CN103880093B - Hollow spherical nickel bicarbonate aggregate - Google Patents
Hollow spherical nickel bicarbonate aggregate Download PDFInfo
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- CN103880093B CN103880093B CN201410151621.XA CN201410151621A CN103880093B CN 103880093 B CN103880093 B CN 103880093B CN 201410151621 A CN201410151621 A CN 201410151621A CN 103880093 B CN103880093 B CN 103880093B
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Abstract
The invention discloses a hollow spherical nickel bicarbonate aggregate which is a pure phase of nickel bicarbonate formed by aggregation of a single layer of nano-particles, wherein the molecular formula of the hollow spherical nickel bicarbonate aggregate is Ni(HCO3)2; the nickel bicarbonate aggregate is infrequent carbonate of nickel and is hollow and spherical in shape, the size of a hollow sphere is 1+/-0.3 microns, the wall thickness is 120+/-50 nanometers, and the size of the nano particles which form the hollow sphere is 100+/-40 nanometers. A preparation method of the hollow spherical nickel bicarbonate aggregate comprises the following steps: dissolving a certain mass of dissolvable nickel salt in water, adding a proper amount of carbonate as a precipitating agent, then adding a proper amount of metal ion complexing agent and a surfactant as a crystal morphology regulating agent, sealing in a reaction kettle, reacting for a certain time at a certain temperature, washing and drying to obtain a product. Compared with the existing reports, the preparation method disclosed by the invention is simple in process, low in cost and more easily realizes large-scale production, and the prepared hollow spherical nickel bicarbonate aggregate has wide application in the fields of catalysts, electroplating, ceramics and the like and has quite good application prospect.
Description
Technical field
The present invention relates to a kind of hydrogen-carbonate nickel hollow ball-shape aggregate, belong to nano material technology and nickel salt industrial technology field.
Background technology
Nickel, having the title of " industrial VITAMIN ", is important non-ferrous metal, is mainly used in Metal smelting, light industry, machinofacture, chemical industry, oil and power industry, and high-technology field etc.The carbonate of nickel is mainly used in the manufacture of catalyzer, the preparation of tinted shade, the production of pigment, and the aspect such as the chemical combination of nickel electroplating solution.The carbonate of nickel is easy to prepare the related productss such as the oxide compound of nickel through calcining in addition, and the oxide compound of nickel all has a wide range of applications in industries such as magneticsubstance, metallurgy and picture tubes.What the carbonate of nickel was common mainly contains nickelous carbonate (NiCO
3) and basic nickel carbonate (NiCO
32Ni (OH)
24H
2o).And hydrogen-carbonate nickel (HCO
3)
2be the acid carbonate of more rare nickel, because it two hydrolysis reaction easily occurs in water, so preparation is more difficult, the report prepared about it is considerably less.Current hydrogen-carbonate nickel (HCO
3)
2preparation also there is no production technique and the route of comparative maturity, therefore its further applied research and exploitation are greatly limited.
Up to the present a small amount of document is only had to carry out report to hydrogen-carbonate nickel.People (the New J.Chem. such as Xu Kaibing, 2013,37,4031) nickelous acetate is used to do raw material, urea does precipitation agent, polyvinylpyrrolidone is as crystal morphology adjusting control agent, and deionized water and dehydrated alcohol mixed solution are as solvent, and under 180 DEG C of reaction conditionss, 8h obtains hydrogen-carbonate nickel solid sphere particle.People (the Synthesis and Reactivity in Inorganic such as Yang yong, Metal-Organic, and Nano-Metal Chemistry, 2013,43,296) nickelous nitrate is used to do raw material, Hexamine does carbonate source, polyoxyethylene glycol-block-polypropylene propylene glycol-block-polyoxyethylene glycol is as crystal morphology adjusting control agent, and deionized water is as solvent, and under 150 ~ 180 DEG C of hydrothermal reaction conditions, 24h obtains the solid nanometer blocks of hydrogen-carbonate nickel.To sum up, in the document reported, the hydrogen-carbonate nickel (HCO of preparation
3)
2product is mostly solid construction, and in document, the size of product grain neither be very homogeneous, does not also have report about hydrogen-carbonate nickel hollow ball-shape aggregate.
Along with the development of nanometer material science technology, increasing result of study shows, the microtexture of material has obvious impact to its physical and chemical performance, the performances such as such as magnetic, optics, electricity, heat conduction, conduction.Thus the material that controlled synthesis possesses special appearance structure becomes the focus of scientific research.In various appearance structure, hollow structure has attracted concern and the favor of more investigators.Hollow structure material is because have the feature such as low density, high-specific surface area, and all comparatively solid construction material is outstanding for the utilization ratio of material and reactive behavior.In addition, the hollow parts of hollow structure can hold guest species, can produce the character based on microcosmic parcel effect that some are peculiar, also can be applied as pharmaceutical carrier potentially and prepare targeting slowly-releasing class medicine.Wide investigation and application prospect is had by the hydrogen-carbonate nickel hollow ball-shape aggregate of nano-particles self assemble as a kind of new function material in view of pure phase, but at present also not about its any report, therefore its development research is had great importance.
Summary of the invention
For at present also not about hydrogen-carbonate nickel hollow ball-shape aggregate material report and the present situation of synthesizing this material prior art deficiency, the object of this invention is to provide a kind of hydrogen-carbonate nickel hollow ball-shape aggregate and the simple preparation method of technique thereof.
Technical scheme of the present invention devises an a kind of simple step hydro-thermal reaction method, take water as solvent, with a certain amount of soluble nickel salt for raw material, add a certain amount of complexing of metal ion agent and tensio-active agent as crystal morphology adjusting control agent, add a certain amount of carbonate as precipitation agent, after sealing, under certain temperature, namely hydro-thermal single step reaction certain hour has synthesized by the hydrogen-carbonate nickel hollow ball-shape aggregate of the pure phase of nanoparticle aggregate.
Hydrogen-carbonate nickel hollow ball-shape aggregate of the present invention, it is characterized in that, described hydrogen-carbonate nickel hollow ball-shape aggregate is by the pure phase hydrogen-carbonate nickel of individual layer nanoparticle aggregate, form is hollow ball-shape, hollow ball is of a size of 1 ± 0.3 micron, hollow ball wall thickness is 120 ± 50 nanometers, and the nanoparticle size of composition hollow ball is 100 ± 40 nanometers; Described hydrogen-carbonate nickel hollow ball-shape aggregate obtains by the following method:
(1) soluble nickel salt is added in distilled water by the amount of 0.01 ~ 5.00g/40mL, be stirred to solution clarification;
(2) amount by 0.01 ~ 5.00g/40mL in above-mentioned solution adds complexing of metal ion agent and tensio-active agent respectively, is stirred to solution clarification;
(3) add carbonate under stirring by the amount of 0.01 ~ 5.00g/40mL in step (2) described solution, and then Keep agitation 10 ~ 30min obtains turbid solution;
(4) transfer in reactor by solution prepared by step (3), sealing, is put in 60 ~ 200 DEG C of baking ovens, reaction 1 ~ 24h;
(5), after reaction terminates, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product successively respectively rinses 3 ± 1 times through water, ethanol, then puts oven dry 5 ~ 12h in 30 ~ 100 DEG C of baking ovens, and the powdery product obtained is hydrogen-carbonate nickel hollow ball-shape aggregate;
Wherein, above-mentioned soluble nickel salt is single nickel salt, nickel ammonium sulfate, nickelous iodide, nickelous nitrate, nickelous chloride, nickelous acetate or nickelous bromide; Above-mentioned complexing of metal ion agent is tripoly phosphate sodium STPP, trisodium phosphate, diethanolamine, trolamine, tartrate, xitix, Sunmorl N 60S or sodium alginate; Above-mentioned tensio-active agent is polyoxyethylene glycol, cetyl trimethylammonium bromide, cetyltrimethylammonium hydroxide, polyvinylpyrrolidone, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate; Above-mentioned carbonate is sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, volatile salt or bicarbonate of ammonia.
Further, step (1) described soluble nickel salt preferably sulfuric acid nickel, nickelous nitrate, nickelous chloride, nickelous acetate or nickelous bromide.The preferred tripoly phosphate sodium STPP of step (2) described complexing of metal ion agent, diethanolamine, tartrate, xitix or sodium alginate.The preferred polyoxyethylene glycol of step (2) described tensio-active agent, cetyl trimethylammonium bromide, polyvinylpyrrolidone or sodium lauryl sulphate.Step (3) described carbonate is preferably sodium carbonate, saleratus, volatile salt or bicarbonate of ammonia.Step (4) described oven temperature is preferably 100 ~ 190 DEG C, and the reaction times is preferably 8 ~ 20h.
The present invention makes public for the first time a kind of hydrogen-carbonate nickel hollow ball-shape structured aggregates.The hydrogen-carbonate nickel hollow ball-shape structured aggregates regular appearance of this patent, size uniformity, even particle size distribution, its obvious hollow structure is shown in the TEM photo of Fig. 1 product, and its homogeneous size is shown in the low enlargement ratio SEM photo of Fig. 3 a product.Hydrogen-carbonate nickel hollow ball-shape aggregate is assembled by individual layer nano particle orientation to form, and sees the high magnification SEM photo of Fig. 3 b product.Hydrogen-carbonate nickel hollow ball-shape aggregate thing is mutually pure, crystallinity good, sees the XRD figure spectrum of Fig. 2 product.
In recent years, performance is surging along with the continuing fiery of non-ferrous metal market for nickel salt market value, directly cause the production-scale continuous expansion of nickel salt industry, but because be subject to the production technique progress of restriction nickel salt industry slow (Yang Fang, Xiao Zeyi, the Guo Xiaobing of techniques and methods, Deng. On Nickel Salt Crystallization Techonlogy [J]. Jiangxi nonferrous metal, 2008,22,32).
The preparation method of hydrogen-carbonate nickel hollow ball-shape aggregate disclosed by the invention is one step hydro thermal method, and method of the present invention is simple and easy to control compared with existing report, nontoxic, and easier scale operation is promoted.Because hydrogen-carbonate nickel hollow ball-shape aggregate structure has bigger serface, high surface and high phase purity, thus the fields such as catalyzer, tinted shade, pottery and plating can be widely used in.This patent has enriched hydrogen-carbonate nickel material kind and controlled synthesis, research, development and utilization etc.
Accompanying drawing explanation
The TEM picture of Fig. 1 hydrogen-carbonate nickel hollow ball-shape aggregate.
The XRD diffraction patterns of Fig. 2 hydrogen-carbonate nickel hollow ball-shape aggregate and with hydrogen-carbonate nickel crystal normal data (JCPDS No.15-0782) contrast figure.
SEM picture (a, the macrograph of Fig. 3 hydrogen-carbonate nickel hollow ball-shape aggregate; B, high power photo).
Embodiment
Embodiment 1:
(1) single nickel salt is added in distilled water by the amount of 0.1g/40mL, be stirred to solution clarification;
(2) amount of pressing 0.1g/40mL in above-mentioned solution adds tripoly phosphate sodium STPP, then the amount of pressing 0.2g/40mL adds polyoxyethylene glycol, is stirred to solution clarification;
(3) add sodium carbonate under stirring by the amount of 0.2g/40mL in step (2) described solution, and then Keep agitation 10min obtains turbid solution;
(4) transfer in reactor by solution prepared by step (3), sealing, is put in 100 DEG C of baking ovens, reaction 8h;
(5), after reaction terminates, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product rinses 3 ± 1 times through water, ethanol are successively each, then puts in 50 DEG C of baking ovens and dry 6h, and the powdery product obtained is hydrogen-carbonate nickel hollow ball-shape aggregate.
Embodiment 2:
(1) nickelous nitrate is added in distilled water by the amount of 1g/40mL, be stirred to solution clarification;
(2) amount of pressing 1g/40mL in above-mentioned solution adds diethanolamine, then the amount of pressing 1.5g/40mL adds cetyl trimethylammonium bromide, is stirred to solution clarification;
(3) add saleratus under stirring by the amount of 1g/40mL in step (2) described solution, and then Keep agitation 12min obtains turbid solution;
(4) transfer in reactor by solution prepared by step (3), sealing, is put in 120 DEG C of baking ovens, reaction 10h;
(5), after reaction terminates, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product rinses 3 ± 1 times through water, ethanol are successively each, then puts in 60 DEG C of baking ovens and dry 8h, and the powdery product obtained is hydrogen-carbonate nickel hollow ball-shape aggregate.
Embodiment 3:
(1) nickelous acetate is added in distilled water by the amount of 1.5g/40mL, be stirred to solution clarification;
(2) amount of pressing 1.5g/40mL in above-mentioned solution adds tartrate, then the amount of pressing 2g/40mL adds polyvinylpyrrolidone, is stirred to solution clarification;
(3) add volatile salt under stirring by the amount of 1.5g/40mL in step (2) described solution, and then Keep agitation 20min obtains turbid solution;
(4) transfer in reactor by solution prepared by step (3), sealing, is put in 150 DEG C of baking ovens, reaction 14h;
(5), after reaction terminates, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product rinses 3 ± 1 times through water, ethanol are successively each, then puts in 80 DEG C of baking ovens and dry 10h, and the powdery product obtained is hydrogen-carbonate nickel hollow ball-shape aggregate.
After testing, obtained hydrogen-carbonate nickel hollow ball-shape structured aggregates regular appearance, size uniformity, even particle size distribution, its obvious hollow structure is shown in the TEM photo of Fig. 1 product, and its homogeneous size is shown in the low enlargement ratio SEM photo of Fig. 3 a product.Hydrogen-carbonate nickel hollow ball-shape aggregate is assembled by individual layer nano particle orientation to form, and sees the high magnification SEM photo of Fig. 3 b product.Hydrogen-carbonate nickel hollow ball-shape aggregate thing is mutually pure, crystallinity good, sees the XRD figure spectrum of Fig. 2 product.
Embodiment 4:
(1) nickelous bromide is added in distilled water by the amount of 3g/40mL, be stirred to solution clarification;
(2) amount of pressing 2g/40mL in above-mentioned solution adds xitix, then the amount of pressing 2.5g/40mL adds sodium lauryl sulphate, is stirred to solution clarification;
(3) add bicarbonate of ammonia under stirring by the amount of 2g/40mL in step (2) described solution, and then Keep agitation 30min obtains turbid solution;
(4) transfer in reactor by solution prepared by step (3), sealing, is put in 180 DEG C of baking ovens, reaction 18h;
(5), after reaction terminates, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product rinses 3 ± 1 times through water, ethanol are successively each, then puts in 100 DEG C of baking ovens and dry 20h, and the powdery product obtained is hydrogen-carbonate nickel hollow ball-shape aggregate.
Claims (7)
1. a hydrogen-carbonate nickel hollow ball-shape aggregate, it is characterized in that, described hydrogen-carbonate nickel hollow ball-shape aggregate is by the pure phase hydrogen-carbonate nickel of individual layer nanoparticle aggregate, form is hollow ball-shape, hollow ball is of a size of 1 ± 0.3 micron, hollow ball wall thickness is 120 ± 50 nanometers, and the nanoparticle size of composition hollow ball is 100 ± 40 nanometers; Described hydrogen-carbonate nickel hollow ball-shape aggregate obtains by the following method:
(1) soluble nickel salt is added in distilled water by the amount of 0.01 ~ 5.00g/40mL, be stirred to solution clarification;
(2) amount by 0.01 ~ 5.00g/40mL in above-mentioned solution adds complexing of metal ion agent and tensio-active agent respectively, is stirred to solution clarification;
(3) add carbonate under stirring by the amount of 0.01 ~ 5.00g/40mL in step (2) described solution, and then Keep agitation 10 ~ 30min obtains turbid solution;
(4) transfer in reactor by solution prepared by step (3), sealing, is put in 60 ~ 200 DEG C of baking ovens, reaction 1 ~ 24h;
(5), after reaction terminates, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product successively respectively rinses 3 ± 1 times through water, ethanol, then puts oven dry 5 ~ 12h in 30 ~ 100 DEG C of baking ovens, and the powdery product obtained is hydrogen-carbonate nickel hollow ball-shape aggregate;
Wherein, above-mentioned soluble nickel salt is single nickel salt, nickel ammonium sulfate, nickelous iodide, nickelous nitrate, nickelous chloride, nickelous acetate or nickelous bromide; Above-mentioned complexing of metal ion agent is tripoly phosphate sodium STPP, trisodium phosphate, diethanolamine, trolamine, tartrate, xitix, Sunmorl N 60S or sodium alginate; Above-mentioned tensio-active agent is polyoxyethylene glycol, cetyl trimethylammonium bromide, cetyltrimethylammonium hydroxide, polyvinylpyrrolidone, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate; Above-mentioned carbonate is sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, volatile salt or bicarbonate of ammonia.
2. hydrogen-carbonate nickel hollow ball-shape aggregate as claimed in claim 1, it is characterized in that, described soluble nickel salt is single nickel salt, nickelous nitrate, nickelous chloride, nickelous acetate or nickelous bromide.
3. hydrogen-carbonate nickel hollow ball-shape aggregate as claimed in claim 1, it is characterized in that, described complexing of metal ion agent is tripoly phosphate sodium STPP, diethanolamine, tartrate, xitix or sodium alginate.
4. hydrogen-carbonate nickel hollow ball-shape aggregate as claimed in claim 1, it is characterized in that, described tensio-active agent is polyoxyethylene glycol, cetyl trimethylammonium bromide, polyvinylpyrrolidone or sodium lauryl sulphate.
5. hydrogen-carbonate nickel hollow ball-shape aggregate as claimed in claim 1, it is characterized in that, described carbonate is sodium carbonate, saleratus, volatile salt or bicarbonate of ammonia.
6. hydrogen-carbonate nickel hollow ball-shape aggregate as claimed in claim 1, it is characterized in that, step (4) described oven temperature is 100 ~ 190 DEG C.
7. hydrogen-carbonate nickel hollow ball-shape aggregate as claimed in claim 1, it is characterized in that, step (4) the described reaction times is 8 ~ 20h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107640761A (en) * | 2017-10-13 | 2018-01-30 | 郑州大学 | The preparation method and stored energy application of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material |
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| CN105481026A (en) * | 2015-12-17 | 2016-04-13 | 宁波繁盛商业管理有限公司 | Preparation method of nickel bicarbonate |
| CN105502523A (en) * | 2015-12-17 | 2016-04-20 | 宁波繁盛商业管理有限公司 | Nickel carbonate preparation method |
| CN107394177B (en) * | 2017-08-02 | 2020-11-24 | 中国石油大学(华东) | Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962211A (en) * | 2010-10-26 | 2011-02-02 | 南京工业大学 | Method for preparing nano nickel bicarbonate |
| CN102757101A (en) * | 2012-02-22 | 2012-10-31 | 太原理工大学 | Method for preparing large-specific-surface-area porous nickel oxide microspheres |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962211A (en) * | 2010-10-26 | 2011-02-02 | 南京工业大学 | Method for preparing nano nickel bicarbonate |
| CN102757101A (en) * | 2012-02-22 | 2012-10-31 | 太原理工大学 | Method for preparing large-specific-surface-area porous nickel oxide microspheres |
Non-Patent Citations (1)
| Title |
|---|
| Hierarchical NiO hollow microspheres assembled from nanosheet-stacked nanoparticles and their application in a gas sensor;Guoxing Zhu et al.;《RSC Advances》;20120228(第2期);4236-4241 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107640761A (en) * | 2017-10-13 | 2018-01-30 | 郑州大学 | The preparation method and stored energy application of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material |
| CN107640761B (en) * | 2017-10-13 | 2019-11-29 | 郑州大学 | The preparation method and stored energy application of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material |
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