CN101259539A - High dispersion metal nano granule and preparation thereof - Google Patents
High dispersion metal nano granule and preparation thereof Download PDFInfo
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- CN101259539A CN101259539A CNA2008101042631A CN200810104263A CN101259539A CN 101259539 A CN101259539 A CN 101259539A CN A2008101042631 A CNA2008101042631 A CN A2008101042631A CN 200810104263 A CN200810104263 A CN 200810104263A CN 101259539 A CN101259539 A CN 101259539A
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Abstract
The invention provides a highly dispersed metal nickel and cobalt nanoparticle which is prepared by a hydrotalcite-like compound/carbon nano-compound precursor and a preparation method thereof. In the preparation method, the compound precursor of the hydrotalcite-like compound and the carbon is prepared firstly, sugar molecules are introduced during the crystallization process of the hydrotalcite-like compound as a carbon source, the crystallization of the hydrotalcite-like and the carbonization of the sugar molecules are carried out simultaneously in certain proper reaction conditions, thus forming the hybrid compound product of the hydrotalcite-like and the carbon. A metal oxide is reduced to the metal particles by utilizing the carbon in the compound during the temperature increase process of the procedure. As the compound precursor is characterized by hybrid and adjustable composition, the size of the obtained metal particles is 8 to 25nm and is controllable, the size distribution is narrow, and the particles have no clustering. As the carbon has the reducibility, the additional reductant does not need to be introduced during the reaction process, and the reduction reaction can be fully carried out.
Description
Technical field
The invention belongs to the metal nano material preparation field.Be specifically related to metallic nickel, cobalt nano-particle and preparation method thereof, the metallic particles that adopts the method to obtain has the characteristics of high dispersive, controllable size, narrow size distribution, good stability.
Background technology
Nickel, cobalt are widely used in fields such as magnetic recording, magnetic fluid, catalysis, sensing, biologic medicals as important metal material.The material of nanostructured is because its size (at least on a dimension) is reduced to the magnitude (1nm=10 of nanometer
-9M), thereby have bigger specific area, and a large amount of surface atom numbers, therefore, this class material can show the peculiar property that is different from block materials at aspects such as power, heat, electricity, magnetic, optical property and surface and interface reactivities.For example: small-size effect, skin effect, quantum effect or the like, thus make nano material produce many special or novel physics, chemical property, this has expanded the range of application of nano material greatly, and can develop the frontier that material is used.Therefore, the new method of development preparation metallic nickel, cobalt nano-particle has great importance.
The metallic nickel of the preparation load of bibliographical information, the method for cobalt nano-particle mainly contain at present: be raw material [1.P.Burattin, M.Che, C.Louis with the slaine, J.Phys.Chem.B 104 (2000) 10482.], or metallo-organic compound is raw material [2.Y.Koltypin, A.Fernandez, T.Cristina Rojas, J.Campora, P.Palma, R.Prozorov, A.Gedanken, Chem.Mater.11 (1999) 1331.], through thermal decomposition and reduction process and obtain.This method normally earlier with the solution of slaine in inorganic carrier material surface impregnation, deposition, a plurality of steps such as drying, thermal decomposition, crystallization obtain metallic particles then, preparation process is complicated, and the metallic particles that makes is easily producing reunion between skewness, particle on the carrier.Perhaps adopting polymer and big molecule is that carrier material is auxiliary synthetic, as [3.A.Sarkar as described in the document, S.Kapoor, G.Yashwant, H.G.Salunke, T.Mukherjee, J.Phys.Chem.B 109 (2005) 7203.4.M.R.Knecht, J.C.Garcia-Martinez, R.M.Crooks, Chem.Mater.18 (2006) 5039.].This method is earlier metal precursor and polymer molecule to be carried out compoundly, is converted into the metallic particles of polymer support under appropriate reaction conditions.This method has the cost of material height, uses the bigger organic solvent of toxicity and the shortcomings such as poor heat stability of product.Therefore, be necessary to develop new technology of preparing overcoming the above-mentioned problem that exists, thus obtain high dispersive, size evenly, the metallic nickel and the cobalt nano-particle of narrow size distribution, good stability.
Summary of the invention
The purpose of this invention is to provide and a kind ofly prepare the metallic nickel of high degree of dispersion, the new method of cobalt nano-particle by houghite/Nano carbon composite precursor, obtain having size evenly, the nickel and the cobalt nano-particle of high dispersive feature.
The preparation method of metal nanoparticle of the present invention is: the composite precursor for preparing houghite (LDHs) and carbon earlier, in the houghite crystallization process, introduce carbohydrate molecule as carbon source, under appropriate reaction conditions, the crystallization of houghite and the carbonization of glycan molecule are taken place simultaneously, and form the hydridization combination product of houghite and carbon.In the temperature programming process, utilize the reproducibility of carbon in the compound that the metal oxide in-situ reducing is become metallic particles then.Because composite precursor has the feature of nanoscale hydridization, and form adjustablely, therefore the metal particle size that obtains is a nanoscale, and narrow size distribution, does not produce reunion in course of reaction.And, because the carbon in the compound has reproducibility, therefore, need not to introduce other reducing substances or reducibility gas in course of reaction.
Houghite is an anionoid type stratified material, and its chemical composition can be expressed as [M
2+ 1-XM
3+ X(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+It is divalent metal; M
3+Be trivalent metal cation; A
N-Be interlayer anion, the X value is between 0.2～0.33.In hydrotalcite-like compound, divalence and trivalent metal cation evenly distribute on laminate in a certain way.
We have prepared the laminate bivalent metal ion earlier is Ni
2+Or Co
2+, trivalent metal ion is Al
3+Houghite, by high-temperature roasting, it is nickel, the cobalt nano-particle of carrier that the process that restores is prepared with composite oxides.Found that there is the shortcoming of two aspects in this method, be that the lamellar compound houghite caves in intensification roasting process la m structure on the one hand, caused agglomeration of particles when forming composite metal oxide, the metallic particles that obtains after reduction is easy to reunite, size increases bad dispersibility; On the other hand,, need to introduce reducing gas (as: hydrogen) and reduce, and reduction reaction often carries out not exclusively, the metal oxide of remnants is arranged in the product owing in reactant, there is not a reducing substances.
At these problems, the present invention proposes at the houghite preparatory phase, introduce glycan molecule as carbon source, in the houghite crystallization, glycan molecule generation carburizing reagent, final houghite/the Nano carbon composite precursor with hybrid structure that forms with composite precursor roasting under inert atmosphere, utilizes the carbon in the compound that the metal oxide (nickel oxide or cobalt oxide) that roasting forms is reduced into metallic particles.Because precursor has the feature of height hydridization, the metal particle size that obtains is little, and particle diameter is even, does not have between particle and reunites.And, because carbon has reproducibility, therefore, need not to introduce other reducing agent, and reduction reaction is carried out fully no metal oxide remnants in course of reaction.In addition, metal particle size can be come modulation by reaction condition.
Concrete preparation process is as follows:
A. contain bivalent metal ion M with deionized water and solubility divalent salts and aluminum soluble salt preparation
2+And Al
3+Mixing salt solution, wherein the molar concentration of metal ion is respectively M
2+: 0.2～1.0mol L
-1, Al
3+: 0.1～0.5mol L
-1With NaOH and soluble sodium salt preparation mixed ammonium/alkali solutions, wherein naoh concentration is 0.48～2.4mol L
-1, the soluble sodium salinity is 0.2～1.0mol L
-1Described bivalent metal ion M
2+Be Ni
2+, Co
2+In a kind; Acid ion in the mixing salt solution is NO
3 -, Cl
-Or SO
4 2-In 1～2 kind; Soluble sodium salt is any a kind in sodium carbonate, sodium chloride or the sodium sulphate;
B. the mixing salt solution that configures is poured rapidly at room temperature with mixed ammonium/alkali solutions into (seeing CN1358691) mixes fully in the full back-mixing liquid film reactor, 1～5min is stirred in violent rotation, then that the suspension that obtains is centrifugal, the washing 3～5 times, promptly obtain the houghite nucleus;
C. compound concentration is the carbon source aqueous solution of 0.05～2g/ml, the M in the houghite nucleus that obtains by carbon source and step B
2+Mol ratio 1: 1～10: 1 scope, preferable ratio is 2: 1～6: 1.The solution of houghite nucleus and carbonaceous sources is added reactor, add deionized water again, be heated to 100～180 ℃ after the sealing, be incubated 8～48 hours to 75～95% of reactor cumulative volume; Preferable condition is at 150～180 ℃, reacts 10～20 hours; Question response finishes, and naturally cools to room temperature, takes out product, through centrifugation, washes 4～5 times, ethanol again and washes 4～5 times, and drying promptly obtains the composite precursor of houghite and carbon.Wherein carbon source is in glucose or the sucrose a kind.
D. the composite precursor that makes is positioned in the tube furnace, feeds nitrogen, the maintenance gas flow is 40～100ml/min, press 0.5～8 ℃/minute of heating rate, rise to 600～800 ℃, be incubated 0.5～8 hour, be chilled to room temperature then, promptly obtain size evenly, the nickel or the cobalt nano-particle of high dispersive.
The product that makes adopts day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument (XRD) to characterize its structure (Cu target, K α 1 radiation, λ=0.15406nm), adopt the H-800 type transmission electron microscope (TEM) of Hitachi company to observe particle size.According to XRD interpretation of result product is metallic nickel or metallic cobalt, draws metallic nickel or cobalt granule by tem observation and is high dispersive and distributes, and particle size is a nanoscale, and size is even, does not have between particle and reunites.By changing preparation condition, the size of nickel or cobalt granule can be at 8～25nm scope modulation.Because the carbon species in the composite precursor also has part to keep after reduction reaction, therefore, metallic nickel or cobalt nano-particle is had protective effect, the product that makes has antiacid preferably or caustic corrosion and oxidation resistant ability.
The present invention has following remarkable result:
(1) relies on the reproducibility that carbon self has in the composite precursor, roasting under inert atmosphere, the metal oxide in-situ reducing can be become metal, reduction reaction is carried out fully, has solved in the traditional handicraft in the solution impregnation and precursor roasting and reduction the particle problem such as grow up, Size Distribution is wide of easily reuniting; Also do not need to introduce other reducing substances (as: hydrogen), raw material is cheap and easy to get, has simplified reduction process, has reduced production cost.
(2) because houghite and carbon composite precursor have the architectural feature of height hydridization on nanoscale, therefore nickel that obtains or cobalt granule size be at nanoscale, and size evenly and high degree of dispersion does not have the generation of reunion.Because nickel or cobalt granule reduce at a certain temperature and obtain, therefore, the product of comparing the solution methods preparation has the high characteristics of heat endurance, and having overcome is the shortcoming of the product poor heat stability that makes of carrier with the polymer molecule.
(3) size of metal nanoparticle can be regulated and control by reaction condition.
Description of drawings
The X-ray diffraction spectrogram of the metallic nickel nano granule of Fig. 1 embodiment 1.
The transmission electron microscope photo of the metallic nickel nano granule of Fig. 2 embodiment 1 (under two different multiplication factors, taking).
The specific embodiment
Embodiment one
With 2.3256g Ni (NO
3)
26H
2O and 1.5006g Al (NO
3)
39H
2Prepare mixing salt solution in the O adding 40ml deionized water, wherein Ni
2+Molar concentration be 0.2mol L
-1, Al
3+Molar concentration is 0.1mol L
-1Prepare 40 milliliters of mixed ammonium/alkali solutions with 0.768g NaOH and 0.848g natrium carbonicum calcinatum, wherein the NaOH molar concentration is 0.48mol L
-1, the Carbon Dioxide na concn is 0.2mol L
-1
The mixing salt solution that configures at room temperature poured into rapidly in the full back-mixing liquid film reactor with mixed ammonium/alkali solutions mix, 2min is stirred in violent rotation, and with the suspension centrifugation that obtains, centrifugal running is 5 minutes under 4000 rev/mins of rotating speeds, wash again 5 times, obtain sediment.
5.400g glucose is dissolved in obtain solution in the 40ml deionized water, with the sediment that makes with pour reactor into after glucose solution mixes, add water to 90% of cumulative volume, the insulation of sealing back is at 150 ℃, 12 hours, be cooled to room temperature and take out, centrifugal and wash 5 times, ethanol respectively and wash 5 times, drying promptly gets NiAl-LDHs/ carbon composite precursor.Place it in the tube furnace, logical nitrogen, flow 60ml/min, and heat up, 2 ℃/minute of heating rates rise to 700 ℃, are incubated 1 hour, are cooled to room temperature then, promptly obtain metallic nickel nano granule, and by transmission electron microscope observing, the average-size of nickel particle is about 9nm.
Embodiment two
With 4.2785g NiCl
26H
2O and 1.4485g AlCl
36H
2Prepare mixing salt solution in the O adding 30ml deionized water, wherein Ni
2+Molar concentration be 0.6mol L
-1, Al
3+Molar concentration is 0.2mol L
-1Prepare 30 milliliters of mixed ammonium/alkali solutions with 1.536g NaOH and 0.7013g sodium chloride, wherein the NaOH molar concentration is 1.28molL
-1, sodium chloride concentration is 0.4mol L
-1
The mixing salt solution that configures at room temperature poured into rapidly in the full back-mixing liquid film reactor with mixed ammonium/alkali solutions mix, 3min is stirred in violent rotation, and the suspension that obtains centrifugal (4000 rev/mins, each 5 minutes)-washing is circulated 4 times, obtains sediment.
12.3228g sucrose is dissolved in obtain solution in the 30ml deionized water, with the sediment that makes with pour reactor into after sucrose solution mixes, add water to 85% of cumulative volume, the insulation of sealing back is at 140 ℃, 36 hours, be cooled to room temperature and take out, centrifugal and wash 4 times, ethanol respectively and wash 4 times, drying gets NiAl-LDHs/ carbon composite precursor.Place it in the tube furnace, logical nitrogen, flow 100ml/min, and heat up, 5 ℃/minute of heating rates rise to 650 ℃, are incubated and are cooled to room temperature after 3 hours, promptly obtain metallic nickel nano granule, and by transmission electron microscope observing, the average-size of nickel particle is about 10nm.
Embodiment three
With 10.5142g NiSO
46H
2O and 7.5026g Al (NO
3)
39H
2Prepare mixing salt solution in the O adding 50ml deionized water, wherein Ni
2+Molar concentration be 0.8mol L
-1, Al
3+Molar concentration is 0.4mol L
-1Prepare 50 milliliters of mixed ammonium/alkali solutions with 3.840g NaOH and 4.2620g sodium sulphate, wherein the NaOH molar concentration is 1.92mol L
-1, sodium sulfate concentration is 0.6mol L
-1
The mixing salt solution that configures at room temperature poured into rapidly in the full back-mixing liquid film reactor with mixed ammonium/alkali solutions mix, 3min is stirred in violent rotation, and the suspension that obtains centrifugal (4000 rev/mins, each 5 minutes)-washing is circulated 4 times, obtains sediment.
28.800g glucose is dissolved in obtain solution in the 50ml deionized water, with the sediment that makes with pour reactor into after glucose solution mixes, add water to 95% of cumulative volume, the insulation of sealing back is at 160 ℃, 12 hours, be cooled to room temperature and take out, centrifugal and wash 5 times, ethanol respectively and wash 5 times, drying gets NiAl-LDHs/ carbon composite precursor.Place it in the tube furnace, logical nitrogen, flow 80ml/min, and heat up, 8 ℃/minute of heating rates rise to 750 ℃, are incubated and are cooled to room temperature after 2 hours, promptly obtain metallic nickel nano granule, and by transmission electron microscope observing, the average-size of nickel particle is about 12nm.
Embodiment four
With 5.8206g Co (NO
3)
26H
2O and 3.7513g Al (NO
3)
39H
2Prepare mixing salt solution in the O adding 50ml deionized water, wherein Co
2+Molar concentration be 0.4mol L
-1, Al
3+Molar concentration is 0.2mol L
-1Prepare 50 milliliters of mixed ammonium/alkali solutions with 1.920g NaOH and 2.12g sodium carbonate, wherein the NaOH molar concentration is 0.96molL
-1, concentration of sodium carbonate is 0.4mol L
-1
The mixing salt solution that configures at room temperature poured into rapidly in the full back-mixing liquid film reactor with mixed ammonium/alkali solutions mix, 2min is stirred in violent rotation, and the suspension that obtains centrifugal (4000 rev/mins, each 5 minutes)-washing is circulated 4 times, obtains sediment.
34.230g sucrose is dissolved in obtain solution in the 50ml deionized water, with the sediment that makes with pour reactor into after sucrose solution mixes, add water to 90% of cumulative volume, the insulation of sealing back is at 120 ℃, 36 hours, be cooled to room temperature and take out, centrifugal and wash 5 times, ethanol respectively with water and wash 5 times, drying gets CoAl-LDHs/ carbon composite precursor.Place it in the tube furnace, logical nitrogen, flow 50ml/min, and heat up, 2 ℃/minute of heating rates rise to 650 ℃, are incubated and are cooled to room temperature after 2 hours, promptly obtain the metallic cobalt nano particle, and by transmission electron microscope observing, the average-size of cobalt granule is about 20nm.
Embodiment five
With 4.2828g CoCl
26H
2O and 1.4485g AlCl
36H
2Prepare mixing salt solution in the O adding 30ml deionized water, wherein Co
2+Molar concentration be 0.6mol L
-1, Al
3+Molar concentration is 0.2mol L
-1Prepare 30 milliliters of mixed ammonium/alkali solutions with 1.5360g NaOH and 0.7013g sodium chloride, wherein the NaOH molar concentration is 1.28molL
-1, sodium chloride concentration is 0.4mol L
-1
The mixing salt solution that configures at room temperature poured into rapidly in the full back-mixing liquid film reactor with mixed ammonium/alkali solutions mix, 3min is stirred in violent rotation, and the suspension that obtains centrifugal (4000 rev/mins, each 5 minutes)-washing is circulated 5 times, obtains sediment.
9.720g glucose is dissolved in obtain solution in the 30ml deionized water, with the sediment that makes with pour reactor into after glucose solution mixes, add water to 80% of cumulative volume, the insulation of sealing back is at 160 ℃, 18 hours, be cooled to room temperature and take out, centrifugal and wash 5 times, ethanol respectively and wash 5 times, drying gets CoAl-LDHs/ carbon composite precursor.Place it in the tube furnace, logical nitrogen, flow 60ml/min, and heat up, 5 ℃/minute of heating rates rise to 700 ℃, are incubated and are cooled to room temperature after 4 hours, promptly obtain the metallic cobalt nano particle, and by transmission electron microscope observing, the average-size of cobalt granule is about 23nm.
Claims (4)
1. the preparation method of a high dispersion metal nano granule, concrete preparation process is as follows:
A. contain bivalent metal ion M with deionized water and solubility divalent salts and aluminum soluble salt preparation
2+And Al
3+Mixing salt solution, wherein the molar concentration of metal ion is respectively M
2+: 0.2～1.0mol L
-1, Al
3+: 0.1～0.5mol L
-1With NaOH and soluble sodium salt preparation mixed ammonium/alkali solutions, wherein naoh concentration is 0.48～2.4mol L
-1, the soluble sodium salinity is 0.2～1.0mol L
-1Described bivalent metal ion M
2+Be Ni
2+, Co
2+In a kind; Acid ion in the mixing salt solution is NO
3 -, Cl
-Or SO
4 2-In 1～2 kind; Soluble sodium salt is any a kind in sodium carbonate, sodium chloride or the sodium sulphate;
B. the mixing salt solution that configures is at room temperature poured into rapidly in the full back-mixing liquid film reactor with mixed ammonium/alkali solutions and mixed fully, 1～5min is stirred in violent rotation, and then that the suspension that obtains is centrifugal, washing 3～5 times promptly obtains the houghite nucleus;
C. compound concentration is the carbon source aqueous solution of 0.05～2g/ml, the M in the houghite nucleus that obtains by carbon source and step B
2+Mol ratio 1: 1～10: 1 scope, the solution of houghite nucleus and carbonaceous sources is added reactor, add deionized water again to 75～95% of reactor cumulative volume, be heated to 100～180 ℃ after the sealing, be incubated 8～48 hours; Question response finishes, and naturally cools to room temperature, takes out product, through centrifugation, washes 4～5 times, ethanol again and washes 4～5 times, and drying promptly obtains the composite precursor of houghite and carbon; Described carbon source is a kind in glucose or the sucrose;
D. the composite precursor that makes is positioned in the tube furnace, feeds nitrogen, the maintenance gas flow is 40～100ml/min, press 0.5～8 ℃/minute of heating rate, rise to 600～800 ℃, be incubated 0.5～8 hour, be chilled to room temperature then, promptly obtain size evenly, the nickel or the cobalt nano-particle of high dispersive.
2. the preparation method of high dispersion metal nano granule according to claim 1 is characterized in that the M in the carbon source and houghite nucleus among the step C
2+Mol ratio be 2: 1～6: 1; Reaction is at 150～180 ℃, reacts 10～20 hours.
3. high dispersion metal nano granule by the preparation of the described method of claim 1, this metallic particles is the particle of metallic nickel or cobalt.
4. high dispersion metal nano granule according to claim 3 is characterized in that metallic particles is high dispersive and distributes, and particle size is at 8～25nm, and size is even, does not have between particle and reunites.
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|---|---|---|---|---|
| CN101811665A (en) * | 2010-04-29 | 2010-08-25 | 上海交通大学 | Method for preparing metal nano-particle modified polysaccharide wrapped carbon nano tube |
| CN101947448A (en) * | 2010-09-21 | 2011-01-19 | 北京化工大学 | Nano-gold catalyst supported on combined metal oxide, preparation method and application thereof |
| CN101698234B (en) * | 2009-10-21 | 2011-02-16 | 北京科技大学 | Chemical preparation method of metal cobalt nanowire |
| CN102218545A (en) * | 2011-05-30 | 2011-10-19 | 陶栋梁 | Method for preparing nano aluminum by utilizing chemical method |
| CN108760854A (en) * | 2018-05-07 | 2018-11-06 | 杭州电子科技大学 | A kind of preparation method of polynary no enzyme electrochemical glucose sensing material |
| CN113522294A (en) * | 2021-08-11 | 2021-10-22 | 中国科学院青岛生物能源与过程研究所 | Ni-based catalyst, preparation method thereof and application thereof in reductive amination |
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2008
- 2008-04-18 CN CNA2008101042631A patent/CN101259539A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698234B (en) * | 2009-10-21 | 2011-02-16 | 北京科技大学 | Chemical preparation method of metal cobalt nanowire |
| CN101811665A (en) * | 2010-04-29 | 2010-08-25 | 上海交通大学 | Method for preparing metal nano-particle modified polysaccharide wrapped carbon nano tube |
| CN101811665B (en) * | 2010-04-29 | 2013-03-20 | 上海交通大学 | Method for preparing metal nano-particle modified polysaccharide wrapped carbon nano tube |
| CN101947448A (en) * | 2010-09-21 | 2011-01-19 | 北京化工大学 | Nano-gold catalyst supported on combined metal oxide, preparation method and application thereof |
| CN101947448B (en) * | 2010-09-21 | 2012-07-04 | 北京化工大学 | Nano-gold catalyst supported on combined metal oxide, preparation method and application thereof |
| CN102218545A (en) * | 2011-05-30 | 2011-10-19 | 陶栋梁 | Method for preparing nano aluminum by utilizing chemical method |
| CN102218545B (en) * | 2011-05-30 | 2012-11-28 | 陶栋梁 | Method for preparing nano aluminum by utilizing chemical method |
| CN108760854A (en) * | 2018-05-07 | 2018-11-06 | 杭州电子科技大学 | A kind of preparation method of polynary no enzyme electrochemical glucose sensing material |
| CN108760854B (en) * | 2018-05-07 | 2020-06-09 | 杭州电子科技大学 | Preparation method of multielement enzyme-free electrochemical glucose sensing material |
| CN113522294A (en) * | 2021-08-11 | 2021-10-22 | 中国科学院青岛生物能源与过程研究所 | Ni-based catalyst, preparation method thereof and application thereof in reductive amination |
| CN113522294B (en) * | 2021-08-11 | 2023-08-29 | 中国科学院青岛生物能源与过程研究所 | Ni-based catalyst, preparation method thereof and application thereof in reductive amination |
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