CN103041816A - Self-protection nano-cobalt catalyst with high cyclic stability - Google Patents
Self-protection nano-cobalt catalyst with high cyclic stability Download PDFInfo
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- CN103041816A CN103041816A CN2012105166659A CN201210516665A CN103041816A CN 103041816 A CN103041816 A CN 103041816A CN 2012105166659 A CN2012105166659 A CN 2012105166659A CN 201210516665 A CN201210516665 A CN 201210516665A CN 103041816 A CN103041816 A CN 103041816A
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Abstract
The invention provides a self-protection nano-cobalt catalyst with high cyclic stability. According to the nano-cobalt catalyst, in air at room temperature, nano-metal cobalt Co is used for catalyzing the hydrolysis of boron amide AB to produce hydrogen reaction, then Co nano-catalyst grains in a solution are converted to Co<2+> ions by oxidation etching, and the Co<2+> ions can be preserved in the solution for a long time so as to realize the self-protection function of the catalyst; then the Co<2+> ions are rapidly reduced to Co nano-particles through sodium borohydride NaBH4 and the AB for realizing the cyclic use of the Co catalyst; and the regenerated Co-nano catalyst grains own the same high catalytic activity with the initial Co-nano catalyst grains. The method has the advantages of simplicity, effectiveness and low cost, and can overcome oxidation and passivation of the non-precious metal catalyst Co nanoparticles during catalysis of production of hydrogen from the AB, realize long-time cyclic stability and promote hydrogen storage-hydrogen desorption practical applications in vehicle-mounted mobile hydrogen source materials.
Description
Technical field
The present invention relates to a kind of self-shield nanometer cobalt catalyst by the standby high cyclical stability of metal-metal ion reversible transition legal system.
Background technology
Along with generation and the greenhouse gases (carbon dioxide, methane etc.) of energy crisis is drained in the ambient air in a large number, seeks an alternative cleaning new energy and become extremely important.Hydrogen Energy has just emerged as a kind of abundant, renewable, free of contamination energy.Therefore, in the process of leading to hydrogen energy source society, seeking a kind of efficient, safe hydrogen storage material just becomes the most difficult challenge.Boron amide (NH
3BH
3, AB) because high hydrogen content (19.6wt%), highly dissoluble, avirulence and stability can be used as a kind of very potential hydrogen storage material.Yet the biggest obstacle that AB is widely applied as hydrogen storage material is to find the catalyst of a kind of simple, efficient, economy and good cycling stability, further improves under proper condition its hydrogen desorption kinetics performance.
With respect to common bulk catalyst material, nano-catalyst material is owing to having large surface volume ratio and high catalytic activity, by a large amount of being applied in a lot of important chemical reactions.An important goal of nano-catalyst material is to make it have high selective, good catalytic activity, strong reaction stability and the performance such as low-cost.
In a lot of important reactions, cobalt element (Co) is with respect to the base metal of precious metal element, rich content in the earth's crust not only, and with respect to precious metal element, it has lower cost, and in a lot of important reactions as: the synthetic pure reaction of high-carbon (C3 or higher), dehydrogenation reaction, hydrogen and oxygen preparation feedback etc., all have good catalytic activity, therefore received increasing concern as catalysis material.Yet, the Co nano particle is easier oxidation in air for noble metal granule, can cause the oxidation passivation of catalyst granules and relatively poor cyclical stability, especially when twice circular response time interval was long, this had just limited its practical application greatly.Recently, the main method that overcomes this problem is to add the stable lapping of last layer on the surface of Co nano particle, such as silicon, carbon, transition metal oxide etc.; Or under inert gas, use and storage nano Co catalyst.These methods exist shortcoming more or less, have occupied the active sites of Co catalyst such as stable outer lapping, and its catalytic activity is reduced; Under the inert gas shielding, the synthetic and complexity used of catalyst and expensive etc.In sum, seek a kind of simple and effective new method and just seem very meaningful in order to the problem of the activity decreased of the long-time use of avoiding the Co nanocatalyst.
Summary of the invention
The object of the present invention is to provide a kind of this catalyst for passing through metal (Co)-metal ion (Co
2+) the self-shield nano Co catalyst of the standby high cyclical stability of free reversible transition legal system.The self-shield nanometer cobalt catalyst of described high cyclical stability, in the air at room temperature environment, after cobalt nanoparticle catalysis AB hydrolysis produced hydrogen reaction, the Co nano particle by in the oxide etch solution made it be converted to Co
2+Ion, and Co
2+Ion can in the medium-term and long-term preservation of solution, be realized the self-protection function of catalyst; And then by sodium borohydride (NaBH
4) and AB with Co
2+Ion is reduced to the Co nano particle rapidly, realizes recycling of catalyst; And the Co nanocatalyst particle of regeneration has and initial Co nanocatalyst Particle Phase high catalytic activity together.
Technical scheme of the present invention is:
A kind of self-shield nanometer cobalt catalyst of high cyclical stability, described nanometer cobalt catalyst prepares by the following method:
The selection of the required chemicals of AB hydrogen production process: boron amide AB, CoCL2 6H2O CoCl
26H
2O, sodium borohydride NaBH
4With ammoniacal liquor H
5NO, the concrete steps of nano Co catalyst granules preparation are as follows:
Step 1 is with the CoCl of 0.01～0.05mmol
26H
2O is dissolved in the distilled water of 2～10mL, obtains peach CoCl
2The aqueous solution;
Step 3 joins the solution in the step 2 solution of step 1;
Step 5, by the hydrogen that produces in the gas burette measuring process four, the hydrolytic hydrogen production equation is:
AB+2H
2O=NH
4 ++BO
2 -+3H
2；
Step 6, under 10-40 ℃, step 4 solution produces hydrogen finish after, in air behind the magnetic agitation 10-200min, black suspension has become pink liquid with black suspension, this peach liquid is CoCl
2Solution;
Step 7, the AB of 30～70mg and the NaBH of 5～30mg
4Be dissolved in the distilled water of 2～10mL;
Step 9, under 10-40 ℃ that solution magnetic agitation in air of step 8 gained is even, can see that the suspended particulate that black is arranged produces, the black suspension particle is the Co metallic catalyst;
Used chemicals is the AB of boron amide 90wt%, the CoCl of CoCL2 6H2O 99wt%
26H
2O,〉the sodium borohydride NaBH of 96wt%
4And the ammoniacal liquor H of 25wt%～28wt%
5NO.
Described step 1 to four is with metal ion Co
2+Change metallic catalyst Co into; Step 6 is to change metallic catalyst Co into metal ion Co
2+Thereby, make metallic catalyst Co obtain self-protection, realize the high cyclical stability of catalyst; Step 9 is with metal ion Co
2+Change again metallic catalyst Co into; Above-mentioned steps one to nine is a reaction cycle, thereby realizes the self-shield nano Co catalyst with the standby high cyclical stability of metal-metal ion reversible transition legal system.
Synthetic Co nano-particles size is 20nm and reunites and arrive together as the nano chain structure first.
Synthetic Co nano-metal particle is dispersity again, and its nano particle size is about 4nm.
Technique effect of the present invention is:
The used simple but effective standby nano Co catalyst of metal-metal ion reversible transition legal system; can effectively avoid the oxidation passivation of non-precious metal catalyst Co; make it be easy to preserve, realize the protection of self and make the nano Co catalyst have very high cyclical stability.In other words, we can be converted to Co fully with the Co nano particle
2+Ion is also preserved in air for a long time, then like a cork with Co
2+Ion is converted to and preserves the Co nano particle that has similar or identical high catalytic activity before, realizes recycling, thereby makes base metal nanocatalyst Co have very high cyclical stability.The method also saved at catalyst and selected, synthetic and use in cost.
Description of drawings
Fig. 1 metal (Co)-metal ion (Co
2+) free reversible transition schematic diagram.
Fig. 2 ultraviolet-visible spectrogram, wherein: (a) be CoCl
2Solution (b) is the Co nano particle, (c) is the solution behind the oxide etch Co nano particle in the air.
The XPS of element figure in Fig. 3 Co nano particle, wherein:
Fig. 3 (a) is the XPS figure of Co,
Fig. 3 (b) is the XPS figure of B.
Fig. 4 different catalysts catalysis AB hydrogen manufacturing curve, wherein: being the first Co nano particle that produces (a), (b) being the Co nano particle of the 5th circular regeneration, (c) is the Co nano particle of the 10th circular regeneration.Insert figure: in pure water, store the Co nano particle catalysis AB hydrogen manufacturing curve after 7 days.
The TEM of Fig. 5 different catalysts and SAED figure, wherein: be first synthetic Co nano particle (a), (b) be the Co nano particle of the 10th circular regeneration.
The specific embodiment
Comparing embodiment 1
CoCl with 0.03mmol
26H
2O is dissolved in the distilled water of 5mL, obtains peach CoCl
2The aqueous solution; The AB of 50mg and the NaBH of 10mg
4Be dissolved in the distilled water of 5mL, under 25 ℃, this solution joined peach CoCl
2Magnetic agitation is even in the aqueous solution, and pink solution becomes rapidly black suspension, and as shown in Figure 3, x-ray photoelectron power spectrum (XPS) result shows that the black suspension particle is the Co metallic catalyst; After the hydrogen manufacturing of AB solution finished, black suspension Co nano particle was stirred 200 minutes under argon gas atmosphere.Black suspension does not still change, and that is to say that the Co nano particle is stable in argon gas.The Co nano particle is described under argon atmosphere, can not under this condition, realizes cobalt nanoparticle and Co
2+Mutually conversion realizes self-protection function when the nano Co catalyst circulation is used.
Comparing embodiment 2
CoCl with 0.03mmol
26H
2O is dissolved in the distilled water of 5mL, obtains peach CoCl
2The aqueous solution; The AB of 50mg and the NaBH of 10mg
4Be dissolved in the distilled water of 5mL, under 25 ℃, this solution joined peach CoCl
2Magnetic agitation is even in the aqueous solution, and pink solution becomes rapidly black suspension, and as shown in Figure 3, x-ray photoelectron power spectrum (XPS) result shows that the black suspension particle is the Co metallic catalyst; After the hydrogen manufacturing of AB solution finishes, the black suspension Co nano particle of washing is placed in the distilled water, under air atmosphere, stirred this solution 200 minutes, find that black suspension does not still change.Illustrate that the Co nano particle is not having C1
-, BO
2 -And NH
4 +In the air that exists, can not realize cobalt nanoparticle and Co
2+Mutually conversion realizes self-protection function when the nano Co catalyst circulation is used.
Comparing embodiment 3
CoCl with 0.03mmol
26H
2O is dissolved in the distilled water of 5mL, obtains peach CoCl
2The aqueous solution; The AB of 50mg and the NaBH of 10mg
4Be dissolved in the distilled water of 5mL, under 25 ℃, this solution joined peach CoCl
2Magnetic agitation is even in the aqueous solution, and pink solution becomes rapidly black suspension, and as shown in Figure 3, x-ray photoelectron power spectrum (XPS) result shows that the black suspension particle is the Co metallic catalyst; After AB hydrogen manufacturing finishes, the black suspension Co nano particle of washing is placed in the ammoniacal liquor of PH=9.4, under air atmosphere, stirred this solution 200 minutes, find that black suspension does not still change.Illustrate that the Co nano particle is having NH
4 +In the air that exists, can not realize cobalt nanoparticle and Co
2+Mutually conversion realizes self-protection function when the nano Co catalyst circulation is used.
Comparing embodiment 4 (embodiments of the invention)
CoCl with 0.03mmol
26H
2O is dissolved in the distilled water of 5mL, obtains peach CoCl
2The aqueous solution; The AB of 50mg and the NaBH of 10mg
4Be dissolved in the distilled water of 5mL, under 25 ℃, this solution joined peach CoCl
2Magnetic agitation is even in the aqueous solution, pink solution becomes rapidly black suspension, as shown in Figure 3, x-ray photoelectron power spectrum (XPS) result shows, the black suspension particle is the Co metallic catalyst, the Co nano-particles size that initial reaction produces is about 20nm and reunites and arrive together as the nano chain structure, shown in Fig. 5 a; After the hydrogen manufacturing of AB solution finished, under 25 ℃, magnetic agitation was after 30 minutes in air with black suspension, and black suspension has become pink liquid.The AB of 50mg and the NaBH of 10mg
4Be dissolved in the distilled water of 5mg, this solution is poured in the pink solution, pink solution becomes black suspension again; Invention has used ultraviolet-visible absorption spectroscopy (UV-Vis) to detect transformation (Fig. 2).Be on the 510nm at wavelength, we have seen and CoCl
2(Fig. 2 a) adds the AB of the 50mg that is dissolved in 5mL distilled water and the NaBH of 10mg to corresponding absworption peak
4After,, this absworption peak disappears, and Co is described
2+Ion has been transformed into Co nano particle (Fig. 2 b).After black suspension was transformed into clearly pink solution, (Fig. 2 c) appearred in the absworption peak at 510nm place again, illustrates that cobalt nanoparticle is transformed into nano Co again
2+Ion is the 420nm place owing to the generation of new reaction product ions has produced new absworption peak at wavelength.The hydrogen manufacturing amount (mL) of this nano Co catalysis AB hydrogen production process and time (minute) figure is shown in Fig. 4 a, the Co nano particle catalysis AB hydrolytic hydrogen production of initial reduction can be finished in 11 minutes, and the amounts of 25 ℃ of lower generation hydrogen are 125mL.
Comparing embodiment 5
CoCl with 0.03mmol
26H
2O is dissolved in the distilled water of 5mL, obtains peach CoCl
2The aqueous solution; The AB of 50mg and the NaBH of 10mg
4Be dissolved in the distilled water of 5mL, under 25 ℃, this solution joined peach CoCl
2Magnetic agitation is even in the aqueous solution, pink solution becomes rapidly black suspension, as shown in Figure 3, x-ray photoelectron power spectrum (XPS) result shows, the black suspension particle is the Co metallic catalyst, the Co nano-particles size that initial reaction produces is about 20nm and reunites and arrive together as the nano chain structure, shown in Fig. 5 a; After the hydrogen manufacturing of AB solution finished, under 25 ℃, magnetic agitation was after 30 minutes in air with black suspension, and black suspension has become pink liquid.This explanation Co nano particle is converted into the Co with self-protection function through oxide etch
2+Behind the ion, preserved 7 days under the air at room temperature, add the AB of the 50mg that is dissolved in 5mL distilled water and the NaBH of 10mg
4After, again with being reduced into the Co nano particle and being applied in the same catalytic reaction.So repeat 5 times, totally 35 days, the Co nano particle of the 5th regeneration and the Co nano particle of initial reaction had identical reactivity as a result, and current catalysis AB hydrolytic hydrogen production can be finished in 11.4 minutes, and the amount that produces hydrogen is 125mL.
Comparing embodiment 6
CoCl with 0.03mmol
26H
2O is dissolved in the distilled water of 5mL, obtains peach CoCl
2The aqueous solution; The AB of 50mg and the NaBH of 10mg
4Be dissolved in the distilled water of 5mL, under 25 ℃, this solution joined peach CoCl
2Magnetic agitation is even in the aqueous solution, pink solution becomes rapidly black suspension, as shown in Figure 3, x-ray photoelectron power spectrum (XPS) result shows, the black suspension particle is the Co metallic catalyst, the Co nano-particles size that initial reaction produces is about 20nm and reunites and arrive together as the nano chain structure, shown in Fig. 5 a; After the hydrogen manufacturing of AB solution finished, under 25 ℃, magnetic agitation was after 30 minutes in air with black suspension, and black suspension has become pink liquid.This explanation Co nano particle is converted into the Co with self-protection function through oxide etch
2+Behind the ion, preserved 7 days under the air at room temperature, add the AB of the 50mg that is dissolved in 5mL distilled water and the NaBH of 10mg
4After, again be reduced into the Co nano particle and be applied in the same catalytic reaction.So repeat 10 times, totally 70 days, the Co nano particle of the 10th regeneration and the Co nano particle of initial reaction have identical reactivity as a result, the TEM of the Co nano particle behind the 10th secondary response knows (Fig. 5 b), the Co nano particle is about 4nm, current catalysis AB hydrolytic hydrogen production can be finished in 11 minutes, and 25 ℃ of lower amounts that produce hydrogen are 125mL.
Comparing embodiment 7
CoCl with 0.03mmol
26H
2O is dissolved in the distilled water of 5mL, obtains peach CoCl
2The aqueous solution; The AB of 50mg and the NaBH of 10mg
4Be dissolved in the distilled water of 5mL, under 25 ℃, this solution joined peach CoCl
2Magnetic agitation is even in the aqueous solution, pink solution becomes rapidly black suspension, as shown in Figure 3, x-ray photoelectron power spectrum (XPS) result shows, the black suspension particle is the Co metallic catalyst, the Co nano-particles size that initial reaction produces is about 20nm and reunites and arrive together as the nano chain structure, shown in Fig. 5 a; In air, the Co nano particle after the washing is stored in the pure water 7 days, then this catalyst granules being applied in the catalyzing manufacturing of hydrogen reaction of AB (does not have NaBH
4Reaction), reaction can only be finished (inserting shown in the figure such as Fig. 4) in 216 minutes.Generally speaking, the reversible transition of metal-metal ion can overcome as a kind of new method the oxidation passivation of Co nano particle, after preserving in air for a long time, the Co nanocatalyst still has very high activity, thereby the commerce that the Co nanocatalyst can be a large amount of is used.
Although the present invention reference example is appreciated that for the person of ordinary skill of the art can carries out the change on the part details in paying claim scope by detailed description.
Commercial Application:
Can simple and effectively avoid the oxidation passivation of non-precious metal catalyst with the standby nano Co catalyst of metal-metal ion reversible transition legal system, make it be easy to preserve, realize the protective effect of self and make the nano Co catalyst have very high cyclical stability.Promoted greatly to store up in the vehicle-mounted mobile hydrogen source material hydrogen-the put practical application of hydrogen.
Claims (5)
1. the self-shield nanometer cobalt catalyst of a high cyclical stability is characterized in that, described nanometer cobalt catalyst prepares by the following method:
The selection of the required chemicals of AB hydrogen production process: boron amide AB, CoCL2 6H2O CoCl
26H
2O, sodium borohydride NaBH
4With ammoniacal liquor H
5NO, the concrete steps of nano Co catalyst granules preparation are as follows:
Step 1 is with the CoCl of 0.01～0.05mmol
26H
2O is dissolved in the distilled water of 2～10mL, obtains peach CoCl
2The aqueous solution;
Step 2 is with the AB of 30～70mg and the NaBH of 5～30mg
4Be dissolved in the distilled water of 2～10mL;
Step 3 joins the solution in the step 2 solution of step 1;
Step 4, under 10-40 ℃ that solution magnetic agitation in air of step 3 gained is even, can see that the suspended particulate that black is arranged produces, the black suspension particle is the Co metallic catalyst;
Step 5, by the hydrogen that produces in the gas burette measuring process four, the hydrolytic hydrogen production equation is:
AB+2H
2O=NH
4 ++BO
2 -+3H
2；
Step 6, under 10-40 ℃, step 4 solution produces hydrogen finish after, in air behind the magnetic agitation 10-200min, black suspension has become pink liquid with black suspension, this peach liquid is CoCl
2Solution;
Step 7, the AB of 30～70mg and the NaBH of 5～30mg
4Be dissolved in the distilled water of 2～10mL;
Step 8 is poured step 7 solution in the step 6 solution into, and pink solution becomes black suspension again;
Step 9, under 10-40 ℃ that solution magnetic agitation in air of step 8 gained is even, can see that the suspended particulate that black is arranged produces, the black suspension particle is the Co metallic catalyst;
2. the self-shield nanometer cobalt catalyst of a kind of high cyclical stability according to claim 1 is characterized in that, used chemicals is the AB of boron amide 90wt%, the CoCl of CoCL2 6H2O 99wt%
26H
2O,〉the sodium borohydride NaBH of 96wt%
4And the ammoniacal liquor H of 25wt%～28wt%
5NO.
3. the self-shield nanometer cobalt catalyst of a kind of high cyclical stability according to claim 1 and 2 is characterized in that, described step 1 to four is with metal ion Co
2+Change metallic catalyst Co into; Described step 6 is to change metallic catalyst Co into metal ion Co
2+Thereby, make metallic catalyst Co obtain self-protection, realize the high cyclical stability of catalyst; Described step 9 is with metal ion Co
2+Change again metallic catalyst Co into; Above-mentioned steps one to nine is a reaction cycle, thereby realizes the self-shield nano Co catalyst with the standby high cyclical stability of metal-metal ion reversible transition legal system.
4. the self-shield nanometer cobalt catalyst of a kind of high cyclical stability according to claim 3 is characterized in that, synthetic Co nano-particles size is 20nm and reunites and arrive together as the nano chain structure first.
5. the self-shield nanometer cobalt catalyst of a kind of high cyclical stability according to claim 3 is characterized in that, synthetic Co nano-metal particle is dispersity again, and its nano particle size is about 4nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589975A (en) * | 2018-12-25 | 2019-04-09 | 吉林大学 | A kind of rhodium nanocatalyst and its preparation method and application of molybdenum oxide modification |
| CN111270263A (en) * | 2020-03-04 | 2020-06-12 | 太原理工大学 | Cobaltosic oxide electrode with foam nickel loaded with rich boron and oxygen vacancies and preparation method thereof |
| CN114713283A (en) * | 2022-04-26 | 2022-07-08 | 沈阳药科大学 | Cobalt nanoparticle efficient selective catalytic system and method for reducing alkyne to generate (Z) -olefin by using same |
-
2012
- 2012-12-05 CN CN2012105166659A patent/CN103041816A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 王建新: "纳米催化剂的制备和使用性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589975A (en) * | 2018-12-25 | 2019-04-09 | 吉林大学 | A kind of rhodium nanocatalyst and its preparation method and application of molybdenum oxide modification |
| CN111270263A (en) * | 2020-03-04 | 2020-06-12 | 太原理工大学 | Cobaltosic oxide electrode with foam nickel loaded with rich boron and oxygen vacancies and preparation method thereof |
| CN111270263B (en) * | 2020-03-04 | 2022-04-19 | 太原理工大学 | Cobaltosic oxide electrode with foam nickel loaded with rich boron and oxygen vacancies and preparation method thereof |
| CN114713283A (en) * | 2022-04-26 | 2022-07-08 | 沈阳药科大学 | Cobalt nanoparticle efficient selective catalytic system and method for reducing alkyne to generate (Z) -olefin by using same |
| CN114713283B (en) * | 2022-04-26 | 2024-05-14 | 沈阳药科大学 | Cobalt nanoparticle high-efficiency selective catalytic system and method for generating (Z) -alkene by reducing alkyne by using same |
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Application publication date: 20130417 |