CN103071503A - Catalyst for generating hydrogen by hydroboron hydrolysis and preparation method of catalyst - Google Patents
Catalyst for generating hydrogen by hydroboron hydrolysis and preparation method of catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst for generating hydrogen by hydroboron hydrolysis and a preparation method of the catalyst, and relates to a catalyst. The catalyst comprises an active component and a carrier, wherein the active component is cobalt monoxide nanocrystal; the carrier is metal oxide powder and carbon material powder; and the mass percent of the active component in the catalyst is 10%-100%. The preparation method comprises the steps of decomposing a metal precursor of cobalt in alkylamine containing trioctylphosphine phosphorous and ether taking alkylamine as a surfactant, conducting a reaction at 210-260 DEG C, cooling, separating, obtaining the active component with a particular pattern, mixing the active component with the carrier, and obtaining the catalyst. The catalyst can act as a substitute of the currently used noble metal catalyst, and has wide application prospects in the fields of fuel cells and the like. As the cobalt monoxide nanocrystal is taken as the active component, the catalyst has high activity for a hydrogen generation reaction by the hydroboron hydrolysis, is high in hydrogen generation speed, simple in preparation process, and low in cost.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind of Catalysts and its preparation method that produces hydrogen for borohydride hydrolytic.
Background technology
Along with the aggravation of environmental pollution, society becomes very urgent to the demand of clean energy resource in recent years, and hydrogen energy source has caused that as a kind of new cleaning fuel that can replace traditional fossil fuel people pay close attention to greatly, has broad application prospects.Hydrogen Energy is applied to fuel cell field, and to have operating temperature low, start fast, the characteristics that energy conversion efficiency is high.Realize the large-scale commercial applications application of fuel cell, hydrogen can be stored safely, efficiently and release is one of problem demanding prompt solution.From existing hydrogen storage method, bulky though high-pressure hydrogen storing is easy to use, poor stability.Liquid hydrogen storage ability is strong, is suitable for high-power Proton Exchange Membrane Fuel Cells, but loss is large in the storage hydrogen process, and existence poisons, and charges and discharge the problem of heat again.The hydride hydrogen-storing bulk density is large, but mass density is low.
Boron hydride has been subject to extensive concern as a kind of novel hydrogen storage material.The advantages such as it is high that it has an energy storage density, is applicable to low power proton exchange membrane fuel cell, stores and discharge safety, and the hydrogen of generation is free from foreign meter.Contained moisture has played the effect to the fuel battery proton exchange film humidification in the hydrogen, is fit to the use of fuel cell.Boron hydride generally can stably be present in the strong basicity environment, in actual use, need use the release of the effective catalyst control hydrogen with good combination property, improves hydrogen production efficiency.In recent years, the effective catalyst of finding in the research generally all contains the noble metal composition, and its expensive price is difficult to generally be accepted.Magnesium-yttrium-transition metal has a wide range of applications at catalytic field.Block cobalt, nickel and the Raney's nickel that has been found that (Raney nickel) all has ability (the J. Chem.Soc.Dalon.Trans.1985 that the catalysis sodium borohydride decomposes, 307), but its catalytic activity is not high enough, can not satisfy the requirement that fast decoupled produces hydrogen.Pt/C nano particle (Mater.Lett.2006,60,2236) and Ni-Ru nano particle (Int.J. Hydrogen Energ., 2009,34,2153), although have higher catalytic activity, but its complex process is expensive, is unfavorable for the heavy industrialization application.Recently, cobalt-base catalyst, such as Co-B(Appl.Catal.A:General.2011,86,394), Co-P-B (J.Power Sources.2009,188,411), Co
3O
4(J.Phys.Chem.C.2010,114,16456) etc. are found to have greater activity, but compare with noble metal catalyst, and its hydrogen-producing speed still has larger gap.From the currently reported catalyst that is applicable to boron hydride, seldom both had high catalytic activity, cheap price is arranged again simultaneously.Therefore, develop high, the cheap new catalyst of catalytic activity and will have important applied value in the technical field that borohydride hydrolytic produces hydrogen.
Summary of the invention
Purpose of the present invention aims to provide take cobalt protoxide (CoO) nanocrystalline as active component, reaction has high activity to borohydride hydrolytic hydrogen production, hydrogen-producing speed is fast, and preparation process is simple, a kind of Catalysts and its preparation method that produces hydrogen for borohydride hydrolytic with low cost.
Described catalyst for borohydride hydrolytic product hydrogen comprises active component and carrier, and active component is that cobalt protoxide is nanocrystalline, and carrier is metal oxide powder or material with carbon element powder, and the mass percent of active component is 10%～100% in the catalyst.
Described cobalt protoxide is nanocrystalline to be the cobalt protoxide particle of crystalline state, and pattern can be octahedra, almost spherical or random shape, and size is at 5～100nm.
Described metal oxide powder can adopt alundum (Al2O3) powder etc.
Described material with carbon element powder can adopt graphite powder etc.
The described preparation method who produces the catalyst of hydrogen for borohydride hydrolytic may further comprise the steps:
1) under inert gas shielding, in the metallic precursor and solvent adding reaction vessel with cobalt, insulation makes its homogenising and removes unnecessary steam;
2) inject surfactant;
3) be warming up to 210～240 ℃ after insulation, can partly form the settled solution of the nanocrystalline or cobalt-oleyl amine complex compound of cobalt protoxide;
4) continue to be warming up to 240～260 ℃, behind insulation 20～120min, be cooled to room temperature, add ethanol and make the product precipitation, the product of gained is cleaned with organic solvent, centrifugation, vacuum drying, it is nanocrystalline that the powder product that obtains is cobalt protoxide;
5) by the catalyst component proportioning that is used for borohydride hydrolytic product hydrogen cobalt protoxide manocrystalline powders and support powder are dispersed in organic solvent, then put into the container of sealing, stir, centrifugation is nanocrystalline in the load not, and vacuum drying namely gets the catalyst that produces hydrogen for borohydride hydrolytic.
In step 1), acetate or the acetylacetonate of the optional cobalt of metal precursor of described cobalt; The metallic precursor of cobalt and the mol ratio of solvent can be 0.003～0.1; Described solvent can adopt at least a in alkylamine, the ethers etc., described alkylamine can be selected from least a in oleyl amine, lauryl amine, the cetylamine etc.; Described ethers can be selected from least a in benzyl ether, the diphenyl ether etc.; The temperature of described insulation can be 100～140 ℃, and the time of insulation can be 5～30min.
In step 2) in, described surfactant can adopt trioctylphosphine phosphorus or alkylamine etc.; Described alkylamine can be selected from a kind of in oleyl amine, lauryl amine, the cetylamine etc.; The mol ratio of the solvent in described surfactant and the step 1) can be 0～0.2.
In step 3), the time of described insulation can be 30～60min.
In step 4), described organic solvent can be selected from least a in n-hexane, toluene, ethanol, the acetone etc.
In step 5), described organic solvent can be selected from least a in n-hexane, toluene, ethanol, the acetone etc.; The time of described stirring can be more than 15h.
When the addition of surfactant is 0, omit step 2).
When the mass percent of the catalyst active component that is used for borohydride hydrolytic product hydrogen is 100%, omit step 5).
Being used for borohydride hydrolytic, to produce the hydrolytic hydrogen production catalytic performance activity rating method of catalyst of hydrogen as follows: a certain amount of catalyst for borohydride hydrolytic product hydrogen is positioned over reactor, reactor is put into the isothermal reaction groove, behind the insulation 10min, inject a certain amount of alkaline borohydride solution, under agitation catalysis produces hydrogen, and with the drainage collection, obtain hydrogen-producing speed by producing hydrogen volume and time relationship.Boron hydride can be: alkali and alkaline earth metal ions boron hydride and borine ammonium complex compound.
The nanocrystalline size of catalyst active component cobalt protoxide and pattern for borohydride hydrolytic product hydrogen provided by the present invention all can be by changing reaction temperature, and temperature retention time and reactant ratio are regulated.The nanocrystalline catalysis behavior of the cobalt protoxide of different-shape is variant, but still keeps very high catalytic activity.The nanocrystalline employing one kettle way preparation of cobalt protoxide, preparation process is simple, and is with low cost, is convenient to suitability for industrialized production.The prepared catalyst that is used for borohydride hydrolytic product hydrogen is used for the borohydride hydrolytic hydrogen production reaction to carry out at normal temperatures and pressures, do not need additionally to provide energy, the catalytic activity that is used for the catalyst of borohydride hydrolytic product hydrogen surpasses most of existing noble metal catalysts, hydrogen-producing speed surpasses most existing base metals and very most of noble metal catalyst, can be used as a substitute of the noble metal catalyst of present use, have a wide range of applications in fields such as fuel cells.
Description of drawings
Fig. 1 is the prepared nanocrystalline transmission electron microscope photo of cobalt protoxide of embodiment 1.Scale is 100nm.
Fig. 2 is the prepared nanocrystalline electron diffraction diagram of cobalt protoxide of embodiment 1.
To be that the prepared cobalt protoxide of embodiment 1 is nanocrystalline produce the output of hydrogen and the curve of time 30 ℃ of lower catalysis sodium borohydrides hydrolysis to Fig. 3.Abscissa is time (min), and ordinate is hydrogen output (ml).
Fig. 4 is the prepared nanocrystalline transmission electron microscope photo of cobalt protoxide of embodiment 2.Scale is 100nm.
Fig. 5 is the prepared nanocrystalline electron diffraction diagram of cobalt protoxide of embodiment 2.
To be that the prepared cobalt protoxide of embodiment 2 is nanocrystalline produce the output of hydrogen and the curve of time 30 ℃ of lower catalysis sodium borohydrides hydrolysis to Fig. 6.Abscissa is time (min), and ordinate is hydrogen output (ml).
Fig. 7 is the prepared nanocrystalline transmission electron microscope photo of cobalt protoxide of embodiment 3.Scale is 100nm.
Fig. 8 is the prepared nanocrystalline electron diffraction diagram of cobalt protoxide of embodiment 3.
Fig. 9 is that the nanocrystalline 30 ℃ of lower catalysis sodium borohydride hydrolysis of embodiment 3 prepared cobalt protoxides produce the output of hydrogen and the curve of time.Abscissa is time (min), and ordinate is hydrogen output (ml).
Figure 10 is the prepared nanocrystalline transmission electron microscope photo of cobalt protoxide of embodiment 4.Scale is 50nm.
Figure 11 is that the embodiment 4 prepared nanocrystalline 30 ℃ of lower catalysis sodium borohydride hydrolysis of cobalt protoxide produce the output of hydrogen and the curve of time.Abscissa is time (min), and ordinate is hydrogen output (ml).
Figure 12 is the prepared nanocrystalline loaded catalyst powder that forms on the alundum (Al2O3) powder that loads to of cobalt protoxide of embodiment 5, produces the output of hydrogen and the curve of time 30 ℃ of lower catalysis sodium borohydrides hydrolysis.Abscissa is time (min), and ordinate is hydrogen output (ml).
Figure 13 is the prepared nanocrystalline loaded catalyst powder that forms on the graphite powder that loads to of cobalt protoxide of embodiment 6, produces the output of hydrogen and the curve of time 30 ℃ of lower catalysis sodium borohydrides hydrolysis.Abscissa is time (min), and ordinate is hydrogen output (ml).
Figure 14 is the prepared nanocrystalline loaded catalyst powder that forms on the graphite powder that loads to of cobalt protoxide of embodiment 7, produces the output of hydrogen and the curve of time 30 ℃ of lower catalysis sodium borohydrides hydrolysis.Abscissa is time (min), and ordinate is hydrogen output (ml).
Figure 15 is the prepared nanocrystalline loaded catalyst powder that forms on the aluminium oxide powder that loads to of cobalt protoxide of embodiment 8, produces the output of hydrogen and the curve of time 30 ℃ of lower catalysis sodium borohydrides hydrolysis.Abscissa is time (min), and ordinate is hydrogen output (ml).
The specific embodiment
The present invention will be further described below by embodiment.
Embodiment 1
0.5mmol Cobalt diacetate tetrahydrate, 10ml oleyl amine are added in the four-hole bottle; under argon shield, stir, mix; then be warming up to 120 ℃, insulation 30min fully mixes it, then injects the 1.5mmol tri octyl phosphine; be cooled to room temperature after being warming up to 240 ℃ of insulation 40min; add ethanol product is precipitated, by centrifugal taking-up reaction mother liquor, then use acetone and n-hexane mixed solution cyclic washing three times; last vacuum drying obtains the powder product.Fig. 1 is the transmission electron microscope photo of product, about the nanocrystalline 40nm of being of a size of that makes, has octahedral shape.Fig. 2 is the electronic diffraction spectrogram of product, confirms that product is the cobalt protoxide of face-centred cubic structure.
Adopt the prepared cobalt protoxide nanocrystalline catalyst (content of active component cobalt protoxide is 100%) of 10mg, produce hydrogen in the hydrolysis of 30 ℃ of lower catalysis 5ml alkalescence sodium borohydride (10wt% sodium borohydride and 10wt% NaOH) solution.Fig. 3 is the curve of hydrogen output and time.The maximum rate that hydrogen produces is: 5950ml/ming, the hydrogen-producing speed decay seldom in the course of reaction.
Embodiment 2
0.5mmol Cobalt diacetate tetrahydrate, 10ml two Bian ethers are added in the four-hole bottle; under argon shield, stir, mix, then be warming up to 130 ℃, insulation 20min; remove unnecessary steam; be warming up to 240 ℃, be cooled to room temperature behind the insulation 20min, add ethanol product is precipitated; by centrifugal taking-up reaction mother liquor; then use acetone and n-hexane mixed solution cyclic washing three times, last vacuum drying obtains the powder product.Fig. 4 is the transmission electron microscope photo of this product, and what make is nanocrystalline for irregular shape.Fig. 5 is the electronic diffraction spectrogram of product, confirms that product is the cobalt protoxide of face-centred cubic structure.
Adopt the prepared cobalt protoxide nanocrystalline catalyst (content of active component cobalt protoxide is 100%) of 10mg, produce hydrogen in the hydrolysis of 30 ℃ of lower catalysis 5ml alkalescence sodium borohydride (10wt% sodium borohydride and 10wt% NaOH) solution.Fig. 6 is the curve of hydrogen output and time.The maximum rate that hydrogen produces is about: 5900ml/ming, the hydrogen-producing speed decay seldom in the course of reaction.
Embodiment 3
0.5mmol Cobalt diacetate tetrahydrate, 10ml two Bian ethers are added in the four-hole bottle; under argon shield, stir, mix; then be warming up to 130 ℃; insulation 20min; remove unnecessary steam; then add the 2ml oleyl amine, be warming up to 220 ℃ after fully mixing, insulation 60min; form the transparent complex compound of yellowish-brown; and then be warming up to 240 ℃, and be cooled to room temperature behind the insulation 20min, add ethanol product is precipitated; by centrifugal taking-up reaction mother liquor; then use acetone and n-hexane mixed solution cyclic washing three times, last vacuum drying obtains the powder product.Fig. 7 is the transmission electron microscope photo of this product, about the nanocrystalline 10nm of being of a size of that makes, is shaped as almost spherical.Fig. 8 is the electronic diffraction spectrogram of product, confirms that product is the cobalt protoxide of face-centred cubic structure.
Adopt the prepared cobalt protoxide nanocrystalline catalyst (content of active component cobalt protoxide is 100%) of 10mg, produce hydrogen in the hydrolysis of 30 ℃ of lower catalysis 5ml alkalescence sodium borohydride (10wt% sodium borohydride and 10wt% NaOH) solution.Fig. 9 is the curve of hydrogen output and time.The maximum rate that initial reaction stage hydrogen produces is: 5890ml/ming, but along with reaction is carried out, hydrogen-producing speed is decayed to some extent.
Embodiment 4
0.25mmol Cobalt diacetate tetrahydrate, 10ml oleyl amine are added in the four-hole bottle; stir under argon shield, mix, then be warming up to 120 ℃, insulation 30min fully mixes it; then inject the 1.5mmol tri octyl phosphine; be warming up to 240 ℃, be cooled to room temperature behind the insulation 40min, add ethanol product is precipitated; by centrifugal taking-up reaction mother liquor; then use acetone and n-hexane mixed solution cyclic washing three times, last vacuum drying obtains the powder product.Figure 10 is the transmission electron microscope photo of this product, about the nanocrystalline 25nm of being of a size of that makes, is shaped as octahedron.
Adopt the prepared cobalt protoxide nanocrystalline catalyst (content of active component cobalt protoxide is 100%) of 10mg, produce hydrogen in the hydrolysis of 30 ℃ of lower catalysis 5ml alkalescence sodium borohydride (10wt% sodium borohydride and 10wt% NaOH) solution.Figure 11 is the curve of hydrogen output and time.The maximum rate that initial reaction stage hydrogen produces is about: 6000ml/ming, along with reaction is carried out, hydrogen-producing speed is decayed seldom.
Embodiment 5
Prepare cobalt protoxide by the method for embodiment 2 nanocrystalline, then get the nanocrystalline 30mg of prepared cobalt protoxide, commercial alundum (Al2O3) powder 150mg, the 10ml hexane solution, in airtight container, mix, more than the vigorous stirring 15h, until nanocrystallinely load on the aluminium oxide powder fully, then centrifugal drying obtains cobalt protoxide content and is 16.67% loaded catalyst powder.
Get described loaded catalyst powder 60mg, wherein the content of active component cobalt protoxide is 10mg, produces hydrogen in the hydrolysis of 30 ℃ of lower catalysis 5ml alkalescence sodium borohydride (10wt% sodium borohydride and 10wt% NaOH) solution.Figure 12 is the curve of its hydrogen output and time.The maximum rate that initial reaction stage hydrogen produces is: 5790ml/ming, along with reaction is carried out, the hydrogen-producing speed decay is less.
Embodiment 6～9
With embodiment 5, the amount that changes the alundum (Al2O3) powder is respectively 7.5mg, 20mg, 30mg and 50mg obtain active component cobalt protoxide content and are respectively 80%, 60%, 50%, 37.5% loaded catalyst is got described loaded catalyst powder 10mg,, wherein the content of active component is respectively 8mg, 6mg, 5mg and 3.75mg,, press embodiment 1 hydrolytic hydrogen production catalytic performance activity rating method, measure respectively its hydrogen-producing speed, the results are shown in table 1.Can find out that dropping into active component diminishes, hydrogen-producing speed decreases, but still keeps high value.
Active component mass percent and the hydrogen-producing speed of table 1. catalyst
| Embodiment | CoO content (mg) | Active CoO mass percent (%) | Hydrogen-producing speed (ml/ming) |
| 6 | 8 | 80 | 4933 |
| 7 | 6 | 60 | 4200 |
| 8 | 5 | 50 | 3560 |
| 9 | 3.75 | 37.5 | 3210 |
Prepare cobalt protoxide by the method for embodiment 2 nanocrystalline, then get the nanocrystalline 20mg of prepared cobalt protoxide, commercial graphite powder 150mg, the 10ml hexane solution, in airtight container, mix, more than the vigorous stirring 15h, until nanocrystallinely load on the graphite powder fully, then centrifugal drying obtains cobalt protoxide content and is 11.76% loaded catalyst powder.
Get described loaded catalyst powder 85mg, wherein the content of active component cobalt protoxide is 10mg, produces hydrogen in the hydrolysis of 30 ℃ of lower catalysis 5ml alkalescence sodium borohydride (10wt% sodium borohydride and 10wt% NaOH) solution.Figure 13 is the curve of its hydrogen output and time.The generation speed of initial reaction stage hydrogen is slow, shows that activationary time is longer, and course of reaction still keeps high hydrogen-producing speed, and the maximum rate that hydrogen produces is 5450ml/ming, and along with reaction is carried out, hydrogen-producing speed is decayed to some extent.
Embodiment 11
Prepare cobalt protoxide by the method for embodiment 1 nanocrystalline, then get the nanocrystalline 20mg of prepared cobalt protoxide, commercial graphite powder 75mg, the 10ml hexane solution, in airtight container, mix, more than the vigorous stirring 15h, until nanocrystallinely load on the graphite powder fully, then centrifugal drying obtains cobalt protoxide content and is 23.53% loaded catalyst powder.
Get described loaded catalyst powder 95mg, wherein the content of cobalt protoxide is 20mg, produces hydrogen in the hydrolysis of 30 ℃ of lower catalysis 5ml alkalescence sodium borohydride (10wt% sodium borohydride and 10wt% NaOH) solution.Figure 14 is the curve of its hydrogen output and time.The maximum rate that hydrogen produces is 8333ml/ming, and the hydrogen-producing speed decay is very little in the course of reaction.
Embodiment 12
Prepare cobalt protoxide by the method for embodiment 1 nanocrystalline, then get the nanocrystalline 10mg of prepared cobalt protoxide, commercial graphite powder 50mg, measure the 10ml hexane solution, in airtight container, mix, more than the vigorous stirring 15h, until nanocrystallinely load on the graphite powder fully, then centrifugal drying obtains cobalt protoxide content and is 16.67% loaded catalyst powder.
Get described loaded catalyst powder 30mg, wherein the content of cobalt protoxide is 5mg, produces hydrogen in the hydrolysis of 30 ℃ of lower catalysis 5ml alkalescence sodium borohydride (10wt% sodium borohydride and 10wt% NaOH) solution.Figure 15 is the curve of its hydrogen output and time.The maximum rate that hydrogen produces is 3640ml/ming.Along with reaction is carried out, hydrogen-producing speed is slightly decayed.
Claims (10)
1. one kind is used for the catalyst that borohydride hydrolytic produces hydrogen, it is characterized in that comprising active component and carrier, active component is that cobalt protoxide is nanocrystalline, and carrier is metal oxide powder or material with carbon element powder, and the mass percent of active component is 10%～100% in the catalyst.
2. a kind of catalyst that produces hydrogen for borohydride hydrolytic as claimed in claim 1 is characterized in that described cobalt protoxide is nanocrystalline and be the cobalt protoxide particle of crystalline state that pattern is octahedron, almost spherical or random shape, and size is at 5～100nm.
3. a kind of catalyst that produces hydrogen for borohydride hydrolytic as claimed in claim 1 is characterized in that described metal oxide powder adopts the alundum (Al2O3) powder; Described material with carbon element powder adopts graphite powder.
4. a kind of preparation method who produces the catalyst of hydrogen for borohydride hydrolytic as claimed in claim 1 is characterized in that may further comprise the steps:
1) under inert gas shielding, in the metallic precursor and solvent adding reaction vessel with cobalt, insulation makes its homogenising and removes unnecessary steam;
2) inject surfactant;
3) be warming up to 210～240 ℃ after insulation, can partly form the settled solution of the nanocrystalline or cobalt-oleyl amine complex compound of cobalt protoxide;
4) continue to be warming up to 240～260 ℃, behind insulation 20～120min, be cooled to room temperature, add ethanol and make the product precipitation, the product of gained is cleaned with organic solvent, centrifugation, vacuum drying, it is nanocrystalline that the powder product that obtains is cobalt protoxide;
5) by the catalyst component proportioning that is used for borohydride hydrolytic product hydrogen cobalt protoxide manocrystalline powders and support powder are dispersed in organic solvent, then put into the container of sealing, stir, centrifugation is nanocrystalline in the load not, and vacuum drying namely gets the catalyst that produces hydrogen for borohydride hydrolytic.
5. a kind of preparation method who produces the catalyst of hydrogen for borohydride hydrolytic as claimed in claim 4 is characterized in that in step 1), and the metal precursor of described cobalt is selected from acetate or the acetylacetonate of cobalt; The metallic precursor of cobalt and the mol ratio of solvent are 0.003～0.1.
6. a kind of preparation method who produces the catalyst of hydrogen for borohydride hydrolytic as claimed in claim 4, it is characterized in that in step 1), described solvent adopts at least a in alkylamine, the ethers, described alkylamine can be selected from least a in oleyl amine, lauryl amine, the cetylamine; Described ethers can be selected from least a in benzyl ether, the diphenyl ether; The temperature of described insulation can be 100～140 ℃, and the time of insulation can be 5～30min.
7. a kind of preparation method who produces the catalyst of hydrogen for borohydride hydrolytic as claimed in claim 4 is characterized in that in step 2) in, described surfactant adopts trioctylphosphine phosphorus or alkylamine; Described alkylamine can be selected from a kind of in oleyl amine, lauryl amine, the cetylamine; The mol ratio of the solvent in described surfactant and the step 1) can be 0～0.2.
8. a kind of preparation method who produces the catalyst of hydrogen for borohydride hydrolytic as claimed in claim 4 is characterized in that in step 3), and the time of described insulation is 30～60min.
9. a kind of preparation method who produces the catalyst of hydrogen for borohydride hydrolytic as claimed in claim 4 is characterized in that in step 4) and 5) in, described organic solvent is selected from least a in n-hexane, toluene, ethanol, the acetone.
10. a kind of preparation method who produces the catalyst of hydrogen for borohydride hydrolytic as claimed in claim 4 is characterized in that in step 5), and the time of described stirring is more than 15h.
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| CN107376916B (en) * | 2017-07-19 | 2020-07-24 | 桂林电子科技大学 | C-Co composite nano material and preparation method and application thereof |
| CN115072660A (en) * | 2022-06-14 | 2022-09-20 | 蓝海易氢动力(青岛)有限公司 | Magnesium hydride composite material, preparation method and application thereof, and hydrogen production method |
| CN115072660B (en) * | 2022-06-14 | 2024-01-26 | 蓝海易氢动力(青岛)有限公司 | Magnesium hydride composite material, preparation method and application thereof, and hydrogen production method |
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