CN107670694A - A kind of metal load type catalyst and its preparation method and application - Google Patents
A kind of metal load type catalyst and its preparation method and application Download PDFInfo
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Abstract
Application the invention discloses a kind of metal load type catalyst and preparation method thereof and in ammonia borane hydrolysis hydrogen manufacturing.Described metal load type catalyst is carrier with metal-organic framework material MIL 101, Cu, Ni, Co presoma is adsorbed in MIL 101 hole completely in regulation and control ratio by solvent evaporated method, then pass through NaBH4Reduction obtains the excellent ternary metal carrier nanometer catalyst Cu Ni Co@MIL 101 of catalytic performance.The features such as there is gained catalyst metallic to be evenly distributed, specific surface area is big, active site is more, compared with traditional noble metal catalyst, have that cost is cheap, it is simple to prepare, raw material is easy to get, it is adapted to industrialized production, is a kind of very promising catalyst.
Description
Technical field
The invention belongs to hydrogen storage material field, is related to a kind of ternary metal for having high catalytic activity for ammonia borane hydrolysis
Loaded catalyst and its preparation method and application.
Background technology
Exhaustive exploitation and use with traditional primary energy, tellurian available traditional energy are fewer and fewer.Hair
Opening up pollution-free and high utilization rate cleaning secondary energy sources becomes particularly important.Hydrogen has as a kind of secondary energy sources of cleaning
Energy density is high, the advantages that environmental nonpollution.However, the efficient preparation and storage of hydrogen are still the one of hydrogen energy source application
Individual important difficult point.
Ammonia borine (NH3BH3, AB), it is a kind of very high light hydrogen occluding material of application prospect, it has up to 19.6wt%
Hydrogen content, it is non-toxic, all there is good chemical stability in air and the aqueous solution at room temperature.
Hydrogen is discharged in AB and mainly passes through three kinds of modes：Thermal decomposition, hydrolysis and alcoholysis.Thermal decomposition needs higher temperature,
And the accessory substances such as a large amount of borines can be produced in decomposable process, it is unfavorable for the purifying of hydrogen；And it is then currently most popular one to hydrolyze
Kind mode, it has, and reaction condition is gentle, and hydrogen discharges the features such as rapid.
It is the key for promoting ammonia borane hydrolysis hydrogen manufacturing application to research and develop excellent performance and cheap catalyst, wherein urging
The factors such as the composition of agent, size, structure have strong influence to its catalytic performance.Noble metal catalyst at present, as Pt,
The hydrolysis for ammonia borine such as Pd, Rh, Ru has high catalytic activity and selectivity, but noble metal catalyst is due to cost
It is too high, limit the large-scale application of such catalyst.For noble metal catalyst, non-precious metal catalyst
Such as Cu, Ni, Co have the characteristics of distinct low cost, aboundresources, higher catalytic activity, are with a wide range of applications.
Under general state, base metal is because own electronic reasons in structure, catalytic performance are simultaneously less than noble metal, so needing
To improve own electronic structure by introducing other elements, and its catalytic performance is lifted by regulating and controlling pattern.In nanometer
Under yardstick, non-noble metal specific surface area is greatly increased, and reactivity, which also has, significantly to be lifted, but high specific surface energy
Cause catalyst granules to be easier that agglomeration occurs, reduce its cycle life.By the way that metal active composition is supported on into carrier
On, it can effectively suppress the generation of its agglomeration, be a kind of effective way for improving catalytic activity.Wherein, metal is organic
Framework MIL-101 has high specific surface area, and internal special cage structure can fix catalytic activity well
Composition, it can greatly suppress the generation of agglomeration.More importantly, metal organic frame MIL-101 at room temperature organic
It can be stabilized in solvent, it also contains a large amount of unsatuated metal positions, and these unsatuated metal positions can be with the nano metal of load
Catalyst produces concerted catalysis effect, so as to farthest give play to stable catalytic performance.
The content of the invention
The problems such as it is an object of the invention to for the high cost of existing catalyst, materials synthesis step complexity, there is provided one
Simple and effective non-noble metal supported composite catalyst of ternary of kind and preparation method thereof.The catalyst and traditional catalyst phase
Than can greatly reduce cost, simplify synthetic method, and its catalytic performance is obtained for significant increase with cycle performance.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of metal load type catalyst, obtained by metal organic frame MIL-101 carrying active ingredients, active component by
The compound composition of base metal Cu, Ni, Co.
By the optimal components for changing source metal proportioning regulation and control catalyst.Using metal-organic framework material MIL-101 as load
Body, Cu, Ni, Co presoma are adsorbed in MIL-101 hole completely in regulation and control ratio by solvent evaporated method, then passed through
NaBH4Reduction obtains the excellent ternary metal carrier nanometer catalyst Cu-Ni-Co@MIL-101 of catalytic performance.
Preferably, in described active component, Cu mole accounts for 20~80%, the Ni and Co of total amount of metal mol ratio
For 1：1.
The average grain diameter of described metal load type catalyst is 2.5~3.0nm, and this mainly utilizes metal organic frame
In nano-scale cage structure to institute's supported catalyst confinement effect, cause synthesized transition metal nano-catalyst to have
There is very big specific surface energy, and the reunion that can effectively suppress transition metal nano-catalyst is grown up.
Present invention also offers the preparation method of above-mentioned metal load type catalyst, comprise the following steps：
(1) chromic nitrate, terephthalic acid (TPA), sodium acetate, water are stirring evenly and then adding into reactor, at 160~200 DEG C
Under the conditions of react 20~30 hours；Obtained suspension is filtered, dried after washing, obtains carrier MIL-101；
(2) it is added in ethanol, surpasses after MIL-101 obtained by above-mentioned steps (1) is mixed with mantoquita, cobalt salt and nickel salt
Sound is stirred at a temperature of 60~80 DEG C after 20~40 minutes and is evaporated to solvent, obtains drying block；
(3) by NaBH4The aqueous solution is added in the block of above-mentioned steps (2), is stirred 0.5~2 hour；Product is located after
Reason obtains metal load type catalyst Cu-Ni-Co@MIL-101.
In above-mentioned preparation method, in step (1), chromic nitrate, terephthalic acid (TPA), the mol ratio of sodium acetate and water are 1：1：
0.25~0.75：300, preferably, chromic nitrate, terephthalic acid (TPA), the mol ratio of sodium acetate and water are 1：1：0.25：300.
In above-mentioned preparation method, the mode of washing for the MIL-101 suspensions being prepared in step (1) is to use DMF first
Solvent cleans 2 times under the conditions of 50 DEG C, is then cleaned with deionized water.
In above-mentioned preparation method, in step (2), the volume of the MIL-101 of addition quality, metal integral molar quantity and ethanol
The ratio between be 50mg：0.03mmol：5mL.Deionized water is substituted using ethanol, by solvent evaporated method, by Cu, Ni, Co presoma
It is adsorbed in completely in MIL-101 hole in regulation and control ratio, the good confinement of nano-metal particle is supported on to MIL-101 cage
In structure.In addition, MIL-101 is in ethanol containing a large amount of constitutionally stable unsatuated metal sites, these unsatuated metal positions
Point can produce concerted catalysis effect with the active component of load, so as to farthest give play to stable catalytic performance
In above-mentioned preparation method, in step (2), the mol ratio of the nickel in cobalt and nickel salt in described cobalt salt is 1:1,
The mole of the copper in mantoquita is controlled to account for the 20~80% of metal integral molar quantity simultaneously.
The mol ratio of the nickel in the cobalt and nickel salt in copper, cobalt salt in the mantoquita is 8:1:1, gained gold under the proportioning
The performance for belonging to loaded catalyst is optimal.
In above-mentioned preparation method, in step (3), NaBH4The concentration of the aqueous solution is 0.5~1mol/L, NaBH4The aqueous solution
100~110 times of the metal integral molar quantity for adding mole to add in step (2).
Present invention also offers a kind of application of above-mentioned metal load type catalyst in ammonia borane hydrolysis hydrogen manufacturing.
Compared with prior art, the invention has the advantages that：
(1) 3622m is up to using specific surface area2g-1Organic metal framework MIL-101 is as carrier, ternary base metal
Cu, Ni, Co are as active component, using multi-element metal composite optimization electronic structure, and point between active component and carrier
Dissipate effect, the significant increase activity of catalyst.And first passage solvent evaporated method, by the good confinement of nano-metal particle
It is supported in MIL-101 basket structure, obtains polymolecularity ternary metal supported catalyst of the average grain diameter in 2.8nm or so
Agent.
(2) present invention also utilizes contained a large amount of structures in the organic solvents of metal organic frame MIL-101 at room temperature
Stable unsatuated metal position, these unsatuated metal positions can produce concerted catalysis effect with the metallic catalyst of load,
So as to farthest give play to stable catalytic performance.At ambient temperature, hydrogen-producing speed is up to catalyst
93.4molH2molcat -1min-1, apparent activation energy 29.1kJ/mol.
Brief description of the drawings
Fig. 1 is Cu prepared by the embodiment of the present invention 10.8Ni0.1Co0.1The transmission electron microscope picture of@MIL-101 catalyst；
Fig. 2 is MIL-101 and Cu prepared by the embodiment of the present invention 10.8Ni0.1Co0.1The nitrogen adsorption of@MIL-101 catalyst
Desorption and graph of pore diameter distribution；
Fig. 3 is that catalyst prepared by the embodiment of the present invention 1~5 is catalyzed the survey of ammonia borane hydrolysis ice thaw characteristics at ambient temperature
Attempt；
Fig. 4 is MIL-101 and Cu prepared by the embodiment of the present invention 10.8Ni0.1Co0.1@MIL-101 catalyst ammonia borines
The XRD picture before and after hydrogen is released in hydrolysis；
Fig. 5 is Cu prepared by the embodiment of the present invention 10.8Ni0.1Co0.1@MIL-101 catalyst in 293.5K, 298.5K,
The Arrhenius activation energy test charts that ammonia borane hydrolysis releases hydrogen are catalyzed under 308.5K, 318.5K；
Fig. 6 is that catalyst prepared by comparative example 1 of the present invention is catalyzed the test of ammonia borane hydrolysis ice thaw characteristics at ambient temperature
Figure；
Fig. 7 is that catalyst prepared by comparative example 2 of the present invention is catalyzed the test of ammonia borane hydrolysis ice thaw characteristics at ambient temperature
Figure；
Fig. 8 is that catalyst prepared by comparative example 3 of the present invention is catalyzed the test of ammonia borane hydrolysis ice thaw characteristics at ambient temperature
Figure.
Embodiment
The present invention is done with reference to specific embodiments and the drawings further it is clear, detailed, intactly illustrate, listed example
Only the present invention is further described, it is not thereby limiting the invention：
Embodiment 1
Ternary base metal Cu0.8Ni0.1Co0.1The preparation of@MIL-101 nanocatalysts:
(1) terephthalic acid (TPA) (0.82g, 5.0mmol), Chromium nitrate (Cr(NO3)3),nonahydrate (2.06g, 5.0mmol), NaAC are weighed
(0.11g, 0.125mmol) and deionized water (25mL), 50mL liners are transferred to as the stainless of polytetrafluoroethylene (PTFE) after stirring 30min
It is transferred in steel reactor, after sealing in the constant temperature of 180 DEG C of constant temperature and reacts 18h.Room temperature is cooled to after the completion of question response, is obtained
To green suspension.Suspension is transferred to centrifuge tube, DMF is added and is centrifuged 2 times after being heated to 70 DEG C of concussion cleanings, by acquisition
Green product is cleaned centrifuge afterwards twice again at room temperature with deionized water, and the green product of acquisition is dried into 12h at 70 DEG C, obtained
To MIL-101 green powders.
(2) weigh the above-mentioned MIL-101 powders of 50.0mg to be scattered in 5ml absolute ethyl alcohols, ultrasonic disperse 30min.Weigh
4.1mg CuCl2·2H2O, 0.74mg NiCl2·6H2O, 0.74mg CoCl2·6H2O is added to above-mentioned MIL-101 solution
In, continue ultrasonic disperse 30min.Heating stirring in 60 DEG C of water-baths is transferred to after ultrasound, until solvent evaporating completely obtains
To the green block of drying.
(3) 111.4mg NaBH are weighed4It is dissolved in 5ml deionized waters, by NaBH4The aqueous solution is disposably added to above-mentioned green
With reducing metal ion in color lump body, continue to stir 1h after addition.After the solution of acquisition is centrifuged with deionized water, it will obtain
The green block obtained is dried in vacuum overnight, and obtains blackish green ternary Cu0.8Ni0.1Co0.1@MIL-101 catalyst, i.e. described gold
Belong to loaded catalyst.
Cu manufactured in the present embodiment0.8Ni0.1Co0.1The transmission electron microscope and grain size distribution such as Fig. 1 of@MIL-101 catalyst
It is shown, wherein, Fig. 1 (a) is transmission electrode figure, and Fig. 2 (b) is grain size distribution, as seen from the figure, Cu0.8Ni0.1Co0.1@MIL-101
The average grain diameter of catalyst is about 2.8nm.
MIL-101 and Cu manufactured in the present embodiment0.8Ni0.1Co0.1The nitrogen adsorption desorption of@MIL-101 catalyst and hole
Footpath distribution map is as shown in Fig. 2 wherein, Fig. 2 (a) is that nitrogen adsorption is desorbed result figure, and Fig. 2 (b) is graph of pore diameter distribution.
Embodiment 2
Ternary base metal Cu0.4Ni0.3Co0.3The preparation of@MIL-101 nanocatalysts:
Weigh the MIL-101 powders prepared in 50.0mg embodiments 1 to be scattered in 5ml absolute ethyl alcohols, ultrasonic disperse
30min.Weigh 2.05mg CuCl2·2H2O, 2.2mg NiCl2·6H2O, 2.2mg CoCl2·6H2O is added to above-mentioned MIL-
In 101 solution, continue ultrasonic disperse 30min.Heating stirring in 60 DEG C of water-baths is transferred to after ultrasound, until solvent is complete
Evaporation obtains drying green block.
Weigh 111.4mg NaBH4It is dissolved in 5ml deionized waters, by NaBH4The aqueous solution is disposably added to above-mentioned green block
With reducing metal ion in body, continue to stir 1h after addition.After the solution of acquisition is centrifuged with deionized water, by acquisition
Green block is dried in vacuum overnight, and obtains blackish green ternary Cu0.4Ni0.3Co0.3@MIL-101 catalyst, i.e. described metal are born
Supported catalyst.
Embodiment 3
Ternary base metal Cu0.6Ni0.2Co0.2The preparation of@MIL-101 nanocatalysts:
Weigh the MIL-101 powders prepared in 50.0mg embodiments 1 to be scattered in 5ml absolute ethyl alcohols, ultrasonic disperse
30min.Weigh 3.08mg CuCl2·2H2O, 1.5mg NiCl2·6H2O, 1.5mg CoCl2·6H2O is added to above-mentioned MIL-
In 101 solution, continue ultrasonic disperse 30min.Heating stirring in 60 DEG C of water-baths is transferred to after ultrasound, until solvent is complete
Evaporation obtains drying green block.
Weigh 111.4mg NaBH4It is dissolved in 5ml deionized waters, by NaBH4The aqueous solution is disposably added to above-mentioned green block
With reducing metal ion in body, continue to stir 1h after addition.After the solution of acquisition is centrifuged with deionized water, by acquisition
Green block is dried in vacuum overnight, and obtains blackish green ternary Cu0.6Ni0.2Co0.2@MIL-101 catalyst, i.e. described metal are born
Supported catalyst.
Embodiment 4
Ternary base metal Cu0.5Ni0.25Co0.25The preparation of@MIL-101 nanocatalysts:
Weigh the MIL-101 powders prepared in 50.0mg embodiments 1 to be scattered in 5ml absolute ethyl alcohols, ultrasonic disperse
30min.Weigh 2.56mg CuCl2·2H2O, 1.9mg NiCl2·6H2O, 1.9mg CoCl2·6H2O is added to above-mentioned MIL-
In 101 solution, continue ultrasonic disperse 30min.Heating stirring in 60 DEG C of water-baths is transferred to after ultrasound, until solvent is complete
Evaporation obtains drying green block.
Weigh 111.4mg NaBH4It is dissolved in 5ml deionized waters, by NaBH4The aqueous solution is disposably added to above-mentioned green block
With reducing metal ion in body, continue to stir 1h after addition.After the solution of acquisition is centrifuged with deionized water, by acquisition
Green block is dried in vacuum overnight, and obtains blackish green ternary Cu0.5Ni0.25Co0.25@MIL-101 catalyst, i.e. described metal are born
Supported catalyst.
Embodiment 5
Ternary base metal Cu0.2Ni0.4Co0.4The preparation of@MIL-101 nanocatalysts:
Weigh the MIL-101 powders prepared in 50.0mg embodiments 1 to be scattered in 5ml absolute ethyl alcohols, ultrasonic disperse
30min.Weigh 1.02mg CuCl2·2H2O, 3.0mg NiCl2·6H2O, 3.0mg CoCl2·6H2O is added to above-mentioned MIL-
In 101 solution, continue ultrasonic disperse 30min.Heating stirring in 60 DEG C of water-baths is transferred to after ultrasound, until solvent is complete
Evaporation obtains drying green block.
Weigh 111.4mg NaBH4It is dissolved in 5ml deionized waters, by NaBH4The aqueous solution is disposably added to above-mentioned green block
With reducing metal ion in body, continue to stir 1h after addition.After the solution of acquisition is centrifuged with deionized water, by acquisition
Green block is dried in vacuum overnight, and obtains blackish green ternary Cu0.2Ni0.4Co0.4@MIL-101 catalyst, i.e. described metal are born
Supported catalyst.
Embodiment 6
Ammonia borane hydrolysis under catalysts conditions releases hydrogen experiment：
To investigate the catalytic effect that catalyst releases hydrogen for ammonia borane hydrolysis, the present invention has carried out the ammonia under catalysts conditions
Borane hydrolysis releases hydrogen experiment, and experimentation is as follows：
Catalysis experiments are carried out in 50ml single necked round bottom flask.50mg catalyst and 4.8ml deionized waters are transferred to circle
In the flask of bottom, the port of flask is connected by rubber tube with filling the 500ml graduated cylinders of water, when hydrogen produces, caused gas
Water isometric in graduated cylinder can be excluded, hydrogen generating quantity can be read by liquid level change.Experimental provision is transferred to
In 25 DEG C of hydrothermal pot and carry out magnetic agitation.30mg ammonia borines are dissolved in 0.2ml deionized waters, and added by syringe
Into round-bottomed flask, now reaction starts, and reads a liquid level every 30s to obtain hydrogen volume.
A series of hydrogen of ternary base metal Cu-Ni-Co@MIL-101 catalyst produces speed as shown in figure 3, through meter
Calculate Cu0.8Ni0.1Co0.1@MIL-101 have highest response speed, and TOF values are 93.4molH2molcat -1min-1。
The gained MIL-101 of the embodiment of the present invention 1 and catalyst Cu0.8Ni0.1Co0.1@MIL-101 catalysis ammonia borane hydrolysis is released
XRD picture before and after hydrogen is as shown in figure 4, wherein, Fig. 4 (a) is that ammonia borane hydrolysis releases the XRD picture before hydrogen, and Fig. 4 (b) is ammonia boron
The XRD picture after hydrogen is released in alkane hydrolysis.
Embodiment 7
The hydrogen speed of releasing of catalyst is tested with activation energy under condition of different temperatures
(20,25,35 and 45 DEG C) at different temperature, the sample prepared using embodiment 1, pass through the side of embodiment 6
Method catalysis ammonia borane hydrolysis releases hydrogen.
The catalyst Cu of embodiment 10.8Ni0.1Co0.1@MIL-101 are in 293.5K, 298.5K, 308.5K, 318.5K catalysis ammonia
Borane hydrolysis releases the Arrhenius activation energy test chart of hydrogen as shown in figure 5, result shows that releasing hydrogen speed and temperature is proportionate pass
System, temperature is higher, and it is higher to release hydrogen speed.By Arrhenius formula, Cu is calculated0.8Ni0.1Co0.1@MIL-101 are catalyzed
The activation energy of reaction is 29.1kJ mol-1。
Comparative example 1
Ternary base metal control sample Cu0.8Ni0.1Co0.1The preparation of@MIL-101* nanocatalysts:
The MIL-101 powders weighed in 50.0mg embodiments 1 are scattered in 10ml deionized waters, ultrasonic disperse 30min.Claim
Take 4.1mg CuCl2H2O, 0.74mg NiCl2·6H2O, 0.74mg CoCl2·6H2O is dissolved in 5ml deionized waters, is mixed
It is transferred to after closing uniformly in above-mentioned MIL-101 dispersion liquids, magnetic agitation 4 hours.
Weigh 111.4mg NaBH4It is dissolved in 5ml deionized waters, by NaBH4The aqueous solution is disposably added to above-mentioned mixed liquor
In, and continue to stir 1h until no longer producing bubble in reaction solution.By mixed liquor deionized water eccentric cleaning after the completion of reaction,
Obtained centrifugation product is transferred under 60 DEG C of environment and is dried overnight, and obtains the blackish green ternary Cu of control sample0.8Ni0.1Co0.1@MIL-
101* catalyst, Fig. 6 are Cu prepared by this comparative example0.8Ni0.1Co0.1@MIL-101* catalyst is prepared with embodiment 1
Cu0.8Ni0.1Co0.1The performance comparision of@MIL-101 catalyst.
Comparative example 2
Binary non-noble metal Ni0.5Co0.5The preparation of@MIL-101 nanocatalysts：
The MIL-101 powders weighed in 50.0mg embodiment 1 are scattered in 5ml absolute ethyl alcohols, ultrasonic disperse 30min.
Weigh 3.7mg NiCl2·6H2O, 3.7mg CoCl2·6H2O is added in above-mentioned MIL-101 solution, continues ultrasonic disperse
30min.Heating stirring in 60 DEG C of water-baths is transferred to after ultrasound, until solvent evaporating completely obtains drying green block.
Weigh 111.4mg NaBH4It is dissolved in 5ml deionized waters, by NaBH4The aqueous solution is disposably added to above-mentioned green block
With reducing metal ion in body, continue to stir 1h after addition.It is dried in vacuo after the solution of acquisition is centrifuged with deionized water
Overnight, bottle green binary Ni is obtained0.5Co0.5@MIL-101 catalyst, gained Ni0.5Co0.5The hydrogen production of@MIL-101 catalyst
Raw speed is as shown in Figure 7.
Comparative example 3
The preparation of unitary base metal Cu@MIL-101 nanocatalysts：
The MIL-101 powders weighed in 50.0mg embodiments 1 are scattered in 5ml absolute ethyl alcohols, ultrasonic disperse 30min.Claim
Take 5.1mg CuCl2·2H2O is added in above-mentioned MIL-101 solution, continues ultrasonic disperse 30min.It is transferred to after ultrasound
Heating stirring in 60 DEG C of water-baths, until solvent evaporating completely obtains drying green block.
Weigh 111.4mg NaBH4It is dissolved in 5ml deionized waters, by NaBH4The aqueous solution is disposably added to above-mentioned green block
With reducing metal ion in body, continue to stir 1h after addition.It is dried in vacuo after the solution of acquisition is centrifuged with deionized water
Overnight, blackish green unitary Cu@MIL-101 catalyst is obtained, the hydrogen of gained Cu@MIL-101 catalyst produces speed such as Fig. 8 institutes
Show.
Claims (8)
- A kind of 1. metal load type catalyst, it is characterised in that obtained by metal organic frame MIL-101 carrying active ingredients, Active component is formed by base metal Cu, Ni, Co are compound.
- 2. metal load type catalyst according to claim 1, it is characterised in that in described active component, Cu's rubs The mol ratio that your amount accounts for 20~80%, the Ni and Co of total amount of metal is 1：1.
- 3. the preparation method of metal load type catalyst according to claim 1, it is characterised in that comprise the following steps：(1) chromic nitrate, terephthalic acid (TPA), sodium acetate, water are stirring evenly and then adding into reactor, in 160~200 DEG C of conditions Lower reaction 20~30 hours；Obtained suspension is filtered, dried after washing, obtains carrier MIL-101；(2) it is added to after MIL-101 obtained by above-mentioned steps (1) is mixed with mantoquita, cobalt salt and nickel salt in ethanol, ultrasound 20 Stir at a temperature of 60~80 DEG C after~40 minutes and be evaporated to solvent, obtain drying block；(3) by NaBH4The aqueous solution is added in the block of above-mentioned steps (2), is stirred 0.5~2 hour；Product is post-treated To metal load type catalyst Cu-Ni-Co@MIL-101.
- 4. the preparation method of metal load type catalyst according to claim 3, it is characterised in that in step (1), nitric acid Chromium, terephthalic acid (TPA), the mol ratio of sodium acetate and water are 1：1：0.25~0.75：300.
- 5. the preparation method of metal load type catalyst according to claim 3, it is characterised in that in step (2), addition MIL-101 quality, the ratio between the volume of metal integral molar quantity and ethanol be 50mg：0.03mmol：5mL.
- 6. the preparation method of metal load type catalyst according to claim 3, it is characterised in that described in step (2) Cobalt salt in cobalt and nickel salt in nickel mol ratio be 1:1, while control the mole of the copper in mantoquita to account for metal and always rub The 20~80% of that amount.
- 7. the preparation method of metal load type catalyst according to claim 6, it is characterised in that in the mantoquita The mol ratio of the nickel in cobalt and nickel salt in copper, cobalt salt is 8:1:1.
- A kind of 8. application of metal load type catalyst according to claim 1 or 2 in ammonia borane hydrolysis hydrogen manufacturing.
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