CN102897828B - Controllable preparation method of PbO1.44 hollow spheroidal aggregate - Google Patents
Controllable preparation method of PbO1.44 hollow spheroidal aggregate Download PDFInfo
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- CN102897828B CN102897828B CN201210445288.4A CN201210445288A CN102897828B CN 102897828 B CN102897828 B CN 102897828B CN 201210445288 A CN201210445288 A CN 201210445288A CN 102897828 B CN102897828 B CN 102897828B
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Abstract
The invention discloses a controllable preparation method of PbO1.44 hollow spheroidal aggregate. The method comprises the following steps: dissolving lead salt, oxidant and alkali into water in a certain proportion; stirring and mixing at room temperature in the presence of a certain amount of surfactant serving as an additive; and sealing in a reaction kettle and reacting for a certain period of time at a certain temperature, and washing and drying to obtain a final product. According to the preparation method, a one-step low-temperature hydrothermal method is adopted, the reaction is simple and easily controlled; the product has pure phase, and the prepared PbO1.44 is of a micro-nano hollow spherical structure which is an aggregate of nano-particles and has uniform size and excellent dispersion. Furthermore, the appearance, size and phase of the PbO1.44 hollow spherical aggregate can be regulated by controlling the type and concentration of the surfactant, and the preparation method is easier for large-scale production due to the low cost.
Description
Technical field
The present invention relates to a kind of PbO
1.44the controllable method for preparing of hollow ball-shape aggregate, belongs to nano material preparing technical field.
Background technology
Plumbous oxide compound common are four kinds: plumbic oxide PbO
2(quadrature phase, Tetragonal, Emission in Cubic), yellow lead oxide PbO(quadrature phase, Tetragonal), lead sesquioxide Pb
2o
3(monoclinic phase) and tri-lead tetroxide Pb
3o
4(quadrature phase, Tetragonal).Plumbous oxide compound is all widely used in actual production and life.PbO
2can be used for dyestuff, match, fireworks and elastomeric manufacture, also can be used for the manufacture of perchlorate, high-voltage arrester, and be used as vulcanized rubber as the vulcanizing agent of solvent-proof thiorubber.Anodal as lead-acid cell, PbO
2there is anti-oxidant and erosion resistance, oxygen overvoltage is high, electroconductibility is good, bonding force is strong, in the aqueous solution during electrolysis oxidation capacity by force, can lead to the features such as super-high-current, be good anode material, can replace platinum anode.PbO can be used as pigment white lead, manufactures lead soap, metallurgical solubility promoter, paint drier, ceramic raw material, thiofide, sterilant, lead salt stabilizer for plastics raw material, lead glass industrial raw material, the intermediate raw material of lead salts industry, on a small quantity as Chinese medicine with for the Storage Battery Industry in China and manufacture radiation-proof rubber goods.Pb
2o
3can be used for electronic industry and produce other plumbous compound.Pb
3o
4can be used for lead storage battery processed, glass, pottery, pottery, and be used as the protection surface layer of rust-stabilising pigment and ironware, and the oxygenant of dyestuff and other organic syntheses.
PbO
1.44be a kind of more rare existence of lead oxides, up to the present only have a small amount of document to carry out report to it.The people such as R.Chelcea (Spectrochimica Acta Part A 79 (2011) 481-485) are in one piece of document about the research of iron-lead-chromic salt glass-ceramic, when the iron-lead to synthetic-chromic salt glass-ceramic product is done X-ray powder diffraction (XRD) sign, in the XRD spectra of product, mix faint PbO
1.44diffraction peak.(J.Vac.Sci.Technol.A 19 for the people such as S.Venkataraj, 2870 (2001)) at one piece, about use direct solenoid keyholed back plate splash legal system, in the document for the structural and optical properties research of lead oxides film, utilize direct solenoid keyholed back plate splash method on plumbous target, to synthesize one deck PbO
1.44film, contains metallic lead or Pb in the XRD spectra of product in document
3o
4impurity peaks, and the PbO to preparation not in document
1.44the pattern of film carries out detailed sign and description.PbO
1.44standard x RD spectrogram (JCPDS card numbering: be 27-1201) by Charles A.Sorrell(J.Am.Ceram.Soc., 56,613 (1973)) PbO that the yellow lead oxide of 293 ℃ of heated oxide Tetragonals is prepared for 180 hours in air
1.44the XRD data of product provide, in document, product does not have regular morphology, and big or small heterogeneity, contain the faint peak of other plumbous oxygen compound in the XRD figure spectrum of the product that it is synthetic yet.To sum up, about PbO
1.44in the document of having reported, the PbO of preparation
1.44in product, mostly contain impurity, and scarcely possess regular special appearance, its preparation method is also generally comparatively complicated.
The result of study of metal oxide shows in recent years, and the microtexture of material has obvious impact to its physical and chemical performance (performances such as magnetic, optics, electricity, heat conduction, conduction).Wherein, hollow structure micro-nano material is because have the features such as low density, high-specific surface area, and its hollow parts can hold guest molecule, can produce some peculiar character based on microcosmic parcel effect.During as secondary battery electrode material, hollow parts can effectively cushion its volumetric expansion and contraction, thereby avoids structural collapse or destruction in charge and discharge cycles process, keeps the good electrochemistry cyclical stability of battery; Meanwhile, hollow structure can make electrolytic solution and active material have sufficient contact, improves the utilization ratio of active ingredient in hollow micro-nano structure, shortens the transmission route of ion or electronics, effectively improves the efficiency for charge-discharge of secondary cell.In view of 100% pure phase PbO
1.44hollow ball-shape aggregate has wide research and application prospect as a kind of functional materials, therefore for 100% pure phase PbO
1.44preparation, research and development utilize etc. and to have great importance.
Summary of the invention
For at present to PbO
1.44the present situation of studying and report less and synthetic this material prior art deficiency, the invention provides a kind of reasonable in design, simple PbO of technique
1.44the controllable method for preparing of hollow ball-shape aggregate.
Technical scheme of the present invention is to have designed an a kind of simple step low-temperature hydrothermal reaction method, with tensio-active agent (polyoxyethylene glycol, cetyl trimethylammonium bromide, cetyltrimethylammonium hydroxide, PVP, Sodium dodecylbenzene sulfonate and sodium lauryl sulphate) as pattern and structure regulating agent, take water as solvent, solubility lead salt (lead nitrate, plumbous silicofluoride, lead acetate and lead perchlorate) be raw material, add a certain amount of oxygenant (Potcrate, ammonium persulphate, potassium permanganate) and alkali (sodium hydroxide, potassium hydroxide), low-temperature hydrothermal single step reaction has synthesized the PbO being formed by nanoparticle aggregate
1.44hollow ball-shape aggregate products.
PbO of the present invention
1.44the controllable method for preparing of hollow ball-shape aggregate, step is:
(1) by solubility lead salt, the amount with 0.10～2.00g/20mL adds in distilled water, and under stirring, the amount with 0.01～1.00g/20mL is added tensio-active agent again, continues to stir 10～30 minutes, and lead salt and tensio-active agent are dissolved completely, obtains solution A; Amount by alkali with 0.10～2.00g/10mL adds in distilled water, and ultrasonic 5 ± 1 minutes, alkali is dissolved completely, obtain solution B; Amount by oxygenant with 0.10～2.00g/10mL adds in distilled water, and ultrasonic 5 ± 1 minutes, oxygenant is dissolved completely, obtain solution C;
(2) above-mentioned solution B is dropwise added drop-wise in solution A, stirs 10～30 minutes, it is mixed, obtain solution D;
(3) above-mentioned solution C is dropwise added drop-wise in solution D, stirs 10～30 minutes, it is mixed, obtain solution E;
(4) solution E is transferred in reactor, sealing, is put in 60～180 ℃ of baking ovens, reacts 1～24 hour;
(5) after step (4) reaction finishes, fast reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product is through the first post-flush of water, ethanol each 3 ± 1 times, then puts in 30～100 ℃ of baking ovens and dry 4～6 hours, and the black powder shape product obtaining is PbO
1.44hollow ball-shape aggregate.
Wherein, the described solubility lead salt of step (1) is lead nitrate, plumbous silicofluoride, lead acetate or lead perchlorate.
Wherein, the described tensio-active agent of step (1) is polyoxyethylene glycol, cetyl trimethylammonium bromide, cetyltrimethylammonium hydroxide, PVP, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
Wherein, the described alkali of step (1) is sodium hydroxide or potassium hydroxide.
Wherein, the described oxygenant of step (1) is Potcrate, ammonium persulphate or potassium permanganate.
Above-mentioned PbO
1.44in the controllable method for preparing of hollow ball-shape aggregate, the described oven temperature of step (4) is preferably 90～180 ℃.
Above-mentioned PbO
1.44in the controllable method for preparing of hollow ball-shape aggregate, the described reaction times of step (4) is preferably 3～12 hours
Above-mentioned PbO
1.44in the controllable method for preparing of hollow ball-shape aggregate, the described bake out temperature of step (6) is preferably 50～80 ℃.
The invention provides a kind of Emission in Cubic PbO
1.44one step low-temperature hydrothermal method for manufacturing of hollow structure aggregate, the method technique is simple, the PbO of gained
1.44for pure phase, hollow ball pattern is regular, size homogeneous, be evenly distributed.
The preparation method of existing lead oxides, product is more common PbO
2, PbO, Pb
2o
3and Pb
3o
4, and synthesize that to have the report of ad hoc rules pattern product less.For the preparation of lead oxides, be mainly electrochemical synthesis and solid phase synthesis process.The requirement of electrochemical synthesis appointed condition is harsh, product is less, is difficult to realize suitability for industrialized production; Solid phase synthesis can not well be controlled the phase purity of product and size pattern regularity etc.
Compared with prior art, PbO provided by the invention
1.44the controllable method for preparing of hollow ball-shape aggregate, adopts a step hydrothermal reaction at low temperature, reacts simple and easy to control; Products therefrom phase is pure, the PbO of preparation
1.44for the size homogeneous being formed by nanoparticle aggregate, the micro-nano hollow ball structure of favorable dispersity.The kind and the concentration that by controlling, add tensio-active agent, can regulate and control PbO
1.44the pattern of hollow ball aggregate, size and phase composite.Due to PbO
1.44hollow ball aggregate structure has bigger serface, high surface and special crystal phase structure, thereby can be widely used as the additive of coating, pottery and rubber, also can be applicable in the fields such as optical technology and lead-acid cell, enriched controlled preparation, research, development and utilization of metallic lead oxide compound etc.
Accompanying drawing explanation
Fig. 1 PbO
1.44the XRD diffraction result of hollow ball-shape aggregate and and PbO thereof
1.44the contrast figure of crystal normal data (JCPDSNo.27-1201).
Fig. 2 PbO
1.44the SEM picture of hollow ball-shape aggregate.
Embodiment
Embodiment 1:
(1) 1.00g lead nitrate is added in 20mL distilled water, under magnetic agitation, add 0.50g PVP, continue to stir 20 minutes, lead nitrate and PVP are dissolved completely, obtain solution A; 0.50g sodium hydroxide is added in 10mL distilled water, ultrasonic 5 minutes, sodium hydroxide is dissolved completely, obtain solution B; 1.00g Potcrate is added in 10mL distilled water, ultrasonic 5 minutes, Potcrate is dissolved completely, obtain solution C;
(2) solution B is dropwise added drop-wise in solution A, magnetic agitation 20 minutes, mixes it, obtains solution D;
(3) solution C is dropwise added drop-wise in solution D, magnetic agitation 20 minutes, mixes it, obtains solution E;
(4) solution E is transferred in 50mL reactor, sealing, is put in 60 ℃ of baking ovens, reacts 12 hours;
(5) treat that step (4) reaction finishes, and is put into subsurface water current from the beginning by reactor and is quickly cooled to room temperature;
(6) remove supernatant liquor, product is washed each 3 times through washing, ethanol, in 60 ℃ of baking ovens, dries 4 hours, and the black powder shape product obtaining is PbO
1.44hollow ball-shape aggregate.
Embodiment 2:
(1) 1.00g lead acetate is added in 20mL distilled water, under magnetic agitation, add 0.50g polyoxyethylene glycol, continue to stir 20 minutes, lead acetate and polyoxyethylene glycol are dissolved completely, obtain solution A; 0.50g potassium hydroxide is added in 10mL distilled water, ultrasonic 5 minutes, potassium hydroxide is dissolved completely, obtain solution B; 1.00g potassium permanganate is added in 10mL distilled water, ultrasonic 5 minutes, potassium permanganate is dissolved completely, obtain solution C;
(2) solution B is dropwise added drop-wise in solution A, magnetic agitation 20 minutes, mixes it, obtains solution D;
(3) solution C is dropwise added drop-wise in solution D, magnetic agitation 20 minutes, mixes it, obtains solution E;
(4) solution E is transferred in 50mL reactor, sealing, is put in 180 ℃ of baking ovens, reacts 3 hours;
(5) treat that step (4) reaction finishes, reactor is put into tap water and flows down and be quickly cooled to room temperature;
(6) remove supernatant liquor, product is washed each 3 times through washing, ethanol, in 80 ℃ of baking ovens, dries 4 hours, and the black powder shape product obtaining is PbO
1.44hollow ball-shape aggregate.
Embodiment 3:
(1) 1.00g lead perchlorate is added in 20mL distilled water, under magnetic agitation, add 0.80g cetyl trimethylammonium bromide, continue to stir 20 minutes, lead perchlorate and cetyl trimethylammonium bromide are dissolved completely, obtain solution A; 1.00g potassium hydroxide is added in 10mL distilled water, ultrasonic 5 minutes, potassium hydroxide is dissolved completely, obtain solution B; 1.00g ammonium persulphate is added in 10mL distilled water, ultrasonic 5 minutes, ammonium persulphate is dissolved completely, obtain solution C;
(2) solution B is dropwise added drop-wise in solution A, magnetic agitation 20 minutes, mixes it, obtains solution D;
(3) solution C is dropwise added drop-wise in solution D, magnetic agitation 20 minutes, mixes it, obtains solution E;
(4) solution E is transferred in 50mL reactor, sealing, is put in 90 ℃ of baking ovens, reacts 10 hours;
(5) treat that step (4) reaction finishes, reactor is put into tap water and flows down quick cooling 20 minutes to room temperature;
(6) remove supernatant liquor, product is washed each 3 times through washing, ethanol, in 50 ℃ of baking ovens, dries 4 hours, and the black powder shape product obtaining is PbO
1.44hollow ball-shape aggregate.
Embodiment 4:
(1) 2.00g plumbous silicofluoride is added in 20mL distilled water, under magnetic agitation, add 1.00g sodium lauryl sulphate, continue to stir 30 minutes, solution is dissolved completely, obtain solution A; 2.00g potassium hydroxide is added in 10mL distilled water, ultrasonic 5 minutes, potassium hydroxide is dissolved completely, obtain solution B; 2.00g potassium permanganate is added in 10mL distilled water, ultrasonic 5 minutes, potassium permanganate is dissolved completely, obtain solution C;
(2) solution B is dropwise added drop-wise in solution A, magnetic agitation 30 minutes, mixes it, obtains solution D;
(3) solution C is dropwise added drop-wise in solution D, magnetic agitation 30 minutes, mixes it, obtains solution E;
(4) solution E is transferred in 50mL reactor, sealing, is put in 120 ℃ of baking ovens, reacts 12 hours;
(5) treat that step (4) reaction finishes, reactor is put into tap water and flows down and be quickly cooled to room temperature;
(6) remove supernatant liquor, product is washed each 3 times through washing, ethanol, in 80 ℃ of baking ovens, dries 5 hours, and the black powder shape product obtaining is PbO
1.44hollow ball-shape aggregate.
Claims (5)
1. a PbO
1.44the controllable method for preparing of hollow ball-shape aggregate, step is:
(1) by solubility lead salt, the amount with 0.10～2.00g/20mL adds in distilled water, and under stirring, the amount with 0.01～1.00g/20mL is added tensio-active agent again, continues to stir 10～30 minutes, and lead salt and tensio-active agent are dissolved completely, obtains solution A; Amount by alkali with 0.10～2.00g/10mL adds in distilled water, and ultrasonic 5 ± 1 minutes, alkali is dissolved completely, obtain solution B; Amount by oxygenant with 0.10～2.00g/10mL adds in distilled water, and ultrasonic 5 ± 1 minutes, oxygenant is dissolved completely, obtain solution C;
(2) above-mentioned solution B is dropwise added drop-wise in solution A, stirs 10～30 minutes, it is mixed, obtain solution D;
(3) above-mentioned solution C is dropwise added drop-wise in solution D, stirs 10～30 minutes, it is mixed, obtain solution E;
(4) solution E is transferred in reactor, sealing, is put in 60～180 ℃ of baking ovens, reacts 1～24 hour;
(5) after step (4) reaction finishes, fast reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product is through the first post-flush of water, ethanol each 3 ± 1 times, then puts in 30～100 ℃ of baking ovens and dry 4～6 hours, and the black powder shape product obtaining is PbO
1.44hollow ball-shape aggregate;
Wherein, the described tensio-active agent of step (1) is polyoxyethylene glycol, cetyl trimethylammonium bromide, cetyltrimethylammonium hydroxide, PVP, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate; The described alkali of step (1) is sodium hydroxide or potassium hydroxide; The described oxygenant of step (1) is Potcrate, ammonium persulphate or potassium permanganate.
2. PbO as claimed in claim 1
1.44the controllable method for preparing of hollow ball-shape aggregate, is characterized in that, the described solubility lead salt of step (1) is lead nitrate, plumbous silicofluoride, lead acetate or lead perchlorate.
3. PbO as claimed in claim 1
1.44the controllable method for preparing of hollow ball-shape aggregate, is characterized in that, the temperature of the described baking oven of step (4) is 90～180 ℃.
4. PbO as claimed in claim 1
1.44the controllable method for preparing of hollow ball-shape aggregate, is characterized in that, the described reaction times of step (4) is 3～12 hours
5. PbO as claimed in claim 1
1.44the controllable method for preparing of hollow ball-shape aggregate, is characterized in that, the bake out temperature of the described baking oven of step (6) is 50～80 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318692A (en) * | 2007-06-04 | 2008-12-10 | 湖南大学 | Method for preparing high quality lead dioxide with plumbum mud in waste lead acid accumulator |
| US7785561B1 (en) * | 2009-02-18 | 2010-08-31 | Toxco. Inc | Recovery of high purity PbO |
| CN102689923A (en) * | 2011-03-24 | 2012-09-26 | 杨春晓 | Preparation method of lead-acid battery PbO nano-powder |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318692A (en) * | 2007-06-04 | 2008-12-10 | 湖南大学 | Method for preparing high quality lead dioxide with plumbum mud in waste lead acid accumulator |
| US7785561B1 (en) * | 2009-02-18 | 2010-08-31 | Toxco. Inc | Recovery of high purity PbO |
| CN102689923A (en) * | 2011-03-24 | 2012-09-26 | 杨春晓 | Preparation method of lead-acid battery PbO nano-powder |
Non-Patent Citations (5)
| Title |
|---|
| "Equilibrium Pressures of Oxygen over Oxides of Lead at Various Temperatures";EM Otto.;《Journal of The Electrochemical Society》;19661231;第113卷(第6期);525-527 * |
| "Preparation of lead and tin oxide thin films by spin coating and their application on the electrodegradation of organic pollutants";OC Monteiro et al.;《Journal of Solid State Electrochem》;20050318;第10卷(第1期);41-47 * |
| EM Otto.."Equilibrium Pressures of Oxygen over Oxides of Lead at Various Temperatures".《Journal of The Electrochemical Society》.1966,第113卷(第6期),525-527. |
| lms by spin coating and their application on the electrodegradation of organic pollutants".《Journal of Solid State Electrochem》.2005,第10卷(第1期),41-47. |
| OC Monteiro et al.."Preparation of lead and tin oxide thin fi |
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