind of electrolyte that has potentiality.Bi
2O
3Mainly be widely used in fields such as electronic ceramics powder body material, photoelectric material, high temperature superconducting materia, catalyzer.In recent years, relevant Bi
2O
3New application also constantly be seen in report.People such as A.Cabot as Barcelona, ESP university discover employing Bi
2O
3As the solid gas sensitive, NO there is good selection gas sensing property.
Nanometer Bi
2O
3The preparation method mainly contain the precipitator method, hydrolysis method, sol-gel method, spray method, microemulsion method etc.The particle diameter that different preparation methods obtain product is different with pattern.But all there is shortcoming separately in these methods.As the Bi that adopts the precipitator method to prepare
2O
3Size-grade distribution is inhomogeneous, and agglomeration is serious, and people such as Li Wei (Chinese patent 1544337A) disclose a kind of preparation nanometer Bi
2O
3Method, this method adopts pearl white concentrate as raw material, and it is leached, and obtains the nano bismuth oxide product with the sodium hydroxide solution precipitation after the removal of impurities.People such as Pati l (Materials letters, 2005,59:2523-2525) obtain bismuth hydroxide by the ammonia precipitation process bismuth nitrate solution, obtain nano bismuth oxide through after the roasting.Adopt hydrolysis method very easily to generate, adopt the raw materials cost of sol-gel method preparation higher, adopt the experiment condition harshness of spray method, need use the experimental installation of having relatively high expectations etc. than coarse particles.(journal of Shandong university (natural science edition) 1997,32 (1): such as Chen Dairong 880～93) with Bi (OR)
3(R:CH
2CH
2OCH
3, Cme
2Et) make presoma, synthesized Bi by the Sol-Gel method
2O
3It is spherical that polycrystal powder, the bismuth oxide micro-powder that obtains at last are approximately, and size range is 60～120nm.Adopt the technical process of molten atomizing oxidation style short, product purity is high, fine size, pollution-free, cost is low, but requires degree higher to equipment and processing parameter.(Wuhan University of Technology's journal, 2006,28 (2): 100～13) adopt bismuth vapor-phase oxidation method to make median size is the bismuth oxide powder of 33.7nm to Hu Hanxiang.The experimental installation of emulsion method is simple slightly, and energy consumption is low, strong operability, and powder monodispersity, interface property and the good stability of gained are compared with additive method, and particle diameter is easy to control, adapts to wide.But this method production cost is higher, needs to consume a large amount of organic solvent and tensio-active agent.There is report to be equipped with nanometer Bi with the polyhydroxy-alcohol legal system
2O
3, adopt this method effectively to stop particulate to be grown up, the Bi for preparing through this method
2O
3Grain diameter is 700～90nm (Journal of Materials Science 36 (2001) 297-299).At present both at home and abroad about ultra-fine Bi
2O
3Research some reports are arranged, but relevant single nanometer Bi
2O
3Research also relatively limited, its preparation method also is the focus of a research.
Bi
2O
3Have a wide range of applications in catalyst field, as bismuth molybdenum titanium mixed oxide, it is a kind of effective and economic catalytic material that is used for oxidizing reaction, to can be used as propylene oxidation in industrial application be propenal, be the catalyzer of processes such as furans from propylene production vinyl cyanide, preparing butadiene with butylene oxo-dehydrogenation, butadiene oxidation, and the bismuth oxide of the yttrium oxide that mixed can be used in the oxidation coupling reaction that methane changes ethane or ethene into.As a kind of phlogiston catalyzer, it is low that bismuth oxide has toxicity, and the ecological safety material that smog is few is progressively replacing plumbous oxide, becomes the important catalyst in the solid propellant.
Catalytic efficiency is an important research project in the photochemical catalysis.Bibliographical information, semi-conductor Bi
2O
3Band-gap energy be 2.8eV (and traditional photocatalyst TiO
2Band-gap energy be 3.2eV), so its energy gap and TiO
2Similar, and because its good stability has good photochemical catalysis development prospect.Nanometer Bi
2O
3Because its specific surface area is big, surfactivity point is many, thereby can show more excellent photocatalysis activity.At present for Bi
2O
3Photochemical catalysis research have only a small amount of report.Have and report the experimental study that contains nitrite waste water and degradating organic dye with the bismuth oxide photochemical catalysis, the result shows, Bi
2O
3Has good photocatalytic activity.(Solid State Chem.1998 72:126-130) has studied semi-conductor Bi to people such as Anthony
2O
3Catalyzed degradation organochlorine contamination thing.The fourth roc of Jilin University (Jilin University's journal, 2004,42 (2): 269～272) studied Bi
2O
3Photochemical catalytic oxidation character to gaseous-phase organic pollutant has obtained certain achievement.But the research of bismuth oxide series photocatalyst is also very not enough at present, and reaction mechanism is also not really clear, therefore is necessary to further investigate.
Metal ion mixing is to improve the active a kind of important channel of conductor photocatalysis.Metal ion mainly by and semiconductor light-catalyst in its photocatalytic activity of function influence and the dynamic process of photo-generated carrier.Dopant ion mainly is to introduce some impurity levels in semi-conductive forbidden band, makes semiconductor material to produce response to the photon of longer wavelength, widens the utilization zone of semiconductor material to light.In addition, dopant ion is captured fast and is discharged photic current carrier by participating in, and controls the diffusion process of photic current carrier in semiconductor particle inside, influences the life-span of photic current carrier, thereby reaches the purpose of the photocatalysis performance that improves semiconductor material.At present domestic have on a small quantity about Bi
2O
3The report of composite oxide semiconductor photocatalyst, but relevant metal ion mixing Bi
2O
3The research of photocatalyst yet there are no report.Therefore, adopt metal ion mixing Bi
2O
3, improve the stability of photocatalyst, thereby be further to study Bi
2O
3Light-catalyzed reaction mechanism lay the first stone.
Summary of the invention
The present invention will carry out on the basis of adopting the synthetic bismuth oxide of brand-new microwave heating.
The preparation method of preparation doped metal ion nano bismuth oxide provided by the invention is called microwave process for synthesizing, may further comprise the steps:
1) dissolving step: the bismuth salt compound is dissolved in the organic solvent, after waiting to dissolve molysite, nickel salt is dissolved in wherein;
2) microwave irradiation step: carry out in the instrument of microwave transmissive member is housed, the reaction times is 3-60 minute, and reaction power is 180-900 watt; And before microwave radiation, add doped metal ion solution.
3) washing step: with step 2) products therefrom water and dehydrated alcohol wash respectively.
4) drying step: drying temperature is 70-100 ℃.
5) calcination steps: maturing temperature is 500-700 ℃, and roasting time is 2-4 hour.
In dissolving step, the bismuth salt compound is selected from five nitric hydrate bismuths; Organic solvent is selected from ethylene glycol (or other polar organic solvent); Doped metal ion solution is selected Bismuth trinitrate and nickelous chloride for use.This step also can be used ultrasonic dispersing, and the time is 15-30 minute.
In microwave irradiation step, instrument can adopt household microwave oven, experiment with microwave oven, industrial microwave oven, preferably adopts the household microwave oven of being furnished with the water-cooled reflux after reequiping.Reactive mode can adopt continuous type of heating or be interrupted type of heating, wherein is interrupted type of heating and can adopts every heating in 0-15 minute once, and heating repeatedly repeatedly.
In drying step, its dry atmosphere is air atmosphere.
In calcination steps, preferred 500 ℃ of temperature; Preferred 2 hours of time.
Beneficial effect of the present invention is:
1) prior art for preparing technology relative complex, production cost is higher relatively and time-consuming; The present invention is with the synthetic metal ion nano bismuth oxide that mixed for preparing of liquid phase microwave, with the bismuth salt compound that is easy to get, alcohols and common containing transition metal ion molysite, nickel salt as the reaction starting material, technology is simple, easy to operate, raw material is easy to get, production cost is low, the synthetic condition is comparatively loose, produces high value-added product.
2) instrument that microwave transmissive member is housed that the present invention is used can adopt the household microwave oven of being furnished with the water-cooled reflux, and this instrument is easy, be easy to get.The present invention adopts microwave radiation, and non-environmental-pollution is a kind of green synthesis process, is fit to the preparation method of the nano bismuth oxide of Small Scale Industry production.
3) the product particle size distribution of the present invention's preparation is narrower, and oxidation capacity is strong, and the catalytic activity height is nontoxic, and chemical stability is good.Be fit to waste gas pollution control and treatment (as the catalytic decomposition of Dioxins etc.), also can be applicable to environmental protection fields such as wastewater treatment, sewage disposal, energy and material.The reduction of discharging that also can be applicable to industrial pollutants is handled, and can be applied to the off gas treatment of domestic iron and steel enterprise, waste incineration industry.
Description of drawings
Fig. 1 is the process flow diagram of the doped metal ion bismuth oxide of preparation;
Fig. 2 microwave product (is mixed Fe
3+) in the XRD figure of 500 ℃ of roastings.
Fig. 3 microwave product (is mixed Ni
2+) in the XRD figure of 500 ℃ of roastings.
Embodiment
The present invention is further elaborated with embodiment below, but these embodiment have any restriction to the present invention absolutely not.Any change that those skilled in the art are done in to the invention process under the enlightenment of this specification sheets all will drop in the scope of claims.
Embodiment 1 prepares the method for doped metal ion bismuth oxide
Accurately take by weighing 3.65g five nitric hydrate bismuths, measure 50ml ethylene glycol (ethylene glycol guarantee Bismuth trinitrate dissolve fully get final product), both are mixed in beaker, ultra-sonic dispersion 30min dissolves fully to Bismuth trinitrate, adds iron nitrate solution (C again
(Fe3+): C
(Bi3+)＜20: 1).Then above-mentioned mixed solution is transferred in the 250ml round-bottomed flask, places and carry out microwave reaction in the microwave oven that is connected to reflux, microwave power is 360W, microwave radiation 8 minutes (each 2 minutes, midfeather 1 minute, totally 4 times).After reaction finishes, collect product, carry out centrifugation, and respectively wash 3 times with deionized water and dehydrated alcohol.Dry 6h under 80 ℃.Obtain the bismuth oxide product at 500 ℃ of following roasting 2h.
Preparation technology's flow process of this method is seen Fig. 1.
The XRD spectra of products therefrom is seen Fig. 2.Therefrom as can be seen, sharp-pointed through the product X RD peak shape after the roasting, with α-Bi
2O
3Standard x RD spectrogram roughly consistent, wherein some peak is not to be α-Bi
2O
3The peak, be Bi by analysis
2O
2.3, and the diffraction peak of not observing ferric oxide in the sample exists, and Fe is described
3+Be doped to Bi uniformly
2O
3Powder in.
Embodiment 2
Accurately take by weighing 3.65g five nitric hydrate bismuths, measure 50ml ethylene glycol (ethylene glycol guarantee Bismuth trinitrate dissolve fully get final product), both are mixed in beaker, ultra-sonic dispersion 30min dissolves fully to Bismuth trinitrate, adds nickel chloride solution (C again
(Fe3+): C
(Bi3+)＜20: 1).Then above-mentioned mixed solution is transferred in the 250ml round-bottomed flask, places and carry out microwave reaction in the microwave oven that is connected to reflux, microwave power is 360W, microwave radiation 8 minutes (each 2 minutes, midfeather 1 minute, totally 4 times).After reaction finishes, collect product, carry out centrifugation, and respectively wash 3 times with deionized water and dehydrated alcohol.Dry 6h under 80 ℃.Obtain the bismuth oxide product at 500 ℃ of following roasting 2h.
Preparation technology's flow process of this method is seen Fig. 1.
The XRD spectra of products therefrom is seen Fig. 3.Therefrom as can be seen, sharp-pointed through the product X RD peak shape after the roasting, with α-Bi
2O
3Standard x RD spectrogram roughly consistent, wherein some peak is not to be α-Bi
2O
3The peak, also be Bi by analysis
2O
2.3, and the diffraction peak of not observing ferric oxide in the sample exists, and Ni is described
2+Be doped to Bi uniformly
2O
3Powder in.
Claims (11)
1. the preparation method of a doped metal ion nano bismuth oxide is characterized in that, may further comprise the steps:
1) dissolving step: the bismuth salt compound is dissolved in the organic solvent, after waiting to dissolve molysite, nickel salt is dissolved in wherein.
2) microwave irradiation step: carry out in the instrument of microwave transmissive member is housed, the reaction times is 3-60 minute, and reaction power is 180-900 watt.
3) washing step: with step 2) products therefrom water and dehydrated alcohol wash respectively.
4) drying step: drying temperature is 60-100 ℃.
5) calcination steps: maturing temperature is 500-700 ℃, and roasting time is 2-4 hour.
2. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 1 is characterized in that, wherein said bismuth salt compound is selected from five nitric hydrate bismuths.
3. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 1 is characterized in that, wherein said organic solvent is selected from ethylene glycol or propylene glycol.
4. as the preparation method of claim 1 or 2 or 3 described a kind of doped metal ion nano bismuth oxides, it is characterized in that wherein said dissolving step is used ultrasonic dispersing, the time is 15-30 minute.
5. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 1 is characterized in that, wherein said instrument is selected from household microwave oven, experiment microwave oven, industrial microwave oven.
6. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 5 is characterized in that, wherein said household microwave oven is furnished with the water-cooled reflux.
7. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 1 is characterized in that, wherein said microwave irradiation step adopts continuous type of heating or is interrupted type of heating.
8. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 7 is characterized in that, wherein said interruption type of heating can adopt every heating in 0-15 minute once, and heating repeatedly repeatedly.
9. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 1 is characterized in that, wherein said drying, and its dry atmosphere is air atmosphere.
10. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 1 is characterized in that, wherein said maturing temperature is 600 ℃.
11. the preparation method of a kind of doped metal ion nano bismuth oxide as claimed in claim 1 is characterized in that, wherein said roasting time is 2 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212878A (en) * | 2011-05-27 | 2011-10-12 | 华东师范大学 | Method for preparing acicular and fungiform Bi2O3 nano materials |
| CN105664958A (en) * | 2016-01-20 | 2016-06-15 | 重庆大学 | Photocatalytic material and method for preparing same |
| CN114229892A (en) * | 2021-12-23 | 2022-03-25 | 株洲科能新材料股份有限公司 | Ion implantation doped bismuth oxide and preparation method and application thereof |
| CN114551828A (en) * | 2022-01-28 | 2022-05-27 | 同济大学 | Bi-MOF derived bismuth oxide-based negative electrode material and preparation and application thereof |
-
2008
- 2008-04-08 CN CNA2008100310229A patent/CN101264930A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212878A (en) * | 2011-05-27 | 2011-10-12 | 华东师范大学 | Method for preparing acicular and fungiform Bi2O3 nano materials |
| CN102212878B (en) * | 2011-05-27 | 2012-11-28 | 华东师范大学 | Method for preparing acicular and fungiform Bi2O3 nano materials |
| CN105664958A (en) * | 2016-01-20 | 2016-06-15 | 重庆大学 | Photocatalytic material and method for preparing same |
| CN105664958B (en) * | 2016-01-20 | 2018-04-13 | 重庆大学 | A kind of catalysis material and preparation method thereof |
| CN114229892A (en) * | 2021-12-23 | 2022-03-25 | 株洲科能新材料股份有限公司 | Ion implantation doped bismuth oxide and preparation method and application thereof |
| CN114229892B (en) * | 2021-12-23 | 2023-10-13 | 株洲科能新材料股份有限公司 | Ion implantation doped bismuth oxide and preparation method and application thereof |
| CN114551828A (en) * | 2022-01-28 | 2022-05-27 | 同济大学 | Bi-MOF derived bismuth oxide-based negative electrode material and preparation and application thereof |
| CN114551828B (en) * | 2022-01-28 | 2023-06-02 | 同济大学 | Bi-MOF-derived bismuth oxide-based negative electrode material and preparation and application thereof |
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Open date: 20080917 |