CN101168196A - Method for preparing nickel-base amorphous nano particles - Google Patents
Method for preparing nickel-base amorphous nano particles Download PDFInfo
- Publication number
- CN101168196A CN101168196A CNA2006101177023A CN200610117702A CN101168196A CN 101168196 A CN101168196 A CN 101168196A CN A2006101177023 A CNA2006101177023 A CN A2006101177023A CN 200610117702 A CN200610117702 A CN 200610117702A CN 101168196 A CN101168196 A CN 101168196A
- Authority
- CN
- China
- Prior art keywords
- nickel
- solution
- microemulsion
- base amorphous
- hexane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to a material technical field, specifically relating to a method of preparing nickel-base amorphous nanometer particles. Positive phase micro emulsion is formed by using sodium-hydroxide, deionized water, ethyl alcohol and skellysolve B, soluble nickel salt and water solution of soluble metal inorganic salt of other alloy elements are added to the micro emulsion, and finally potassium borohydride is splashed and added in the micro emulsion to proceed a reduction reaction. The grain diameter of the made and required product is 5 to 15 nanometers. The method can control the grain diameters which form the nickel-base amorphous nanometer particles, and the grain diameters distribute a little narrowly. The nickel-base amorphous nanometer particles have good dispersity, and are not easy to reunite with high practicability. The invention further has the advantages of relatively stable reaction system, simple technical operation, especially convenient and easy processing of products, and low costs of raw materials, thereby being easy for industrial production.
Description
Technical field
The invention belongs to the nickel-bass alloy material field, relate in particular to a kind of new method for preparing nickel-base amorphous metal alloy nano particle.
Background technology
Amorphous alloy also claims amorphous alloy, and its microstructure is different from the crystalline state metal, and is in shakiness or metastable state on thermodynamics, thereby demonstrates unique physicochemical properties: (1) amorphous alloy shortrange order.Contain the unsaturated atom of a lot of coordinations, be imbued with reactivity.Thereby has higher surface activity center density.(2) the amorphous alloy long-range is unordered, is a kind of material that does not have three dimensions atom periodic arrangement.
Since early 1980s, numerous researchers has visited the possibility of amorphous alloy as new high activated catalyst, think and exist unexistent catalytic active center in the alloy crystalline on its surface, this may be the activated centre that is made of several atomic groups, and in most cases all is the coordination unsaturated bond.Studies show that its activity is higher than corresponding crystal alloy, special selectivity is arranged, and cost being lower, can not pollute, is a kind of novel green catalysis material.In addition, it has the unexistent characteristic of general crystal alloy, as higher resistivity, partly leads and the characteristic of superconduction good radiation resistance and resistance to corrosion.
Nano material has the not available unusual or unusual physics of traditional material, chemical characteristic, can produce four big effects: small-size effect, quantum effect (containing macro quanta tunnel effect), skin effect and interfacial effect.Use the new synthetic method of our this nickel base amorphous alloy nano particle, can simply prepare the monodispersity excellence, the uniform nickel base amorphous alloy nano particle of particle diameter, thus have excellent physicochemical property.In a lot of reactions, all have excellent catalytic performance, especially having more advantage aspect the hydrogenation reaction of catalysis unsaturated compound. nickel base amorphous alloy be wherein study and be most widely used, deep a kind of, almost can be applied in the various hydrogenation reactions.
From the report of other document, the method for preparing the nickel base amorphous alloy nano particle is mainly high-energy ball milling method, the precipitation method, quench etc.We have introduced a kind of forward microemulsion chemical reduction method here, and this method mainly is based on nickel, copper, simple inorganic salts such as cobalt in microemulsion by KBH
4Reduction.Thereby obtain the nickel base amorphous alloy nano particle of the particle diameter of excellent dispersion less than 15nm.
Summary of the invention
There is equipment at prior art, the specification requirement harshness, problems such as prices of raw and semifnished materials cost height the object of the present invention is to provide the new method of the excellent nickel base amorphous alloy nano particle of at room temperature a kind of, easy to operate, easy to control preparation monodispersity.
The nickel base amorphous alloy nanometer particle process method that the present invention proposes, with NaOH/potassium hydroxide, deionized water, ethanol, oleic acid/linoleic acid, n-hexane forms the positive microemulsion solution, the soluble inorganic salt aqueous solution nickeliferous and alloying metal with it is joined in the above-mentioned positive microemulsion solution, generation contains the microemulsion of metal ion, at last the aqueous solution of potassium borohydride/sodium borohydride is added drop-wise at normal temperatures and carries out reduction reaction in the above-mentioned microemulsion, obtain the nano particle of nickel base amorphous alloy, product washs, be kept at after the drying in the n-hexane, the product particle diameter is 5～15nm.
The monodisperse nickel base amorphous alloy nanometer particle process method that the present invention proposes, its concrete steps are as follows:
(1) preparation parfacies microemulsion solution
Take by weighing 0.5-0.1mmol part NaOH or KOH, be dissolved in the mixed liquor of 0.55mol part deionized water and 0.33mol part ethanol, add 0.1-0.2mmol part oleic acid (C successively
17H
31COOH) or linoleic acid and 0.01-0.02mol part n-hexane, form lurid positive microemulsion solution.
(2) cationic introducing
With 0.5mmol part Ni
2+Deionized water solution pour in the above-mentioned microemulsion, stir, in synthetic nickel based metal alloy, this step also adds the second metal cation salt in system, as CuSO
45H
2O, FeCl
24H
2O, CoCl
26H
2O; And determine ingredient proportion according to required product.
(3) adding of reducing agent
With 0.5mmol part concentration at 0.1-0.4*10
-3KBH between the M
4Or NaBH
4The aqueous solution, with 20-40 drip/minute speed add in the microemulsion of above-mentioned formation, with reaction temperature and being advisable, continue to stir about 10min.This moment, microemulsion became black, and had macroscopic precipitation to generate.
(4) post processing of product
In the solution that has reacted, add the n-hexane breakdown of emulsion.After stirring 30s, leave standstill a moment, solution is divided into two-layer.The upper strata mainly is n-hexane, a large amount of ethanol and the oleic acid in the microemulsion system.Lower floor mainly is the ethanol of water and part.Because the colloidal particle surface that generates is coating the oleic acid anion, be hydrophobic, so colloidal particle almost completely is extracted in the upper oil phase.Owing to contain a large amount of ethanol in the upper solution, make colloidal particle become cotton-shaped and separate out in addition.Separatory is transferred to upper strata liquid in the centrifuge tube, adds ethanol colloidal particle is separated out fully.Rotating speed centrifugation with 4500rpm/min goes out precipitation, discards centrifugate.At last, the precipitation that newly makes is scattered in the n-hexane, sealing is stored in the sample cell.
Among the present invention, described nickeliferous and second metal inorganic salt is water miscible inorganic salts.
Among the present invention, described Ni
2+The concentration of solution is at 0.1-0.4*10
-3Between the M.
Among the present invention, described water-soluble second metal inorganic salt comprises CuSO
4, FeCl
2, CoCl
2And hydrate one or more mixtures wherein.
Stirring described in the present invention is ultrasonic concussion, magnetic agitation, mechanical agitation etc.
Among the present invention, the centrifugation rotating speed is 4500 rev/mins described in the step (4), 10-20 minute.
Utilize the inventive method to prepare that monodispersity is good, the nickel base amorphous alloy nano particle of uniform particle diameter, have excellent physicochemical property.For example at catalytic, there is excellent performance aspects such as storage hydrogen and wave absorbtion and uses widely.
The inventive method is easy to operate, easy to control, and the product of preparing can be prepared alloy firm as methods such as Langmuir-Blodgett films by further operation
The present invention has the following advantages:
1. this method can be controlled the particle diameter of nickel base amorphous alloy nano particle, and the particle diameter narrow distribution, has very high practicality.
2. the particle surface that generates of this method coats the layer of surface activating agent, is difficult for coalescently, and the collosol stability that obtains is good, but the long period stores.
3. the reaction system that the present invention relates to is more stable relatively, and the technology operation more simply, particularly the product processing is convenient simple and direct, is easy to industrialization.
4. the present invention adopts simple inorganic salts as reactant respectively, has very strong versatility.
Description of drawings
Product transmission electron microscope (TEM) photo that Fig. 1 obtains for embodiment 1;
The product TEM photo that Fig. 2 obtains for embodiment 1;
The product TEM photo that Fig. 3 obtains for embodiment 2;
The product TEM photo that Fig. 4 obtains for embodiment 2;
The product TEM photo that Fig. 5 obtains for embodiment 3;
The product TEM photo that Fig. 6 obtains for embodiment 4;
The product TEM photo that Fig. 7 obtains for embodiment 5.
The specific embodiment
All reagent in the present embodiment are all purchased in Chemical Reagent Co., Ltd., Sinopharm Group, and purity is chemical pure and agents useful for same all through being further purified.The pattern of sample and particle diameter are observed and are undertaken by JEOL JEM-1230 type transmission electron microscope (company of NEC).
Embodiment 1:Ni-B amorphous alloy nano particle
The first step takes by weighing 400mgNaOH, is dissolved in the mixed liquor of 10ml deionized water and 15ml ethanol, adds 6.4ml oleic acid and 2ml n-hexane successively, forms lurid positive microemulsion solution.
Second step, accurately weighing 0.119g NiCl
26H
2O is dissolved in the deionized water, solution is joined in the system of the first step ultrasonic agitation 10 minutes.
The 3rd step, accurately weighing 0.54gKBH
4, be dissolved in the 5ml deionized water, the speed of solution with 30 of per minutes is added drop-wise in the above-mentioned microemulsion stirring reaction 20 minutes.
In the 4th step, after reaction finishes, in solution, add 15ml n-hexane breakdown of emulsion.After stirring 30s, leave standstill a moment, solution is divided into two-layer.Separatory is transferred to upper solution in the centrifuge tube, adds 20ml ethanol colloidal particle is separated out fully.Rotating speed centrifugation with 4500rpm/min goes out precipitation, discards centrifugate.Promptly get required product, its particle diameter is 5-10nm, and final particle can be dispersed in the n-hexane again.From Fig. 1, TEM electromicroscopic photograph shown in Figure 2, just can clearly see the existence of product.
Embodiment 2:Ni-Cu-B amorphous alloy nano particle
The first step takes by weighing 400mgNaOH, is dissolved in the mixed liquor of 10ml deionized water and 15ml ethanol, adds 6.4ml oleic acid and 2ml n-hexane successively, forms lurid positive microemulsion solution.
Second step, accurately weighing 0.0625gNiCl
26H
2O and 0.0594gCuSO
45H
2O is dissolved in the deionized water, solution is joined in the system of the first step ultrasonic agitation 10 minutes.
The 3rd step, accurately weighing 0.54gKBH
4, be dissolved in the 5ml deionized water, the speed of solution with 30 of per minutes is added drop-wise in the above-mentioned microemulsion stirring reaction 20 minutes.
In the 4th step, after reaction finishes, in solution, add 15ml n-hexane breakdown of emulsion.After stirring 30s, leave standstill a moment, solution is divided into two-layer.Separatory is transferred to upper solution in the centrifuge tube, adds 20ml ethanol colloidal particle is separated out fully.Rotating speed centrifugation with 4500rpm/min goes out precipitation, discards centrifugate.Promptly get required product, its particle diameter is 5-10nm, and final particle can be dispersed in the n-hexane again.From Fig. 3, TEM electromicroscopic photograph shown in Figure 4, just can clearly see the existence of product.
Embodiment 3:Ni-Fe-B amorphous alloy nano particle
The first step takes by weighing 400mgNaOH, is dissolved in the mixed liquor of 10ml deionized water and 15ml ethanol, adds 6.4ml oleic acid and 2ml n-hexane successively, forms lurid positive microemulsion solution.
Second step, accurately weighing 0.0625gNiCl
26H
2O and 0.0497gFeCl
24H
2O is dissolved in the deionized water, solution is joined in the system of the first step ultrasonic agitation 10 minutes.
The 3rd step, accurately weighing 0.54gKBH
4, be dissolved in the 5ml deionized water, the speed of solution with 30 of per minutes is added drop-wise in the above-mentioned microemulsion stirring reaction 20 minutes.
In the 4th step, after reaction finishes, in solution, add 15ml n-hexane breakdown of emulsion.After stirring 30s, leave standstill a moment, solution is divided into two-layer.Separatory is transferred to upper solution in the centrifuge tube, adds 20ml ethanol colloidal particle is separated out fully.Rotating speed centrifugation with 4500rpm/min goes out precipitation, discards centrifugate.Promptly get required product, its particle diameter is 5-10nm, and final particle can be dispersed in the n-hexane again.From TEM electromicroscopic photograph shown in Figure 5, just can clearly see the existence of product.
Embodiment 4:Ni-Co-B amorphous alloy nano particle
The first step takes by weighing 400mgNaOH, is dissolved in the mixed liquor of 10ml deionized water and 15ml ethanol, adds 6.4ml oleic acid and 2ml n-hexane successively, forms lurid positive microemulsion solution.
Second step, accurately weighing 0.0625gNiCl
26H
2O and 0.0625gCoCl
26H
2O is dissolved in the deionized water, solution is joined in the system of the first step ultrasonic agitation 10 minutes.
The 3rd step, accurately weighing 0.54gKBH
4, be dissolved in the 5ml deionized water, the speed of solution with 30 of per minutes is added drop-wise in the above-mentioned microemulsion stirring reaction 20 minutes.
In the 4th step, after reaction finishes, in solution, add 15ml n-hexane breakdown of emulsion.After stirring 30s, leave standstill a moment, solution is divided into two-layer.Separatory is transferred to upper solution in the centrifuge tube, adds 20ml ethanol colloidal particle is separated out fully.Rotating speed centrifugation with 4500rpm/min goes out precipitation, discards centrifugate.Promptly get required product, its particle diameter is 5-10nm, and final particle can be dispersed in the n-hexane again.From Fig. 5, TEM electromicroscopic photograph shown in Figure 6, just can clearly see the existence of product.From TEM electromicroscopic photograph shown in Figure 6, just can clearly see the existence of product.
Embodiment 5:Ni-Fe-Co-B amorphous alloy nano particle
The first step takes by weighing 400mgNaOH, is dissolved in the mixed liquor of 10ml deionized water and 15ml ethanol, adds 6.4ml oleic acid and 2ml n-hexane successively, forms lurid positive microemulsion solution.
Second step, accurately weighing 0.0625g NiCl
26H
2O and 0.0318g CoCl
26H
2O and 0.0249gFeCl
24H
2O is dissolved in the deionized water, solution is joined in the system of the first step ultrasonic agitation 10 minutes.
The 3rd step, accurately weighing 0.54gKBH
4, be dissolved in the 5ml deionized water, the speed of solution with 30 of per minutes is added drop-wise in the above-mentioned microemulsion stirring reaction 20 minutes.
In the 4th step, after reaction finishes, in solution, add 15ml n-hexane breakdown of emulsion.After stirring 30s, leave standstill a moment, solution is divided into two-layer.Separatory is transferred to upper solution in the centrifuge tube, adds 20ml ethanol colloidal particle is separated out fully.Rotating speed centrifugation with 4500rpm/min goes out precipitation, discards centrifugate.Promptly get required product, its particle diameter is 5-10nm, and final particle can be dispersed in the n-hexane again.From TEM electromicroscopic photograph shown in Figure 7, just can clearly see the existence of product.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (9)
1. the preparation method of a nickel-base amorphous nano particles, form the positive microemulsion solution with NaOH/potassium hydroxide, deionized water, ethanol, oleic acid/linoleic acid, n-hexane, the aqueous solution and the second metal inorganic saline solution of nickel inorganic salts are added in the positive microemulsion solution of above-mentioned formation, formation contains the microemulsion of metal ion, at last the aqueous solution of sodium borohydride/potassium borohydride is added drop-wise at normal temperatures and carries out reduction reaction in the above-mentioned microemulsion, obtain the nano particle of nickel base amorphous alloy, product washs, and is stored in the n-hexane after the drying.
2. the preparation method of nickel-base amorphous nano particles according to claim 1, it is characterized in that: concrete steps are as follows:
(1) gets 0.5-0.1mmol part NaOH/potassium hydroxide, be dissolved in the mixed liquor of 0.55mol part water and 0.33mol part ethanol, add 0.1-0.2mmol part oleic acid/linoleic acid and 0.01-0.02mol part n-hexane successively, mix forming the positive microemulsion solution;
(2) with 0.5mmol part Ni
2+The aqueous solution and the second metal ion aqueous solution are poured in the above-mentioned microemulsion, stir;
(3) be the solution of sodium borohydride/potassium borohydride with 0.5mmol part concentration, with 20-40 drip/minute speed add in the above-mentioned microemulsion, continue to be stirred to microemulsion and become black, and have macroscopic precipitation to generate;
(4) add the n-hexane breakdown of emulsion in the 3rd solution that makes of step, fully stir, leave standstill, separatory is got upper strata liquid, adds ethanol to colloidal particle and separates out fully, and centrifugation goes out precipitation, discards centrifugate, and precipitation is scattered in the n-hexane, and sealing is preserved.
3. method according to claim 1 is characterized in that: the particle diameter of nickel base amorphous alloy nano particle is between 5～15nm.
4. method according to claim 2 is characterized in that: described water-soluble nickel inorganic salts comprise NiCl
2And hydrate.
5. method according to claim 2 is characterized in that: described Ni
2+The concentration of the aqueous solution is at 0.1-0.4*10
-3Between the M.
6. method according to claim 2 is characterized in that: the concentration of described sodium borohydride/potassium borohydride aqueous solution is at 0.1-0.4*10
-3Between the M.
7. method according to claim 2 is characterized in that: described water-soluble second metal inorganic salt comprises CuSO
4, FeCl
2, CoCl
2And hydrate one or more mixtures wherein.
8. method according to claim 2 is characterized in that: the stirring described in the step (2) is ultrasonic concussion or magnetic agitation or mechanical agitation.
9. the monodisperse nickel base amorphous alloy nano particle of the preparation of either party's method described in the claim 1-8 is applied to store hydrogen, catalysis, suction ripple field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101177023A CN101168196B (en) | 2006-10-27 | 2006-10-27 | Method for preparing nickel-base amorphous nano particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101177023A CN101168196B (en) | 2006-10-27 | 2006-10-27 | Method for preparing nickel-base amorphous nano particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101168196A true CN101168196A (en) | 2008-04-30 |
| CN101168196B CN101168196B (en) | 2010-09-15 |
Family
ID=39389040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101177023A Expired - Fee Related CN101168196B (en) | 2006-10-27 | 2006-10-27 | Method for preparing nickel-base amorphous nano particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101168196B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538692B (en) * | 2009-04-24 | 2011-01-19 | 同济大学 | Method for preparing two-dimensional Ni-based amorphous alloy nanophase material by soft and hard composite template method |
| CN101728044B (en) * | 2009-12-15 | 2012-09-19 | 陕西北美基因股份有限公司 | Method for preparing gold magnetic particles |
| CN104014815A (en) * | 2014-06-19 | 2014-09-03 | 厦门大学 | Cobalt-based amorphous nanometer wave-absorbing material and synthetic method of cobalt-based amorphous nanometer wave-absorbing material |
| CN104028780A (en) * | 2014-02-17 | 2014-09-10 | 瑞安市浙工大技术转移中心 | Preparation method of amorphous nickel nanometer particles |
| CN104923804A (en) * | 2015-07-02 | 2015-09-23 | 吉林大学 | Preparation method of nickel nanoparticles |
| CN105598462A (en) * | 2015-10-23 | 2016-05-25 | 中国科学院深圳先进技术研究院 | Preparation method of micro-nano Sn and application of micro-nano Sn |
| CN105710384A (en) * | 2015-11-04 | 2016-06-29 | 中国科学院上海高等研究院 | One-dimensional nano bimetal alloy with hexagonal nail head structure and preparation method thereof |
| CN105834450A (en) * | 2016-05-13 | 2016-08-10 | 浙江光达电子科技有限公司 | Preparing method for silver powder |
| CN108912739A (en) * | 2018-07-16 | 2018-11-30 | 吉林大学 | A kind of preparation method of super-hydrophobic amorphous metal boride Nanoalloy material |
| CN115870492A (en) * | 2022-10-24 | 2023-03-31 | 广州大学 | Preparation method of oil-soluble amorphous nickel-boron alloy |
-
2006
- 2006-10-27 CN CN2006101177023A patent/CN101168196B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538692B (en) * | 2009-04-24 | 2011-01-19 | 同济大学 | Method for preparing two-dimensional Ni-based amorphous alloy nanophase material by soft and hard composite template method |
| CN101728044B (en) * | 2009-12-15 | 2012-09-19 | 陕西北美基因股份有限公司 | Method for preparing gold magnetic particles |
| CN104028780A (en) * | 2014-02-17 | 2014-09-10 | 瑞安市浙工大技术转移中心 | Preparation method of amorphous nickel nanometer particles |
| CN104028780B (en) * | 2014-02-17 | 2016-04-20 | 瑞安市浙工大技术转移中心 | A kind of preparation method of amorphous nickel nano particle |
| CN104014815A (en) * | 2014-06-19 | 2014-09-03 | 厦门大学 | Cobalt-based amorphous nanometer wave-absorbing material and synthetic method of cobalt-based amorphous nanometer wave-absorbing material |
| CN104923804A (en) * | 2015-07-02 | 2015-09-23 | 吉林大学 | Preparation method of nickel nanoparticles |
| CN105598462A (en) * | 2015-10-23 | 2016-05-25 | 中国科学院深圳先进技术研究院 | Preparation method of micro-nano Sn and application of micro-nano Sn |
| CN105598462B (en) * | 2015-10-23 | 2018-10-16 | 中国科学院深圳先进技术研究院 | The application of the preparation method of micro-nano Sn and micro-nano Sn |
| CN105710384A (en) * | 2015-11-04 | 2016-06-29 | 中国科学院上海高等研究院 | One-dimensional nano bimetal alloy with hexagonal nail head structure and preparation method thereof |
| CN105834450A (en) * | 2016-05-13 | 2016-08-10 | 浙江光达电子科技有限公司 | Preparing method for silver powder |
| CN105834450B (en) * | 2016-05-13 | 2019-03-19 | 浙江光达电子科技有限公司 | The preparation method of silver powder |
| CN108912739A (en) * | 2018-07-16 | 2018-11-30 | 吉林大学 | A kind of preparation method of super-hydrophobic amorphous metal boride Nanoalloy material |
| CN115870492A (en) * | 2022-10-24 | 2023-03-31 | 广州大学 | Preparation method of oil-soluble amorphous nickel-boron alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101168196B (en) | 2010-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101168196B (en) | Method for preparing nickel-base amorphous nano particles | |
| Bang et al. | Applications of ultrasound to the synthesis of nanostructured materials | |
| Lai et al. | Rational design of nanosized light elements for hydrogen storage: Classes, synthesis, characterization, and properties | |
| CN102553581A (en) | Active component morphology controllable loaded noble metal catalyst and preparation method thereof | |
| CN101157034B (en) | Preparing method of non-crystal alloy catalyst | |
| Ren et al. | Green synthesis of reduced graphene oxide/chitosan/gold nanoparticles composites and their catalytic activity for reduction of 4-nitrophenol | |
| Ma et al. | Carrageenan asissted synthesis of palladium nanoflowers and their electrocatalytic activity toward ethanol | |
| Peng et al. | Fabrication of multiple-phase magnesium-based hydrides with enhanced hydrogen storage properties by activating NiS@ C and Mg powder | |
| CN102228994A (en) | Method for preparing monodisperse silver core-nickel shell nanoparticles | |
| CN103263915A (en) | Hydrotalcite-loaded nanometer platinum catalyst as well as preparation method and application thereof | |
| Zhu et al. | Nanocatalysis: Recent advances and applications in boron chemistry | |
| Du et al. | Support-free 3D hierarchical nanoporous Cu@ Cu2O for fast tandem ammonia borane dehydrogenation and nitroarenes hydrogenation under mild conditions | |
| Wang et al. | Universal strategy for homogeneously doping noble metals into cyano-bridged coordination polymers | |
| CN1442260A (en) | Method for preparing metal nano powder | |
| Wang et al. | Controlled assembly of hierarchical metal catalysts with enhanced performances | |
| CN100503094C (en) | A method for preparing Co-Ni-Cu architecture amorphous alloy monodispersity nanometer particle | |
| CN108246332A (en) | A kind of non-noble metal supported catalyst of two dimension and its preparation method and application | |
| Guo et al. | Modulating the chemical microenvironment of Pt nanoparticles within ultrathin nanosheets of isoreticular MOFs for enhanced catalytic activity | |
| Kazıcı et al. | Co-Mn-B nanoparticles supported on epoxy-based polymer as catalyst for evolution of H2 from ammonia borane semi-methanolysis | |
| Qin et al. | Hydrogel-based catalysts for hydrogen generation by the hydrolysis of B–H compounds under external physical fields | |
| CN111111652B (en) | Self-supporting AuPd alloy mesoporous nanosphere and preparation method and application thereof | |
| CN108927154A (en) | A kind of preparation method of intermetallic compound nanocatalyst | |
| CN102451688B (en) | Hollow nanocomposite oxide material and preparation thereof | |
| CN108554421A (en) | A kind of preparation method of transient metal doped iridium base nanodendrites elctro-catalyst | |
| Li et al. | Preparation and catalytic applications of amorphous alloys |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100915 Termination date: 20121027 |