CN106140166B - A kind of loaded catalyst, preparation method and applications - Google Patents
A kind of loaded catalyst, preparation method and applications Download PDFInfo
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- CN106140166B CN106140166B CN201610494201.0A CN201610494201A CN106140166B CN 106140166 B CN106140166 B CN 106140166B CN 201610494201 A CN201610494201 A CN 201610494201A CN 106140166 B CN106140166 B CN 106140166B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of preparation methods of loaded catalyst, comprising the following steps: S1, carbon material is dispersed in isopropanol or normal propyl alcohol, forms carbon material mixed solution；S2, binary transition metal salting liquid is added into carbon material mixed solution, rapidly joins deionized water after 0.5-1.5h is reacted at 70-100 DEG C, and continue to react 10-40min at 70-100 DEG C；S3, the reaction product in step S2 is washed, and the product after washing is dried, the catalyst of carbon material supported bimetallic oxide nano particle is prepared.The method of the present invention utilizes water and isopropanol or normal propyl alcohol system, and the characteristic that acetate hydrolyzes at high temperature is prepared for bimetallic oxide and is loaded to that catalyst is prepared on carbon material, preparation method is simple, strong operability, the lower cost for material used, and being capable of mass production.
Description
Technical field
The present invention relates to hydrogen storage material field more particularly to a kind of loaded catalysts, preparation method and applications.
Background technique
With the development of industry, population is continuously increased, develop sustainable green energy resource for example, wind energy, solar energy and
Hydrogen Energy has extremely important meaning.And in these clean energy resourcies, because Hydrogen Energy energy density is high, without dirt when use
The byproduct of metachromia generates (only water generation), will not cause damages to environment, the economy based on Hydrogen Energy has obtained
More and more concerns.But a urgent problem is exactly to develop one kind to can store a large amount of hydrogen, and price
Cheap nontoxic solid storage material.In a variety of materials developed at present, ammonia borine (Ammonia Borane) is
A kind of more satisfactory hydrogen storage material is most basic boron-nitrogen compound, because of its high hydrogen storage content (19.6 wt%) and room
Temperature the characteristics such as is stablized and is received more and more attention, and a kind of one of potential hydrogen storage material is had become.
In order to efficiently be catalyzed ammonia borane hydrolysis, hydrogen is quickly discharged from ammonia borine, many researchers pay
A large amount of effort, Wenyao Chen etc. load to Pt nano particle in carbon nanotube, obtain very efficient catalyst；
Effective catalyst will be made in Serdar Akbayrak and Saim O zkar on Ru nanometer particle load to multi-walled carbon nanotube.
It removes noble metal Pt, Ru as introduced above etc. to be applied in this field, a large amount of base metal (Cu, Ni, Co etc.) catalyst
Also it is prepared out, Jun Li et al. loads to copper-cobalt alloy on metal organic frame；Hoang Yen and Freddy Kleitz
By the way that copper oxide nickel oxide mixture is made in high-temperature heat treatment after metal precursor physical mixed.Therefore, noble metal catalyst
(such as platinum, ruthenium, rhodium) although effect is good, price is too high, limits the application of ammonia borine in actual production.And base metal
Catalyst (such as copper, cobalt, nickel), although at low cost, catalytic efficiency is not high.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation method of loaded catalyst, including it is following
Step:
S1, carbon material is dispersed in isopropanol or normal propyl alcohol, forms carbon material mixed solution；
S2, binary transition metal salting liquid is added into carbon material mixed solution, reacts 0.5-1.5h at 70-100 DEG C
After rapidly join deionized water, and continue to react 10-40min at 70-100 DEG C；
S3, the reaction product in step S2 is washed, and the product after washing is dried, be prepared
The catalyst of carbon material supported bimetallic oxide nano particle.
Further, the carbon material in the step S1 is in graphene oxide, carbon nanotube, porous carbon and graphene
One or more combinations；
Binary transition metal salting liquid in the step S2 is any two kinds in molysite, cobalt salt, mantoquita and nickel salt
Combination.
Further, the molysite is ferric acetate, and the cobalt salt is cobalt acetate, and the mantoquita is copper acetate, the nickel salt
For nickel acetate.
Further, the summation of the amount of the binary transition metal salting liquid substance is 0.1-0.5mmol.
Further, the mass ratio of carbon material and isopropanol or normal propyl alcohol is 1-2:1 in the step S1；The step S1
The volume ratio of deionized water is 1:1 in middle isopropanol or normal propyl alcohol and step S2.
Further, the binary transition metal salting liquid is preferably copper acetate and cobalt acetate；
The mass ratio of the material of the copper acetate and cobalt acetate is 1-4:1.
Correspondingly, the present invention also provides a kind of loaded catalyst, the catalyst is prepared by above-mentioned method
It arrives, the catalyst is carbon material supported bimetallic oxide nano particle.
Further, the carbon material is one of graphene oxide, carbon nanotube, porous carbon and graphene or a variety of
Combination；
The bimetallic oxide is any two kinds of combination in the oxide of iron, cobalt, copper and mickel；
The size of the bimetallic oxide nano particle is 2-10nm.
Further, the bimetallic oxide is preferably the oxide of copper and cobalt, wherein the ratio of the amount of copper and cobalt substance
For 1-4:1.
Correspondingly, the present invention also provides a kind of application of loaded catalyst, the catalyst is above-mentioned catalyst,
The catalyst is dispersed in ammonia borine aqueous solution, the dehydrogenation of ammonia borane hydrolysis is used for.
In the present invention between bimetallic oxide nano particle have synergistic effect, and bimetallic oxide nano particle with
Also there is certain synergistic effect, so that the catalytic effect of catalyst is high between carrier carbon material.
In addition, the water and isopropanol or normal propyl alcohol system in the present invention are extremely important, if there was only isopropanol or just without water
Propyl alcohol can not then form nano particle, if there was only water without isopropanol or normal propyl alcohol, nano particle can be considerably less, catalysis effect
Fruit is very undesirable, and therefore, water, isopropanol or normal propyl alcohol system are extremely important.
Loaded catalyst of the invention, preparation method and applications, have the following beneficial effects:
1, the characteristic system that the method for the present invention is hydrolyzed at high temperature using water and isopropanol or normal propyl alcohol system and acetate
Standby bimetallic oxide is simultaneously loaded to catalyst is prepared on carbon material, and preparation method is simple, strong operability, makes
Lower cost for material, and being capable of mass production.
2, carbon material supported bimetallic oxide nano-particle material is applied in ammonia borane hydrolysis hydrogen manufacturing in the present invention,
Very high catalytic effect is obtained, not only catalytic efficiency is higher than other non-precious metal catalysts in the prior art, and is catalyzed
The stability and repeatability of agent are very good.
3, in ammonia borane hydrolysis catalyst, the catalyst using metal oxide as catalyst body is less, and will be double
Metal oxide nanoparticles are combined with carbon material, even more unprecedented.And in the present invention catalyst preparation method letter
Single efficient, catalyst cost is very low, and catalytic effect is very good.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the schematic diagram of the loaded catalyst preparation process in the embodiment of the present invention one；
Fig. 2 is the catalyst Cu in the embodiment of the present invention one0.8Co0.2The transmission electron microscope picture and X-ray energy spectrum element of O-GO
Figure；
Fig. 3 is the catalyst Cu in the embodiment of the present invention one0.8Co0.2The grain size distribution of O-GO；
Fig. 4 is the Raman figure for the catalyst that in the embodiment of the present invention one prepared by copper cobalt different proportion；
Fig. 5 is the XRD diagram for the catalyst that in the embodiment of the present invention one prepared by copper cobalt different proportion；
Fig. 6 is the comparison diagram of bimetallic oxide and the catalytic performance of single metal oxides in the embodiment of the present invention one；
Fig. 7 is the catalytic performance comparison diagram for the catalyst that in the embodiment of the present invention one prepared by copper cobalt different proportion；
Fig. 8 is the Cu in the embodiment of the present invention one in different time0.8Co0.2The stability test figure of O-GO sample；
Fig. 9 be in the embodiment of the present invention one different temperatures to Cu0.8Co0.2The influence of the catalytic performance of O-GO sample；
Figure 10 is the comparison chart of the catalytic performance of three kinds of catalyst in the embodiment of the present invention one to three.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art without creative labor it is obtained it is all its
His embodiment, shall fall within the protection scope of the present invention.
Embodiment one:
The embodiment of the invention provides a kind of preparation methods of loaded catalyst, comprising the following steps:
Step 1: the preparation (i.e. carbon material is graphene oxide) of graphene oxide (Graphene Oxide, GO), GO
It is prepared using improved Hummers, freeze-drying obtains product.
1) 2g graphite and 1.0g sodium nitrate are added in the flask of 500ml, forms the concentrated sulfuric acid of addition 46ml after mixture,
And flask is placed under condition of ice bath；
2) mechanical stirring is used, after twenty minutes by said mixture stirring, within a hour, point 12 height by 6g
Potassium manganate (0.5g potassium permanganate is added per minute) is slowly added thereto (can be i.e. slow slowly), and it is one small to continue stirring after adding
When；
3) flask is moved in oil bath pan, and temperature is risen to 35 DEG C, kept for 2 hours of reaction；
4) 2 hours after reaction, are slowly added to 92ml deionized water using liquid-transfering gun, add water later for temperature liter
To 98 DEG C, this thermotonus is kept 20 minutes；
5) heating device is closed, the deionized water of 280ml is added into flask, 5ml hydrogen peroxide is and then added
(30wt%) keeps mechanical stirring in whole process；
Etc. 6) when temperature are down to 60 DEG C or so, centrifugal filtration while hot, and washed with the dilute hydrochloric acid of 400ml 10%；
7) using deionized water by mixture centrifuge washing obtained in step 6), 500 turns first centrifugations removal in 3 minutes compared with
Heavy seeds, then 8800 turns of centrifugation 3min are until supernatant liquor pH value detects upper layer to neutrality, and using silver nitrate and barium chloride
Not chloride ion-containing (Cl in clear liquid-) and sulfate ion (SO4 2-)；
8) -70 DEG C of freezings in deionized water by the dispersion of obtained precipitating, are placed on, using freeze drier, are done
Graphene oxide powder is made in dry 48h.
Step 2: the preparation of loaded catalyst, as shown in FIG. 1, FIG. 1 is the loaded catalysts in the embodiment of the present invention
The schematic diagram of preparation process；
1) GO of 80mg is dispersed in 80ml isopropanol, ultrasonic 1h, forms GO mixed solution；
2) by graphene oxide GO mixed solution import three-necked flask in, and thereto be added 0.192mmol copper acetate and
0.048 mmol cobalt acetate, three-necked flask is placed in oil bath pan, rapidly joins 80 ml after one hour of 80 DEG C of back flow reactions
Ionized water, and the reaction was continued 30 minutes for 80 DEG C of holding；
3) after obtaining mixed solution, using dehydrated alcohol filtration washing 2 times, then after being washed with deionized 2 times, 70 DEG C of skies
It is 12 hours dry in gas；
The ratio for changing the step the amount of the substance of copper and cobalt in 2) is 10:0,8:2,6:4,5:5,4:6,2:8,0:
10, keeping the amount summation of the substance of copper and cobalt is 0.24 mmol, remaining experimental procedure is same as described above, and 7 groups of preparation is different to urge
Agent is used for the test of ammonia borane hydrolysis.
Correspondingly, the embodiment of the invention also provides a kind of loaded catalyst, the catalyst is above method preparation
It obtains, the catalyst is GO supported copper cobalt dual-metal oxide nano particles；The bimetallic oxide nano particle
Having a size of 3 ± 0.5nm nm, wherein the ratio of the amount of copper and cobalt substance is 1-4:1.
As shown in table 1 below, table 1 is the tenor and corresponding TOF of copper and cobalt in each sample in the embodiment of the present invention
It is worth comparison diagram.
Table 1
Fig. 2 is the catalyst Cu in the embodiment of the present invention0.8Co0.2The transmission electron microscope picture and X-ray energy spectrum elemental map of O-GO,
Available particle size is 3nm or so by analysis, and nanoparticle is dispersed on carrier graphene oxide.Fig. 3 is
Catalyst Cu in the embodiment of the present invention0.8Co0.2The grain size distribution of O-GO, by demonstrating the particle size of Fig. 2 kind in figure,
Grain average-size is 3 ± 0.5nm.
Fig. 4 and Fig. 5 is the Raman figure and XRD diagram for the catalyst that in the embodiment of the present invention prepared by copper cobalt different proportion respectively,
It can prove the presence of graphene oxide simultaneously by Raman figure and XRD diagram, and XRD diagram also demonstrates CuxCo1-xO-GO nanoparticle
Son is a kind of unformed structure.
Fig. 6 is the comparison diagram of bimetallic oxide and the catalytic performance of single metal oxides in the embodiment of the present invention, by scheming
It is found that the catalytic effect of bimetallic oxide is far better than single metal oxides.
Fig. 7 is the catalytic performance comparison diagram for the catalyst that in the embodiment of the present invention prepared by copper cobalt different proportion, as seen from the figure,
When copper cobalt ratio difference, the catalyst performance being prepared is different, by can be seen that in upper table 1, wherein especially with
Cu0.8Co0.2O-GO and Cu0.6Co0.4The catalytic performance of O-GO is best, according to its corresponding TOF value is tested, wherein highest be
Cu0.8Co0.2O-GO, value are 70 molH2·min-1·molmetal -1。
Fig. 8 is the Cu in the embodiment of the present invention in different time0.8Co0.2The stability test figure of O-GO sample, can by figure
Know, Cu0.8Co0.2The stability of O-GO sample be it is extraordinary, there is no apparent performance loss first 6 times, be maintained at 90%
Left and right.
1-8 respectively represents the Cu of differential responses time in Fig. 80.8Co0.2O-GO sample, the 1-8 sample effect compare such as
Shown in the following table 2.
Table 2
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
| Effect (%) | 100 | 88.9 | 88.9 | 94.7 | 88.9 | 94.7 | 63.2 | 58.3 |
| TOF | 70 | 62.2 | 62.2 | 66.3 | 62.2 | 66.3 | 44.2 | 40.8 |
| Reaction time (min) | 2 | 2.25 | 2.25 | 2.12 | 2.25 | 2.12 | 3.16 | 3.43 |
Fig. 9 be in the embodiment of the present invention different temperatures to Cu0.8Co0.2The influence of the catalytic performance of O-GO sample, can by figure
Know, as the temperature rises, catalytic performance promotion it is obvious that and according to the different performance under different temperatures, according to Allan
Ni Wusi formula (Arrhenius equation), can calculate Cu0.8Co0.2The activation energy of O-GO is 45.53KJ/mol.
Loaded catalyst of the invention, preparation method and applications, have the following beneficial effects:
1, the method for the present invention is prepared for double gold using the characteristic that water and Isopropanol Solvent and acetate hydrolyze at high temperature
Belong to oxide and loaded to catalyst is prepared on carbon material, preparation method is simple, strong operability, the material used
It is low in cost, and being capable of mass production.
2, acquisition when best preparation ratio is 4:1 is found by regulating and controlling the ratio of the amount of the substance of copper and cobalt in the present invention
The maximum rate of optimal catalytic effect, catalysis ammonia borane hydrolysis dehydrogenation reaches 22.8LH2·min-1·gmetal -1, the unit time
Activate site conversion reactant molecule number TOF(turnover frequency) value be 70 molH2·min-1·molmetal -1,
Catalytic efficiency is better than other non-precious metal catalysts in the prior art, and stability and repeatability are also optimal.This external oxidation
Graphene and deionized water: when isopropanol is 1:1:1, the catalytic effect of the catalyst of acquisition is also best.
Embodiment two:
The embodiment of the invention provides a kind of preparation methods of loaded catalyst, comprising the following steps:
S1, the porous carbon of 80mg is dispersed in the normal propyl alcohol of 90ml, ultrasonic 40min, forms porous carbon mixed solution；
S2, by porous carbon mixed solution import three-necked flask in, and thereto be added 0.043mmol ferric acetate and
0.057mmol nickel acetate, three-necked flask is placed in oil bath pan, and 90 ml deionizations are rapidly joined after 70 DEG C of back flow reaction 1.5h
Water, and keep 70 DEG C of the reaction was continued 40min；
3) after obtaining mixed solution, using dehydrated alcohol centrifuge washing 2 times, then after being washed with deionized 2 times, 60 DEG C of skies
It is 12 hours dry in gas.
Correspondingly, the embodiment of the invention also provides a kind of loaded catalyst, the catalyst is above method preparation
It obtains, the catalyst is porous carbon load iron nickel bimetal oxide nano particles；The bimetallic oxide nanometer
The size of grain is 4 ± 0.5nm nm, and wherein the ratio of the amount of iron and nickel substance is 1.3:1.
Correspondingly, the embodiment of the invention also provides a kind of application of loaded catalyst, the catalyst is above-mentioned
The catalyst is dispersed in ammonia borine aqueous solution by catalyst, is used for the dehydrogenation of ammonia borane hydrolysis.
The preparation method of porous carbon in the embodiment of the present invention is any one method in the prior art.
Embodiment three:
The embodiment of the invention provides a kind of preparation methods of loaded catalyst, comprising the following steps:
S1, by the graphene dispersion of 80mg in the isopropanol of 51ml, ultrasonic 40min, formed graphene mixed solution；
S2, by graphene mixed solution import three-necked flask in, and thereto be added 0.35mmol copper acetate and
0.15mmol nickel acetate, three-necked flask is placed in oil bath pan, rapidly joins 51ml deionization after 100 DEG C of back flow reaction 0.5h
Water, and keep 100 DEG C of the reaction was continued 10min；
S3, after obtaining mixed solution, using dehydrated alcohol filtration washing 2 times, then after being washed with deionized 2 times, 80 DEG C
Air drying 12 hours.
Correspondingly, the embodiment of the invention also provides a kind of loaded catalyst, the catalyst is above method preparation
It obtains, the catalyst is that porous carbon loads cuprum nickle duplex metal oxide nano particles；The bimetallic oxide nanometer
The size of grain is 3 ± 0.25nm nm, and wherein the ratio of the amount of copper and mickel substance is 2.3:1.
Correspondingly, the embodiment of the invention also provides a kind of application of loaded catalyst, the catalyst is above-mentioned
The catalyst is dispersed in ammonia borine aqueous solution by catalyst, is used for the dehydrogenation of ammonia borane hydrolysis.
Loaded catalyst of the invention, preparation method and applications, have the following beneficial effects:
1, the characteristic system that the method for the present invention is hydrolyzed at high temperature using water and isopropanol or normal propyl alcohol system and acetate
Standby bimetallic oxide is simultaneously loaded to catalyst is prepared on carbon material, and preparation method is simple, strong operability, makes
Lower cost for material, and being capable of mass production.
2, carbon material supported bimetallic oxide nano-particle material is applied in ammonia borane hydrolysis hydrogen manufacturing in the present invention,
Very high catalytic effect is obtained, not only catalytic efficiency is higher than other non-precious metal catalysts in the prior art, and is catalyzed
The stability and repeatability of agent are very good.
3, in ammonia borane hydrolysis catalyst, the catalyst using metal oxide as catalyst body is less, and will be double
Metal oxide nanoparticles are combined with carbon material, even more unprecedented.And in the present invention catalyst preparation method letter
Single efficient, catalyst cost is very low, and catalytic effect is very good.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (7)
1. a kind of preparation method of loaded catalyst, which comprises the following steps:
S1, carbon material is dispersed in isopropanol or normal propyl alcohol, forms carbon material mixed solution；
S2, binary transition metal salting liquid is added into carbon material mixed solution, it is fast after reaction 0.5-1.5h at 70-100 DEG C
Deionized water is added in speed, and continues to react 10-40min at 70-100 DEG C；
S3, the reaction product in step S2 is washed, and the product after washing is dried, carbon materials are prepared
Expect the catalyst of supported bi-metallic oxide nano particles；
Carbon material in the step S1 is one of graphene oxide, carbon nanotube, porous carbon and graphene or a variety of
Combination；
Binary transition metal salting liquid in the step S2 is mantoquita and molysite, mantoquita and cobalt salt or mantoquita and nickel salt, institute
Stating molysite is ferric acetate, and the cobalt salt is cobalt acetate, and the mantoquita is copper acetate, and the nickel salt is nickel acetate；
The summation of the amount of the binary transition metal salting liquid substance is 0.1-0.5mmol；
The volume ratio of isopropanol or normal propyl alcohol and deionized water in step S2 is 1:1 in the step S1.
2. the preparation method of loaded catalyst according to claim 1, which is characterized in that carbon material in the step S1
It is 1-2:1 with the mass ratio of isopropanol or normal propyl alcohol.
3. the preparation method of loaded catalyst according to claim 2, which is characterized in that the binary transition metal salt
Solution is copper acetate and cobalt acetate；
The mass ratio of the material of the copper acetate and cobalt acetate is 1-4:1.
4. a kind of loaded catalyst, which is characterized in that the catalyst is the side as described in any one of claim 1-3
What method was prepared, the catalyst is carbon material supported bimetallic oxide nano particle.
5. loaded catalyst according to claim 4, which is characterized in that the carbon material is graphene oxide, carbon is received
One of mitron, porous carbon and graphene or a variety of combinations；
The bimetallic oxide is oxide, the oxide of copper and cobalt or the oxide of copper and mickel of copper and iron；
The size of the bimetallic oxide nano particle is 2-10nm.
6. loaded catalyst according to claim 5, which is characterized in that the bimetallic oxide is the oxygen of copper and cobalt
Compound, wherein the ratio of the amount of copper and cobalt substance is 1-4:1.
7. a kind of application of loaded catalyst, which is characterized in that the catalyst is described in claim 4-6 any one
The catalyst is dispersed in ammonia borine aqueous solution by catalyst, is used for the dehydrogenation of ammonia borane hydrolysis.
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| High-performance solid catalysts for H2 generation from ammonia borane: progress through synergetic Cu–Ni interactions;Hoang Yen et al.;《Journal of Materials Chemistry A》;20131003;第1卷;第14790-14796页 * |
| Probing the electronic structure of M-graphene oxide (M=Ni,Co,NiCo) catalysts for hydrolytic dehydrogenation of ammonia borane;Binhua Zhao et al.;《Applied Surface Science》;20151202;第362卷;第79-85页 * |
| Rapid and energy-efficient synthesis of a graphene–CuCo hybrid as a high performance catalyst;Junmin Yan et al.;《Journal of Materials Chemistry》;20120329;第22卷;第10990-10993页 * |
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