CN105481009B - Preparation method of bismuth subcarbonate nanoribbon - Google Patents

Preparation method of bismuth subcarbonate nanoribbon Download PDF

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Publication number
CN105481009B
CN105481009B CN201510922593.1A CN201510922593A CN105481009B CN 105481009 B CN105481009 B CN 105481009B CN 201510922593 A CN201510922593 A CN 201510922593A CN 105481009 B CN105481009 B CN 105481009B
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nano belt
preparation
bismuthyl carbonate
reaction kettle
carbonate nano
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CN105481009A (en
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李海斌
黄国游
付圣豪
陈曙光
李富进
刘鹏
张健
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Changsha University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/17—Nanostrips, nanoribbons or nanobelts, i.e. solid nanofibres with two significantly differing dimensions between 1-100 nanometer

Abstract

The invention provides a preparation method of a bismuth subcarbonate nanoribbon. The method comprises the steps that Bi(NO3)3.5H2O serves as the raw material and is added to a mixed solution of ethanolamine and water, and magnetic stirring and ultrasonic treatment are conducted; obtained white suspension is transferred to a hydrothermal reaction kettle for a reaction, after the reaction is completed, cooling is conducted, white precipitate in the reaction kettle is taken out, washed and dried, and the bismuth subcarbonate nanoribbon is obtained. The method has the advantages that devices are simple, the temperature ranging from 120 DEG C to 140 DEG C is low, and environmental protection is achieved due to the fact that the synthesis reaction is conducted in a sealed system; a chemical reagent capable of being decomposed to generate CO2 does not need to be introduced to serve as the raw material, powder is synthesized in one time through a solvent-thermal method, high-temperature calcination is not needed, synthesized powder is high in purity, high in crystallinity and regular in morphology, and the preparation method is simple in technology, high in efficiency, low in energy consumption, low in cost and environmentally friendly.

Description

A kind of preparation method of bismuthyl carbonate nano belt
Technical field
The invention belongs to field of functional materials is and in particular to a kind of preparation method of bismuthyl carbonate nano belt.
Background technology
Carry out sewage disposal using photocatalysis technology, can effective degradation of organic substances, reducing heavy metal ion.And this technology institute Need that energy consumption is low, easy and simple to handle, reaction condition gentle, do not have secondary pollution.Therefore, photocatalysis are that the very promising environment of one kind is controlled Reason technology.Bismuthyl carbonate (bi2o2co3) also known as bismuth subcarbonate, bismuth subcarbonate.bi2o2co3Crystal structure be by (bi2o2)2+ Layer and co3 2-Layer is staggered and forms, and belongs to typical " sillen " structure.(bi2o2)2+Layer and co3 2-Layer replaces symbiosis and is formed Interior electrostatic field, may advantageously facilitate light induced electron and separate with hole.Therefore, analyze from configuration aspects, bi2o2co3As photocatalysis Agent has huge potential value.
Have between the performance of catalysis material and its microscopic appearance and closely contact, the nanostructured of different-shape is due to it Different specific surface areas, has large effect to photocatalytic activity.Research shows, nano belt had both had the height ratio of nano material Face value, has relatively thin thickness and larger surface tension again, also has the micron-scale of macroscopic view in a dimension simultaneously. Such construction featuress are conducive to migration and the separation in electronics and hole, are also beneficial to photocatalyst and separate back from degradation solution Receive.Therefore, prepare bi2o2co3Nano belt has very important theoretical and realistic meaning.
In recent years, bi2o2co3As a kind of novel photocatalyst, its morphology control has prepared concern.At present, bi2o2co3Preparation method mainly have hydro-thermal method, solvent-thermal method, using carbamide or na2co3As co2Source, introduces citric acid Cooperation adjusts ph value or adds surfactant or organic polymer to realize morphology control synthesis, has obtained lamellar, classification For example flower-shaped, the spongiform structure of superstructure.There is not yet there being bi2o2co3The report of nanometer band structure, also having not seen need not be extra Introduce and contain co2Reagent and morphology control additive (surfactant, organic polymer), and directly realized using solvent simultaneously The simple solvent full-boiled process preparation bi of thing phase and morphology control2o2co3The report of nano belt.
Content of the invention
It is an object of the invention to provide a kind of bismuthyl carbonate (bi2o2co3) nano belt preparation method, solvent thermal is once Synthesis, without high-temperature calcination, has that process is simple, efficiency high, energy consumption be low, with low cost, eco-friendly feature, the powder of synthesis Body purity is high, degree of crystallinity is high, pattern rule.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
A kind of preparation method of bismuthyl carbonate nano belt, comprises the following steps:
1) by ethanolamine and deionized water ethanolamine by volume: deionized water=(0.6-1.7): 1 ratio mixing, magnetic Mixed solution is obtained after power stirring；
2) by bi (no3)3·5h2O is added in described mixed solution, carries out magnetic agitation and supersound process, obtains white Suspension, as hydro-thermal reaction precursor liquid, the bi (no in described precursor liquid3)3Concentration be 0.05-0.15mol/l；
3) described hydro-thermal reaction precursor liquid is proceeded in hydrothermal reaction kettle, stop after insulation 15-20 hour at 120-140 DEG C Only react；
4) after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the white precipitate that reaction obtains Thing, carries out to precipitate washing, is dried, that is, obtain bismuthyl carbonate nano belt.
Preferred version: described step 1) in ethanolamine and deionized water volume ratio be (0.8-1.5): 1, magnetic agitation Time is 5-10min.
Preferred version: described step 2) in the magnetic agitation time be 20-30min, sonication treatment time be 10-15min.
Preferred version, described step 2) in bi (no in precursor liquid3)3Concentration be 0.1mol/l.
Preferred version, described step 3) in hydrothermal reaction kettle liner be politef material, hydrothermal reaction kettle packing ratio For 60%-80%.
Preferred version, described step 4) in washing deionized water and dehydrated alcohol by white depositions wash in Property, described drying is 10-20h to be dried at 70 DEG C -80 DEG C.
Bi obtained by the present invention2o2co3The crystal formation of nano belt is consistent with card jcpds no.84-1752, described carbonic acid The width of oxygen bismuth nano belt is 100-400nm, and length is 10-20 μm, and thickness is 20-30nm.
The present invention will be further explained below:
By the method for the present invention, inventor's first passage simple solvent full-boiled process has prepared bi2o2co3Nano belt.Can Realize the present invention, the reaction condition of the present invention is most important.
Ethanolamine is to generate bi2o2co3The key factor of thing phase.Ethanolamine is a kind of organic base, can adsorb in the air simultaneously Co2, therefore by its by a certain percentage with h2O mixing is made into weakly alkaline solution and after stirring a period of time under atmospheric environment, molten Oh had just both been contained in liquid-, contain co again3 2-.bi(no3)3After being dissolved in this solution, bi3+With oh-And co3 2-Effect, under High Temperature High Pressure Generate bi2o2co3Crystal.If ethanolamine is substituted for other organic solvents, bi will not be generated2o2co3Or it is difficult to obtain Pure bi2o2co3Thing phase.Such as it is substituted for ethylene glycol, because ethylene glycol is to co2There is no adsorption, the product generating after solvent thermal Product are bi2o3Rather than bi2o2co3；And for example it is substituted for ethylenediamine, although ethylenediamine is to the co in air2Also there is adsorption, but by Too strong in ethylenediamine alkalescence, that final solvent thermal obtains is bi2o3And bi2o2co3Mixture phase.
Ethanolamine both mutually had crucial effect to the thing of product with the proportioning of water, and had crucial effect to the pattern of product.As The proportioning of fruit ethanolamine and water is more than 1.7, and dephasign occurs in product.If the proportioning of ethanolamine and water is less than 0.6, though product For pure bi2o2co3, but its pattern is lath-shaped rather than nano belt.Only control the proportioning of ethanolamine and water 0.6-1.7's Interval, preferably in the interval of 0.8-1.5, is only possible to obtain pure bi2o2co3Nano belt.
Compared with prior art, the present invention has following beneficial outcomes:
The bi that the present invention provides2o2co3The preparation method of nano belt, with bi (no3)3·5h2O is raw material, by bi (no3)3· 5h2O is added in ethanolamine and the mixed solution of water, carries out magnetic agitation and supersound process.Gained white suspension is proceeded to Reacted in hydrothermal reaction kettle, after the completion of question response, cooling, take out the white depositions in reactor, wash, be dried, that is, Obtain bi2o2co3Nano belt.
The method need not additionally introduce containing co2Reagent and morphology control additive (surfactant, organic polymer), and It is directly to realize thing phase and morphology control using solvent simultaneously.Have that device is simple, low temperature (120-140 DEG C), environmental protection (synthesis Reaction is carried out in enclosed system) the features such as.Solvent thermal single sintering powder body, without high-temperature calcination, and the powder purity synthesizing High, degree of crystallinity is high, pattern rule, is the environmentally friendly preparation low, with low cost of a kind of process is simple, efficiency high, energy consumption Method.
Brief description
Fig. 1 is the bi of the embodiment of the present invention 1 preparation2o2co3The xrd figure of nano belt
Fig. 2 is the bi of the embodiment of the present invention 1 preparation2o2co3The sem figure of nano belt
Specific embodiment
By specific embodiment, the method for the present invention is illustrated below in conjunction with the accompanying drawings, but the invention is not limited in This, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., should be included in the present invention Protection domain within.
Experimental technique described in following embodiments, if no special instructions, is conventional method；Described reagent and material, such as No specified otherwise, all commercially obtains.
Reactant bi (no used in the present invention3)3·5h2It is pure that o, ethanolamine etc. are commercially available analysis.
Embodiment 1
Step 1: ethanolamine and deionized water 0.8:1 mixing by volume obtain mixed solution after magnetic agitation 7min；
Step 2: by bi (no3)3·5h2O is added in above-mentioned mixed solution, after magnetic agitation 25min, is then sonicated 13min, obtains white suspension, as hydro-thermal reaction precursor liquid.Bi (no in precursor liquid3)3Concentration be 0.1mol/l；
Step 3: precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 74%, puts into constant temperature air blast Drying baker, stopped reaction after being incubated 16 hours at 140 DEG C；
Step 4: after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the white that reaction obtains Precipitate, using deionized water and absolute ethanol washing precipitate to neutrality, at 75 DEG C, hour is dried 15h, that is, obtain bi2o2co3Nano belt, as shown in Figure 1 it is seen that its purity is high, impurity peaks are few for its xrd figure.Sem figure is as shown in Figure 2 it is seen that it is Width is 100-400nm, and length is 10-20 μm, and thickness is the nano strip of 20-30nm.
Embodiment 2
Step 1: ethanolamine and deionized water 1:1 mixing by volume obtain mixed solution after magnetic agitation 6min；
Step 2: by bi (no3)3·5h2O is added in above-mentioned mixed solution, after magnetic agitation 22min, is then sonicated 12min, obtains white suspension, as hydro-thermal reaction precursor liquid.Bi (no in precursor liquid3)3Concentration be 0.08mol/l；
Step 3: precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 72%, puts into constant temperature air blast Drying baker, stopped reaction after being incubated 18 hours at 130 DEG C；
Step 4: after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the white that reaction obtains Precipitate, using deionized water and absolute ethanol washing precipitate to neutrality, at 78 DEG C, hour is dried 11h, that is, obtain bi2o2co3Nano belt, its xrd testing result and sem testing result are similar to Example 1.
Embodiment 3
Step 1: ethanolamine and deionized water 1.5:1 mixing by volume obtain mixed solution after magnetic agitation 5min；
Step 2: by bi (no3)3·5h2O is added in above-mentioned mixed solution, after magnetic agitation 20min, is then sonicated 10min, obtains white suspension, as hydro-thermal reaction precursor liquid.Bi (no in precursor liquid3)3Concentration be 0.05mol/l；
Step 3: precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 70%, puts into constant temperature air blast Drying baker, stopped reaction after being incubated 20 hours at 120 DEG C；
Step 4: after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the white that reaction obtains Precipitate, using deionized water and absolute ethanol washing precipitate to neutrality, at 80 DEG C, hour is dried 10h, that is, obtain bi2o2co3Nano belt, its xrd testing result and sem testing result are similar to Example 1.
Comparative example 1
Step 1: ethanolamine and deionized water 3:1 mixing by volume obtain mixed solution after magnetic agitation 8min；
Step 2: by bi (no3)3·5h2O is added in above-mentioned mixed solution, after magnetic agitation 28min, is then sonicated 14min, obtains white suspension, as hydro-thermal reaction precursor liquid.Bi (no in precursor liquid3)3Concentration be 0.12mol/l；
Step 3: precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 76%, puts into constant temperature air blast Drying baker, stopped reaction after being incubated 16 hours at 140 DEG C；
Step 4: after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the white that reaction obtains Precipitate, using deionized water and absolute ethanol washing precipitate to neutrality, at 78 DEG C, hour is dried 12h, the product obtaining For bi2o3And bi2o2co3Mixture.
Comparative example 2
Step 1: the 0.3:1 mixing by volume of ethanolamine and deionized water obtains mixing molten after magnetic agitation 10min Liquid；
Step 2: by bi (no3)3·5h2O is added in above-mentioned mixed solution, after magnetic agitation 30min, is then sonicated 15min, obtains white suspension, as hydro-thermal reaction precursor liquid.Bi (no in precursor liquid3)3Concentration be 0.15mol/l；
Step 3: precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 80%, puts into constant temperature air blast Drying baker, stopped reaction after being incubated 15 hours at 140 DEG C；
Step 4: after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the white that reaction obtains Precipitate, using deionized water and absolute ethanol washing precipitate to neutrality, at 80 DEG C, hour is dried 10h, that is, obtain lath Shape bi2o2co3Powder body.

Claims (6)

1. a kind of preparation method of bismuthyl carbonate nano belt is it is characterised in that comprise the following steps:
1) by ethanolamine and deionized water ethanolamine by volume: deionized water=(0.6-1.7): 1 ratio mixing, magnetic force stirs Mixed solution is obtained after mixing；The time of described magnetic agitation is 5-10min；
2) by bi (no3)3·5h2O is added in described mixed solution, carries out magnetic agitation and supersound process, obtains white suspended Liquid, as hydro-thermal reaction precursor liquid, the bi (no in described precursor liquid3)3Concentration be 0.05-0.15mol/l；Step 2) in magnetic Power mixing time is 20-30min, and sonication treatment time is 10-15min；
3) described hydro-thermal reaction precursor liquid is proceeded in hydrothermal reaction kettle, stop anti-after insulation 15-20 hour at 120-140 DEG C Should；
4) after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the white depositions that reaction obtains, right Precipitate carries out washing, is dried, that is, obtain bismuthyl carbonate nano belt.
2. according to claim 1 bismuthyl carbonate nano belt preparation method it is characterised in that: described step 1) in ethanol The volume ratio of amine and deionized water is (0.8-1.5): 1, the magnetic agitation time is 5-10min.
3. according to claim 1 bismuthyl carbonate nano belt preparation method it is characterised in that: described step 2) in precursor liquid In bi (no3)3Concentration be 0.1mol/l.
4. according to claim 1 bismuthyl carbonate nano belt preparation method it is characterised in that: described step 3) in hydro-thermal anti- Kettle liner is answered to be politef material, hydrothermal reaction kettle packing ratio is 60%-80%.
5. according to claim 1 bismuthyl carbonate nano belt preparation method it is characterised in that: described step 4) in washing Deionized water and dehydrated alcohol wash white depositions to neutrality, and described drying is 10- to be dried at 70 DEG C -80 DEG C 20h.
6. the preparation method according to one of claim 1-5 described bismuthyl carbonate nano belt it is characterised in that: prepared bi2o2co3The crystal formation of nano belt is consistent with card jcpds no.84-1752, and the width of described bismuthyl carbonate nano belt is 100- 400nm, length is 10-20 μm, and thickness is 20-30nm.
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CN106423286B (en) * 2016-09-14 2018-08-24 江南大学 A kind of BiOCOOH-Bi2O2CO3Composite photo-catalyst and preparation method thereof
CN106391076B (en) * 2016-09-14 2018-10-16 江南大学 A kind of grey Bi2O2CO3Photochemical catalyst and preparation method thereof
CN106732524B (en) * 2017-02-24 2021-01-01 云南大学 Alpha/beta-bismuth oxide phase heterojunction photocatalyst and preparation method and application thereof

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CN101817555B (en) * 2010-03-25 2012-06-27 山东大学 Bismuthyl carbonate micro flowery material with graded structure and preparation method thereof
CN102275987B (en) * 2011-05-25 2013-04-03 中国地质大学（武汉） Nano/micro-scale sheet bismuthyl carbonate material and preparation method thereof
CN103708551B (en) * 2013-12-26 2015-12-30 湛江师范学院 The preparation method of a kind of ethylene glycol-water mixed solvent thermal synthesis bismuth oxycarbonate flower-like microsphere
CN104229882B (en) * 2014-09-24 2015-11-04 浙江大学 A kind of preparation method of bismuthyl carbonate micron ball and product
CN104229883B (en) * 2014-09-24 2015-11-04 浙江大学 Preparation method of a kind of bismuthyl carbonate micron film and products thereof

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