CN101824625B - Method for controllably synthesizing bismuth-based nano-material by directly electrolyzing metal bismuth - Google Patents
Method for controllably synthesizing bismuth-based nano-material by directly electrolyzing metal bismuth Download PDFInfo
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title abstract 3
- 239000002184 metal Substances 0.000 title abstract 3
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 126
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 46
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 44
- 239000011780 sodium chloride Substances 0.000 claims abstract description 22
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 31
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 239000013077 target material Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 abstract 1
- 238000010923 batch production Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 60
- 238000005260 corrosion Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 20
- 229910000474 mercury oxide Inorganic materials 0.000 description 16
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical class [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 16
- 239000011858 nanopowder Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- -1 bismuth oxide compound Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229940073609 bismuth oxychloride Drugs 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a method for controllably synthesizing a bismuth-based nano-material by directly electrolyzing metal bismuth. In the electrolysis process of the method, metal bismuth serves as a sacrificial anode, mixed aqueous solution of sodium chloride, disodium ethylene diamine tetraacetic acid and sodium hydroxide serves as electrolyte, direct current is electrified for electrolyzing, and the proportion of electrolyte components is adjusted so as to prepare the bismuth-base nano-material. The method has the advantages of cheap and ready available raw materials used in the preparing process, controllable batch production of nano-grade high-purity Bi, BiOCl, Bi24O31CL10 or Bi2O2.33, reusable electrolyte, high compatibility with the environment.
Description
Technical field
The present invention relates to a kind of compound method of bismuth based nano-material, particularly a kind of method from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal.
Background technology
The distinctive surface effects of nano material, small-size effect, quantum effect, macro quanta tunnel effect and dielectric confinement effect; Make when nano material has the macroscopic material performance; Also have excellent physics, chemical property concurrently, receive much concern at high-technology field.Bismuth manifests unique advantage as a kind of important dopant material at aspects such as light, magnetic, electricity.Wherein, six side's bismuths are good thermoelectric materials under a kind of potential room temperature, and theoretical investigation has foretold that the nanometer bismuth has excellent more thermoelectricity capability; Nanometer bismuth oxychloride is showing excellent performance aspect catalyzed oxidation, mineral dye, the pl-; The bismuth oxide compound is the important raw and processed materials of synthetic at present bismuth-containing oxygen functional materials, and nano level bismuth oxide compound has significant advantage to the raising of performances such as the catalytic performance of complex functionality material, non-linear optical property, superconductivity, oxonium ion transmission performance, ferroelectricity, ferromegnetism.
At present, the method for bismuth based nano-materials such as synthetic bismuth, bismuth oxychloride, bismuth oxide compound mainly contains chemical precipitation method, sol-gel method, solvent thermal synthesis method, anti-microemulsion method, chemical Vapor deposition process (Journal of Solid State Chemistry 180 (2007): 2510-2516).In chemical precipitation method, solvent thermal synthesis method, the anti-microemulsion method nano materials process, the industrial pollution of generation is bigger, and production cost is higher, and industry is at present gone up mainly, and purity, the size of the chemical precipitation method products therefrom of employing are restricted; Sol-gel method and chemical Vapor deposition process need the high temperature pyrolysis of organic precursor, and building-up process is complicated, and equipment is disposable to have high input, and operator are had relatively high expectations.The electrochemical synthesis nano material is that a kind of with low cost, simple to operate, productive rate and purity are higher relatively, is suitable for the desirable preparation method of industrialized mass production.Research through electrochemical synthesis bismuth based compound is more, and has successfully obtained a series of bismuth based compounds.But, the direct bright rare report of research from bismuth metal control electrolytic synthesis nanometer bismuth based compound.
Summary of the invention
The object of the present invention is to provide a kind of with low cost, high, the pattern homogeneous of product purity, technical process is short, and is simple to operate, the method from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal that production efficiency is high, environment friendly and pollution-free.
The technical solution that realizes the object of the invention is: a kind of method from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal, at first, NaCl, EDTA are placed container, and add zero(ppm) water stirring, dissolving; Then, regulate the pH value, make solution be alkalescence dripping NaOH solution in the solution that makes; Then, be electrolytic solution with the mixing solutions that is alkalescence, be anode with the bismuth metal, be worth target material after the electrolysis; At last, under agitation condition, title product is used distilled water wash,, be worth the ultimate aim nano material being lower than drying under 200 ℃ of temperature.
The present invention compared with prior art, its remarkable advantage: 1, the present invention is anode material with the bismuth metal, through regulating the ratio of sodium-chlor, EDTA and sodium hydroxide each component in the aqueous solution, can control synthetic a large amount of title product, nanometer Bi, BiOCl, Bi
24O
31Cl
10Or Bi
2O
2.33, output and purity are higher; 2, in the electrolytic process, the complexing of the Bi that produces through EDTA and electrolysis increases bi content in the solution, impels reaction to continue to carry out, and effectively controls Bi ionic concn in the solution, thereby obtain the nano level title product; 3, this electrolytic solution can be reused, and only has hydrogen to discharge in the process, does not have other " three wastes " pollutents, is suitable for industrialized mass production high-purity nm Bi, BiOCl, Bi
24O
31Cl
10Or Bi
2O
2.334, this electrolytic process is raw materials used cheap and easy to get, uniform product appearance, and technical process is short, and is simple to operate.
Description of drawings
Fig. 1 is the electrolytic synthesis process flow sheet of the present invention from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
Fig. 2 is the SEM figure of the present invention from the method synthetic Bi nanometer sheet of the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
Fig. 3 is the XRD figure of the present invention from the method synthetic Bi nanometer sheet of the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
Fig. 4 is the SEM figure of the present invention from the method synthetic BiOCl nano powder of the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
Fig. 5 is the XRD figure of the present invention from the method synthetic BiOCl nano powder of the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
Fig. 6 is the method synthetic Bi of the present invention from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
24O
31Cl
10The SEM figure of nano powder
Fig. 7 is the method synthetic Bi of the present invention from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
24O
31Cl
10The XRD figure of nano powder
Fig. 8 is the method synthetic Bi of the present invention from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
2O
2.33The SEM figure of nano powder
Fig. 9 is the method synthetic Bi of the present invention from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
2O
2.33The XRD figure of nano powder.
Embodiment
The invention discloses a kind of method, it is characterized in that it comprises the steps: from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal
The first step: NaCl, EDTA are placed container, add zero(ppm) water and stir, dissolve, the proportionlity NaCl amount of substance of each material: EDTA amount of substance: the volume of zero(ppm) water is (0.005～0.2): (0.002～0.05): 100; Wherein the unit of volume is ml, and the unit of amount of substance is mol;
Second step: in the solution that the first step makes, drip NaOH solution and regulate the pH value, make pH >=7;
The 3rd step: the mixing solutions that makes with second step is an electrolytic solution, is anode with the bismuth metal, and electrolysis voltage 10V makes target material after the electrolysis;
The 4th step: under the agitation condition, target material is used distilled water wash,, make the ultimate aim nano material being lower than drying under 200 ℃ of temperature.
When the NaCl amount of substance: the EDTA amount of substance is (0.005～0.2): (0.002～0.05), the scope of pH value are greater than 7 less than 9 o'clock, and the ultimate aim nano material that makes is Bi; When the NaCl amount of substance: the EDTA amount of substance is (0.005～0.2): (0.002～0.015), the scope of pH value are 9～11 o'clock, and the ultimate aim nano material that makes is BiOCl; When the NaCl amount of substance: the EDTA amount of substance is (0.005～0.2): (0.016～0.05), the scope of pH value are 9～11 o'clock, and the ultimate aim nano material that makes is Bi
24O
31Cl
10When the NaCl amount of substance: the EDTA amount of substance is (0.005～0.2): (0.002～0.05), the scope of pH value is＞11 o'clock, the ultimate aim nano material that makes is Bi
2O
2.33
Below in conjunction with specific embodiment the present invention is described in further detail.
Get the commercially available analytical pure NaCl of 0.05mol, the commercially available analytical pure EDTA of 0.02mol places beaker, adds that 100ml zero(ppm) water stirs, dissolving, further with commercially available analytical pure NaOH prepared NaOH aqueous solution adjusting pH=8.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, electrolysis 2h separates out the metallic sponge bismuth at negative electrode.Black metallic sponge bismuth is taken out, add 20ml zero(ppm) water, strong mixing 20min filters, and drying obtains the 0.4472g black powder, and this powder is analyzed through SEM (as shown in Figure 2), XRD (as shown in Figure 3), and this black powder is the Bi nanometer sheet.
Embodiment 2
In the electrolytic solution of case 1, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate pH=10, insert direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of faint yellow depositions appear in electrolysis 4h in the solution.Should faint yellow deposition take out and use the 20ml distilled water wash, and filter, drying obtains the 0.8651g yellow powder, and this powder is analyzed through SEM (as shown in Figure 6), XRD (as shown in Figure 7), and this yellow powder is Bi
24O
31Cl
10Nano powder.
Embodiment 3
The 5mol/LNaOH aqueous solution that in the electrolytic solution of case 2, continues to drip with commercially available analytical pure NaOH preparation is regulated pH=13, inserts direct supply, is the anodic corrosion electrode with the bismuth metal; Logical direct current; Voltage is 10V, and a large amount of yellow mercury oxides appear in electrolysis 2h in the solution.This yellow mercury oxide is taken out and use the 20ml distilled water wash, filter, drying obtains the 0.4211g yellow powder, and this powder is analyzed through SEM (as shown in Figure 8), XRD (as shown in Figure 9), and this yellow powder is Bi
2O
2.33Nanometer sheet.
Embodiment 4
Get the commercially available analytical pure NaCl of 0.05mol, the commercially available analytical pure EDTA of 0.005mol places beaker, adds that 100ml zero(ppm) water stirs, dissolving, further with commercially available analytical pure NaOH prepared NaOH aqueous solution adjusting pH=8.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, electrolysis 3h separates out the metallic sponge bismuth at negative electrode.Black metallic sponge bismuth is taken out, add 20ml zero(ppm) water, strong mixing 1h filters, and drying obtains the 0.6230g black powder, and this powder is analyzed through SEM (as shown in Figure 2), XRD (as shown in Figure 3), and this black powder is the Bi nanometer sheet.
Embodiment 5
In the electrolytic solution of case 4, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate pH=11, insert direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of white precipitates appear in electrolysis 4h in the solution.This white precipitate is taken out and use the 20ml distilled water wash, filter, drying obtains the 0.8712g white powder, and this powder is analyzed through SEM (as shown in Figure 4), XRD (as shown in Figure 5), and this white powder is the BiOCl nano powder.
Embodiment 6
In the electrolytic solution of case 5, continue to drip to regulate pH=14, stir with the commercially available analytical pure NaOH prepared NaOH aqueous solution.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of yellow mercury oxides appear in electrolysis 3h in the solution.This yellow mercury oxide is taken out and use the 20ml distilled water wash, and repeated washing twice or thrice filters, and drying obtains the 3.2416g yellow powder, and this powder is analyzed through SEM (as shown in Figure 8), XRD (as shown in Figure 9), and this yellow powder is Bi
2O
2.33Nanometer sheet.
Embodiment 7
Get the commercially available analytical pure NaCl of 0.005mol, the commercially available analytical pure EDTA of 0.002mol places beaker, adds that 100ml zero(ppm) water stirs, dissolving, further with commercially available analytical pure NaOH prepared NaOH aqueous solution adjusting pH=8.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, electrolysis 2h separates out the metallic sponge bismuth at negative electrode.Black metallic sponge bismuth is taken out, add 20ml zero(ppm) water, strong mixing 20min filters, and drying obtains the 0.1196g black powder, and this powder is analyzed through SEM (as shown in Figure 6), XRD (as shown in Figure 7), and this black powder is the Bi nanometer sheet.
Embodiment 8
In the electrolytic solution of case 7, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate pH=11, insert direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of white precipitates appear in electrolysis 4h in the solution.This white precipitate is taken out and use the 20ml distilled water wash, filter, drying obtains the 0.0826g white powder, and this powder is analyzed through SEM (as shown in Figure 4), XRD (as shown in Figure 5), and this white powder is the BiOCl nano powder.
Embodiment 9
In the electrolytic solution of case 8, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate the pH=11 stirring and dissolving, insert direct supply, is the anodic corrosion electrode with the bismuth metal; Logical direct current; Voltage is 10V, and a large amount of yellow mercury oxides appear in electrolysis 3h in the solution.This yellow mercury oxide is taken out and use the 20ml distilled water wash, and repeated washing twice or thrice filters, and drying obtains the 0.3214g yellow powder, and this powder is analyzed through SEM (as shown in Figure 8), XRD (as shown in Figure 9), and this yellow powder is Bi
2O
2.33Nanometer sheet.
Get the commercially available analytical pure NaCl of 0.005mol, the commercially available analytical pure EDTA of 0.016mol places beaker, adds that 100ml zero(ppm) water stirs, dissolving, further with commercially available analytical pure NaOH prepared NaOH aqueous solution adjusting pH=8.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, electrolysis 2h separates out the metallic sponge bismuth at negative electrode.Black metallic sponge bismuth is taken out, add 20ml zero(ppm) water, strong mixing 20min filters, and drying obtains the 0.1084g black powder, and this powder is analyzed through SEM (as shown in Figure 2), XRD (as shown in Figure 3), and this black powder is the Bi nanometer sheet.
Embodiment 11
In the electrolytic solution of case 10, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate pH=11, insert direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of faint yellow depositions appear in electrolysis 4h in the solution.Should faint yellow deposition take out and use the 20ml distilled water wash, and filter, drying obtains the 0.0914g yellow powder, and this powder is analyzed through SEM (as shown in Figure 6), XRD (as shown in Figure 7), and this yellow powder is Bi
24O
31Cl
10Nano powder.
Embodiment 12
The 5mol/LNaOH aqueous solution that in the electrolytic solution of case 11, continues to drip with commercially available analytical pure NaOH preparation is regulated pH=13, inserts direct supply, is the anodic corrosion electrode with the bismuth metal; Logical direct current; Voltage is 10V, and a large amount of yellow mercury oxides appear in electrolysis 3h in the solution.This yellow mercury oxide is taken out and use the 20ml distilled water wash, and repeated washing twice or thrice filters, and drying obtains the 0.2765g yellow powder, and this powder is analyzed through SEM (as shown in Figure 8), XRD (as shown in Figure 9), and this yellow powder is Bi
2O
2.33Nanometer sheet.
Embodiment 13
Get the commercially available analytical pure NaCl of 0.2mol, the commercially available analytical pure EDTA of 0.015mol places beaker, adds that 100ml zero(ppm) water stirs, dissolving, further with commercially available analytical pure NaOH prepared NaOH aqueous solution adjusting pH=8.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, electrolysis 2h separates out the metallic sponge bismuth at negative electrode.Black metallic sponge bismuth is taken out, add 20ml zero(ppm) water, strong mixing 20min filters, and drying obtains the 0.0643g black powder, and this powder is analyzed through SEM (as shown in Figure 2), XRD (as shown in Figure 3), and this black powder is the Bi nanometer sheet.
Embodiment 14
In the electrolytic solution of case 13, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate pH=9, insert direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of white precipitates appear in electrolysis 4h in the solution.This white precipitate is taken out and use the 20ml distilled water wash, filter, drying obtains the 0.0437g white powder, and this powder is analyzed through SEM (as shown in Figure 4), XRD (as shown in Figure 5), and this white powder is the BiOCl nano powder.
Embodiment 15
In the electrolytic solution of case 14, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate pH=13, insert direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of yellow mercury oxides appear in electrolysis 3h in the solution.This yellow mercury oxide is taken out and use the 20ml distilled water wash, and repeated washing twice or thrice filters, and drying obtains the 0.2177g yellow powder, and this powder is analyzed through SEM (as shown in Figure 8), XRD (as shown in Figure 9), and this yellow powder is Bi
2O
2.33Nanometer sheet.
Get the commercially available analytical pure NaCl of 0.2mol, the commercially available analytical pure EDTA of 0.05mol places beaker, adds that 100ml zero(ppm) water stirs, dissolving, further with the 5mol/LNaOH aqueous solution adjusting pH=8 of commercially available analytical pure NaOH preparation.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, electrolysis 2h separates out the metallic sponge bismuth at negative electrode.Black metallic sponge bismuth is taken out, add 20ml zero(ppm) water, strong mixing 20min filters, and drying obtains the 0.1304gBi black powder, and this powder is analyzed through SEM (as shown in Figure 2), XRD (as shown in Figure 3), and this black powder is a nanometer sheet.
Embodiment 17
In the electrolytic solution of case 16, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate pH=9, insert direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of faint yellow depositions appear in electrolysis 4h in the solution.Should faint yellow deposition take out and use the 20ml distilled water wash, and filter, drying obtains the 0.0844g yellow powder, and this powder is analyzed through SEM (as shown in Figure 6), XRD (as shown in Figure 7), and this yellow powder is Bi
24O
31Cl
10Nano powder.
Embodiment 18
In the electrolytic solution of case 17, continuing to drip with the commercially available analytical pure NaOH prepared NaOH aqueous solution to regulate pH=13, insert direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of yellow mercury oxides appear in electrolysis 3h in the solution.This yellow mercury oxide is taken out and use the 20ml distilled water wash, and repeated washing twice or thrice filters, and drying obtains the 0.4117g yellow powder, and this powder is analyzed through SEM (as shown in Figure 8), XRD (as shown in Figure 9), and this yellow powder is Bi
2O
2.33Nanometer sheet.
Embodiment 19
Get the commercially available analytical pure NaCl of 0.05mol, the commercially available analytical pure EDTA of 0.02mol places beaker; Adding 100ml zero(ppm) water stirs, dissolves; Further add the 5mol/l.NaOH 20ml solution with commercially available analytical pure NaOH preparation, the pH value of mixing solutions is much larger than 11.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of yellow mercury oxides appear in electrolysis 3h in the solution.This yellow mercury oxide is taken out and use the 20ml distilled water wash, and repeated washing twice or thrice filters, and drying obtains the 4.2115g yellow powder, and this powder is analyzed through SEM (as shown in Figure 8), XRD (as shown in Figure 9), and this yellow powder is Bi
2O
2.33Nanometer sheet.
Get the commercially available analytical pure NaCl of 0.005mol, the commercially available analytical pure EDTA of 0.002mol; Place beaker; Add 100ml zero(ppm) water and stir, dissolve, further add the 10mol/l.NaOH 20ml solution with commercially available analytical pure NaOH preparation, the pH value of mixing solutions is much larger than 11.Inserting direct supply, is the anodic corrosion electrode with the bismuth metal, logical direct current, and voltage is 10V, a large amount of yellow mercury oxides appear in electrolysis 2h in the solution.This yellow mercury oxide is taken out and use the 20ml distilled water wash, and repeated washing twice or thrice filters, and drying obtains the 0.2457g yellow powder, and this powder is analyzed through SEM (as shown in Figure 8), XRD (as shown in Figure 9), and this yellow powder is Bi
2O
2.33Nanometer sheet.
Claims (5)
1. the method from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal is characterized in that it comprises the steps:
The first step: NaCl, EDTA are placed container, add zero(ppm) water and stir, dissolve, the proportionlity NaCl amount of substance of each material: EDTA amount of substance: the volume of zero(ppm) water is (0.005～0.2): (0.002～0.05): 100; Wherein the unit of volume is ml, and the unit of amount of substance is mol;
Second step: in the solution that the first step makes, drip NaOH solution and regulate the pH value, make pH >=7;
The 3rd step: the mixing solutions that makes with second step is an electrolytic solution, is anode with the bismuth metal, and electrolysis voltage 10V makes target material after the electrolysis;
The 4th step: under the agitation condition, target material is used distilled water wash,, make the ultimate aim nano material being lower than drying under 200 ℃ of temperature.
2. the method from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal according to claim 1; It is characterized in that: when the NaCl amount of substance: the EDTA amount of substance is (0.005～0.2): (0.002～0.05); The scope of pH value is greater than 7 less than 9 o'clock, and making the ultimate aim nano material is Bi.
3. the method from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal according to claim 1; It is characterized in that working as: when the NaCl amount of substance: the EDTA amount of substance is (0.005～0.2): (0.002～0.015); The scope of pH value is 9～11 o'clock, and making the ultimate aim nano material is BiOCl.
4. the method from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal according to claim 1; It is characterized in that: when the NaCl amount of substance: the EDTA amount of substance is (0.005～0.2): (0.016～0.05); The scope of pH value is 9～11 o'clock, and making the ultimate aim nano material is Bi
24O
31Cl
10
5. the method from the synthetic bismuth based nano-material of the direct electrolysis control of bismuth metal according to claim 1; It is characterized in that: when the NaCl amount of substance: the EDTA amount of substance is (0.005～0.2): (0.002～0.05); The scope of pH value is＞11 o'clock, and making the ultimate aim nano material is Bi
2O
2.33
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| CN103785426B (en) * | 2014-01-09 | 2016-01-20 | 河北科技大学 | BiOCl base heterojunction of a kind of visible light catalysis activity and preparation method thereof |
| CN105060341B (en) * | 2015-08-06 | 2016-08-24 | 中国科学院合肥物质科学研究院 | Micro-nano structure bismuth oxide material and preparation method thereof |
| CN108190952B (en) * | 2018-01-19 | 2020-03-24 | 中南大学 | Bi2O2.33Preparation method of nanosheet |
| CN108745386A (en) * | 2018-04-28 | 2018-11-06 | 广州大学 | A kind of preparation method of BiOX photocatalyst |
| CN111530481A (en) * | 2020-05-26 | 2020-08-14 | 广东石油化工学院 | Method for rapidly preparing BiOBr nanosheet |
| CN114669308A (en) * | 2022-04-01 | 2022-06-28 | 哈尔滨理工大学 | BiOCl/Bi preparation by means of electrochemical method in-situ reaction24O31Cl10Method for compounding powder |
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| CN101177302A (en) * | 2006-11-10 | 2008-05-14 | 宝山钢铁股份有限公司 | Method for preparing nano bismuth oxide |
| CN101186337A (en) * | 2007-12-10 | 2008-05-28 | 湖南金旺实业有限公司 | Method for producing high purity nano-level bismuth oxide micro-powder |
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| CN1995468A (en) * | 2006-12-18 | 2007-07-11 | 天津理工大学 | Diameter-controllable metal nm-line array preparation method |
| CN101186337A (en) * | 2007-12-10 | 2008-05-28 | 湖南金旺实业有限公司 | Method for producing high purity nano-level bismuth oxide micro-powder |
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