CN103880093A - Hollow spherical nickel bicarbonate aggregate - Google Patents
Hollow spherical nickel bicarbonate aggregate Download PDFInfo
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- CN103880093A CN103880093A CN201410151621.XA CN201410151621A CN103880093A CN 103880093 A CN103880093 A CN 103880093A CN 201410151621 A CN201410151621 A CN 201410151621A CN 103880093 A CN103880093 A CN 103880093A
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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, has 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 products such as 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 two hydrolysis reaction easily occur in water for it, so preparation is more difficult, the report of preparing about it is considerably less.Hydrogen-carbonate nickel (HCO at present
3)
2also ripe production technique and route without comparison of preparation, therefore its further applied research and exploitation are greatly limited.
Up to the present only there is a small amount of document to carry out report to hydrogen-carbonate nickel.People (the New J.Chem. such as Xu Kaibing, 2013,37,4031) use nickelous acetate 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 ℃ 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) use nickelous nitrate 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 ℃ of hydrothermal reaction conditions, 24h obtains the solid nanometer blocks of hydrogen-carbonate nickel.To sum up, in the document of having reported, the hydrogen-carbonate nickel (HCO of preparation
3)
2product is mostly solid construction, and the very homogeneous of size of product particle in document, also there is no report about hydrogen-carbonate nickel hollow ball-shape aggregate.
Along with the development of nanometer material science technology, more and more 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.Thereby the controlled preparation material that possesses special appearance structure becomes the focus of scientific research.In various appearance structure, hollow structure has attracted more investigators' concern and favor.Hollow structure material is because have the feature such as low density, high-specific surface area, and the utilization ratio of material and reactive behavior are all outstanding compared with solid construction material.In addition, the hollow parts of hollow structure can hold guest species, can produce some peculiar character based on microcosmic parcel effect, also can be applied as potentially pharmaceutical carrier and prepare targeting slowly-releasing class medicine.In view of the hydrogen-carbonate nickel hollow ball-shape aggregate being formed by nano particle self-assembly of pure phase has wide research and application prospect as a kind of new function material, but also not about its any report, therefore have great importance for its development research at present.
Summary of the invention
Also not about the present situation of hydrogen-carbonate nickel hollow ball-shape aggregate material report and synthetic 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 at present.
Technical scheme of the present invention is to have designed an a kind of simple step hydro-thermal reaction method, take water as solvent, take a certain amount of soluble nickel salt as 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, hydro-thermal single step reaction certain hour has synthesized the hydrogen-carbonate nickel hollow ball-shape aggregate of the pure phase being formed by 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 the pure phase hydrogen-carbonate nickel being formed by 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 makes 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) in above-mentioned solution, add respectively complexing of metal ion agent and tensio-active agent by the amount of 0.01～5.00g/40mL, be stirred to solution clarification;
(3) in the described solution of step (2), stir the lower carbonate that adds by the amount of 0.01～5.00g/40mL, and then the lasting 10～30min that stirs obtains turbid solution;
(4) solution of being prepared by step (3) is transferred in reactor, and sealing, is put in 60～200 ℃ of baking ovens, reaction 1～24h;
(5) after reaction finishes, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product is through water, ethanol successively each flushing 3 ± 1 times, then puts in 30～100 ℃ of baking ovens and dry 5～12h, and the powdery product obtaining 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, the described soluble nickel salt preferably sulfuric acid of step (1) nickel, nickelous nitrate, nickelous chloride, nickelous acetate or nickelous bromide.The preferred tripoly phosphate sodium STPP of the described complexing of metal ion agent of step (2), diethanolamine, tartrate, xitix or sodium alginate.The preferred polyoxyethylene glycol of the described tensio-active agent of step (2), cetyl trimethylammonium bromide, polyvinylpyrrolidone or sodium lauryl sulphate.Preferably sodium carbonate, saleratus, volatile salt or bicarbonate of ammonia of the described carbonate of step (3).The described oven temperature of step (4) is preferably 100～190 ℃, and the reaction times is preferably 8～20h.
The present invention discloses a kind of hydrogen-carbonate nickel hollow ball-shape structure aggregate first.The hydrogen-carbonate nickel hollow ball-shape structure aggregate pattern of this patent is regular, size homogeneous, even particle size distribution, and its obvious hollow structure is shown in the TEM photo of Fig. 1 product, and the size of its homogeneous is shown in the low enlargement ratio SEM photo of Fig. 3 a product.Hydrogen-carbonate nickel hollow ball-shape aggregate is to be formed by directed gathering of individual layer nano particle, sees the high magnification SEM photo of Fig. 3 b product.Hydrogen-carbonate nickel hollow ball-shape aggregate thing is mutually pure, crystallinity is 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 progress of restriction nickel salt industry production technique slow (Yang Fang, Xiao Zeyi, the Guo Xiaobing of technology and method, 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, thereby can be widely used in the fields such as catalyzer, tinted shade, pottery and plating.This patent has enriched hydrogen-carbonate nickel material kind and controlled preparation thereof, research, development and utilization etc.
Accompanying drawing explanation
The TEM picture of Fig. 1 hydrogen-carbonate nickel hollow ball-shape aggregate.
The XRD diffraction result of Fig. 2 hydrogen-carbonate nickel hollow ball-shape aggregate and with the figure that contrasts of hydrogen-carbonate nickel crystal normal data (JCPDS No.15-0782).
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) in above-mentioned solution, press the amount interpolation tripoly phosphate sodium STPP of 0.1g/40mL, then press the amount interpolation polyoxyethylene glycol of 0.2g/40mL, be stirred to solution clarification;
(3) stir the lower sodium carbonate that adds to the amount of pressing 0.2g/40mL in the described solution of step (2), and then continue to stir 10min and obtain turbid solution;
(4) solution of being prepared by step (3) is transferred in reactor, and sealing, is put in 100 ℃ of baking ovens, reaction 8h;
(5) after reaction finishes, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product is through water, ethanol successively each flushing 3 ± 1 times, then puts in 50 ℃ of baking ovens and dry 6h, and the powdery product obtaining 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) in above-mentioned solution, press the amount interpolation diethanolamine of 1g/40mL, then press the amount interpolation cetyl trimethylammonium bromide of 1.5g/40mL, be stirred to solution clarification;
(3) stir the lower saleratus that adds to the amount of pressing 1g/40mL in the described solution of step (2), and then continue to stir 12min and obtain turbid solution;
(4) solution of being prepared by step (3) is transferred in reactor, and sealing, is put in 120 ℃ of baking ovens, reaction 10h;
(5) after reaction finishes, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product is through water, ethanol successively each flushing 3 ± 1 times, then puts in 60 ℃ of baking ovens and dry 8h, and the powdery product obtaining 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) in above-mentioned solution, press the amount interpolation tartrate of 1.5g/40mL, then press the amount interpolation polyvinylpyrrolidone of 2g/40mL, be stirred to solution clarification;
(3) stir the lower volatile salt that adds to the amount of pressing 1.5g/40mL in the described solution of step (2), and then continue to stir 20min and obtain turbid solution;
(4) solution of being prepared by step (3) is transferred in reactor, and sealing, is put in 150 ℃ of baking ovens, reaction 14h;
(5) after reaction finishes, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product is through water, ethanol successively each flushing 3 ± 1 times, then puts in 80 ℃ of baking ovens and dry 10h, and the powdery product obtaining is hydrogen-carbonate nickel hollow ball-shape aggregate.
After testing, the hydrogen-carbonate nickel hollow ball-shape structure aggregate pattern that makes is regular, size homogeneous, even particle size distribution, and its obvious hollow structure is shown in the TEM photo of Fig. 1 product, and the size of its homogeneous is shown in the low enlargement ratio SEM photo of Fig. 3 a product.Hydrogen-carbonate nickel hollow ball-shape aggregate is to be formed by directed gathering of individual layer nano particle, sees the high magnification SEM photo of Fig. 3 b product.Hydrogen-carbonate nickel hollow ball-shape aggregate thing is mutually pure, crystallinity is 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) in above-mentioned solution, press the amount interpolation xitix of 2g/40mL, then press the amount interpolation sodium lauryl sulphate of 2.5g/40mL, be stirred to solution clarification;
(3) stir the lower bicarbonate of ammonia that adds to the amount of pressing 2g/40mL in the described solution of step (2), and then continue to stir 30min and obtain turbid solution;
(4) solution of being prepared by step (3) is transferred in reactor, and sealing, is put in 180 ℃ of baking ovens, reaction 18h;
(5) after reaction finishes, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product is through water, ethanol successively each flushing 3 ± 1 times, then puts in 100 ℃ of baking ovens and dry 20h, and the powdery product obtaining 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 the pure phase hydrogen-carbonate nickel being formed by 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 makes 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) in above-mentioned solution, add respectively complexing of metal ion agent and tensio-active agent by the amount of 0.01～5.00g/40mL, be stirred to solution clarification;
(3) in the described solution of step (2), stir the lower carbonate that adds by the amount of 0.01～5.00g/40mL, and then the lasting 10～30min that stirs obtains turbid solution;
(4) solution of being prepared by step (3) is transferred in reactor, and sealing, is put in 60～200 ℃ of baking ovens, reaction 1～24h;
(5) after reaction finishes, reactor is cooled to room temperature;
(6) discard the supernatant liquor in reactor, product is through water, ethanol successively each flushing 3 ± 1 times, then puts in 30～100 ℃ of baking ovens and dry 5～12h, and the powdery product obtaining 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, 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, 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, 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, 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, is characterized in that, the described oven temperature of step (4) is 100～190 ℃.
7. hydrogen-carbonate nickel hollow ball-shape aggregate as claimed in claim 1, is characterized in that, the described reaction times of step (4) is 8～20h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107394177A (en) * | 2017-08-02 | 2017-11-24 | 中国石油大学(华东) | A kind of sodium-ion battery negative pole bicarbonate nickel/graphene composite material and preparation method and application |
| 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 |
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 |
-
2014
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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 |
|---|
| GUOXING ZHU ET AL.: "Hierarchical NiO hollow microspheres assembled from nanosheet-stacked nanoparticles and their application in a gas sensor", 《RSC ADVANCES》, no. 2, 28 February 2012 (2012-02-28), pages 4236 - 4241 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107394177A (en) * | 2017-08-02 | 2017-11-24 | 中国石油大学(华东) | A kind of sodium-ion battery negative pole bicarbonate nickel/graphene composite material and preparation method and application |
| 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 |
| 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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