CN107376996A - A kind of ammonia borane hydrolysis releases hydrogen ruthenium cobalt dual-metal manometer load-type catalyst and preparation method thereof - Google Patents
A kind of ammonia borane hydrolysis releases hydrogen ruthenium cobalt dual-metal manometer load-type catalyst and preparation method thereof Download PDFInfo
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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Abstract
The present invention provides a kind of ammonia borane hydrolysis and releases hydrogen ruthenium cobalt dual-metal manometer load-type catalyst and preparation method thereof, is carrier with metal organic framework MIL 110, with NaBH using ruthenium and cobalt as active component4For reducing agent, predecessor ruthenium salt and cobalt salt are reduced to RuCo and are carried on MIL 110, obtain ruthenium cobalt dual-metal manometer load-type catalyst RuCo@MIL 110.RuCo alloy particle average grain diameters are about 2.3nm.At room temperature, the catalyst shows high catalytic activity in catalysis ammonia borane hydrolysis releases hydrogen, and the activation energy (Ea) of reaction is 31.7kJmol‑1, transformation frequency (TOF) be 533.2molH2·min‑1(mol·Ru)‑1.The catalyst still retains 79.0% catalytic activity after 5 circulations, has high mithridatism and cyclical stability.This bimetal supported catalyst shows higher catalytic activity compared with monometallic support type and the non-loaded catalyst of bimetallic.Compared with traditional noble metal catalyst, the catalyst has that cost is cheap, prepares simple, and raw material is easy to get, and is adapted to industrialized production, has a extensive future.
Description
Technical field
The present invention relates to a kind of catalyst, and in particular to a kind of ammonia borane hydrolysis releases hydrogen ruthenium cobalt dual-metal manometer load-type
Catalyst and preparation method thereof, belong to nano catalytic material field.
Background technology
Due to energy crisis and environmental degradation, scientists tap a new source of energy with instead of fossil energy one after another.Numerous
In novel energy, Hydrogen Energy is a kind of preferable energy, has the characteristics that safety and environmental protection, wide material sources, applied widely, is fired in hydrogen
Expect automobile, generating, illumination and urban life etc., its importance is more and more significant.In many hydrogen storage materials, hydrogen content
It is high and release the fast ammonia borine (NH of hydrogen speed3BH3, abbreviation AB) and it is a kind of hydrogen storage material of great application potential.Ammonia borine is hydrogeneous
Amount is up to 19.6wt%, nontoxic, stable under normal temperature, environment-friendly, when without catalyst, hydrolysis does not occur at room temperature and releases hydrogen.Cause
The excellent catalyst of this processability is the core that can ammonia borine turn into the hydrogen storage material with practical value.
Metallic catalyst has higher catalytic activity and stability, is to be catalyzed the first choice that ammonia borane hydrolysis releases hydrogen, each
In kind metallic catalyst, the catalytic activity highest of noble metal, conventional noble metal mainly has Pt, Pd, Rh, Ru etc..But due to expensive
Metal reserves are rare, expensive, hinder it to apply and develop.Although base metal cost is low, catalytic performance have it is to be hoisted,
If by noble metal and base metal concerted catalysis, production cost can be both reduced, and can improves its catalytic activity and stability, is
The optimal selection of catalyst.In addition, bimetallic particle size, composition and dispersiveness etc. are also to influence the pass of catalyst activity
Key factor.When the metal particle size of catalyst reaches nanoscale, specific surface area will be caused to increase, avtive spot increases, metal
The contact area of particle and guest molecule also increases, so as to improve its catalytic activity.Due to metal organic framework (MOFs) material
Empty structure big with specific surface area, excellent, load capacity is strong, stable performance, is the suitable carrier of metallic, particularly
Metal organic framework MIL-110 loads Ru and Co, due to its loose structure and huge specific surface area, can make metallic in hole
Uniformly inlay and disperse inside and outside hole.MIL-110 concerted catalysis ammonia borine water is carried on to so far, yet there are no relevant RuCo
Explain the relevant report or data of hydrogen.Therefore, that develops a kind of inexpensive high activity releases hydrogen for being catalyzed ammonia borane hydrolysis
Bimetal supported catalyst RuCo MIL-110 tools are of great significance.
The applicant is in Chinese invention patent (application number before this：201610613243.1 the applying date：2016.07.29)
Propose it is a kind of release ternary nanocatalyst of hydrogen and preparation method thereof for ammonia borane hydrolysis, the catalyst with noble metal Ru and
Base metal CuCo is active component, and using metal-organic framework materials MIL-101 as carrier, three metals are loaded with MIL-101
RuCuCo nano-particles, ternary nanocatalyst RuCuCo@MIL-101 are obtained by reducing presoma ruthenium salt, mantoquita, cobalt salt.
During 25 DEG C of room temperature, it is 241.2molH that it, which is catalyzed ammonia borane hydrolysis and releases the TOF values of hydrogen,2×min-1(mol×Ru)-1, by five times
After circulation, the activity of catalyst is only original 54%, it is seen that the catalytic effect and stability of the catalyst are not ideal enough.
The applicant is in Chinese invention patent (application number before this：201610607703.X the applying date：2016.07.29)
A kind of core shell structure load type carbon nano tube catalyst and preparation method thereof is proposed, the catalyst is with CNT (CNTs)
Carrier, using ruthenium salt, cobalt salt, nickel salt as reactant, using ammonia borine as reducing agent, catalyst is obtained using Liquid infiltration and reduction legal system
Ru@CoNi/CNTs.During 25 DEG C of room temperature, it is 408.9molH that it, which is catalyzed ammonia borane hydrolysis and releases the TOF values of hydrogen,2×min-1(mol×
Ru)-1, after the circulation of five times, the activity of catalyst is only original 60%, it is seen that the catalytic effect of the catalyst and stably
Property is not ideal enough.
In view of this, the present invention propose a kind of ammonia borane hydrolysis release hydrogen ruthenium cobalt dual-metal manometer load-type catalyst and its
Preparation method.
The content of the invention
It is an object of the invention to overcome the shortcomings of existing product, realize low cost, be rapidly and efficiently catalyzed ammonia borane hydrolysis
Release hydrogen.The present invention provides a kind of ammonia borane hydrolysis and releases hydrogen ruthenium cobalt dual-metal manometer load-type catalyst and preparation method thereof, adopts
Metal organic carrier MIL-110 is obtained with easy hydrothermal technique, then passes through NaBH4Reducing process is carried on metal Ru and Co
On MIL-110, technique is simple, raw material is easy to get, cost is low, is suitable for industrialized production；And the ruthenium cobalt dual-metal nanometer prepared
Loaded catalyst RuCo@MIL-110 are catalyzed ammonia borane hydrolysis and release hydrogen with very high catalytic activity and circulate steady at room temperature
It is qualitative.
In order to achieve the above object, the technical solution adopted in the present invention is：It is double that a kind of ammonia borane hydrolysis releases hydrogen ruthenium cobalt
Metal nano loaded catalyst, using ruthenium and cobalt as active component, using metal organic framework MIL-110 as carrier, ruthenium cobalt is closed
Golden nanometer particle, which is carried on MIL-110, obtains ruthenium cobalt dual-metal manometer load-type catalyst RuCo@MIL-110.
A kind of ammonia borane hydrolysis releases the preparation method of hydrogen ruthenium cobalt dual-metal manometer load-type catalyst, including following step
Suddenly：
(1) first by Al (NO3)3·9H2O, trimethyl trimesate, NaOH, deionized water are stirring evenly and then adding into poly-
In the stainless steel cauldron of tetrafluoroethene liner, 210 DEG C of reaction 3h obtain suspension, and suspension is filtered, washed, is dried, is obtained
To white solid thing；Obtained white solid thing is added in the reactor containing DMF solution again, 150
DEG C reaction 5h；Reaction terminate after by solids in deionized water 100 DEG C backflow 12h, wash, vacuum drying, obtaining metal has
Machine skeleton MIL-110 white powders；
(2) MIL-110 white powders obtained by above-mentioned steps (1) are added in deionized water, ultrasonic disperse is uniform, and ruthenium is added dropwise
Salt and cobalt salt solution, 6h is stirred, obtains suspension；
(3) by reducing agent NaBH4Solid dissolving is added dropwise to the suspended of above-mentioned steps (2) in deionized water, by the solution
In liquid, continue to stir 3h after being added dropwise, product is filtered, wash, is dried in vacuum overnight, obtains ruthenium cobalt alloy manometer load-type
Catalyst RuCo@MIL-110.
Further, Al (NO described in step (1)3)3·9H2O, trimethyl trimesate, NaOH, deionized water
Mol ratio is 1：0.5：2.3：309.
Further, the mol ratio of the cobalt in the ruthenium and cobalt salt described in step (2) in ruthenium salt is 1:1.
Further, ruthenium salt described in step (2) is ruthenium trichloride, and described cobalt salt is soluble cobalt.
The beneficial effects of the invention are as follows：
(1) noble metal Ru and base metal Co is formed into two-metal alloy nanoparticle, had not only reduced cost but also given full play to
Concerted catalysis effect between noble metal and base metal.Metal organic framework MIL-110 is obtained by hydrothermal technique, and by its
For carrier, MIL-110 has loose structure and huge specific surface area, and RuCo alloy nano particles can be made a large amount of inside and outside hole
Inlay and dispersed, there is provided a large amount of catalysis ammonia borane hydrolysis release the avtive spot of hydrogen；RuCo alloy nano particles are carried on
On metal organic framework MIL-110, the difunctional effect between metallic and carrier is given full play to, the catalysis of the catalyst is lived
Property, mithridatism and stability are much better than non-loaded type, monometallic support type or three metal load type catalysts；
(2) in 25 DEG C of room temperature, the TOF values that the catalyst ammonia borane hydrolysis releases hydrogen are 533.2molH2×min-1(mol×
Ru)-1, it is 883.6molH in the TOF values that 40 DEG C of catalysis ammonia borane hydrolysis release hydrogen2×min-1(mol×Ru)-1, by five times
After circulation, the activity of catalyst is still original 79%, it is seen that catalytic effect, mithridatism and the stability of the catalyst are all very
It is good；
(3) technique of whole preparation process is simple, raw materials used to be easy to get, and cost is low, is suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the TEM photos of the catalyst RuCo@MIL-110 prepared by the embodiment of the present invention one；
Ru XPS spectrum figure in catalyst RuCo@MIL-110 of the Fig. 2 prepared by the embodiment of the present invention one；
Co XPS spectrum figure in catalyst RuCo@MIL-110 of the Fig. 3 prepared by the embodiment of the present invention one；
Fig. 4 is in catalyst MIL-110 (a), RuCo@MIL-110 (b) and embodiment six prepared by the embodiment of the present invention one
The FT-IR spectrograms of RuCo@MIL-110 (c) after recycling five times；
Fig. 5 is catalyst MIL-110 and RuCo@MIL-110 prepared by the embodiment of the present invention one, prepared by embodiment two
RuCo nano-particles prepared by Ru@MIL-110 and Co@MIL-110, embodiment three are catalyzed the speed that ammonia borane hydrolysis releases hydrogen respectively
Rate figure.
Embodiment
In order to be better understood from the present invention, below in conjunction with the accompanying drawings with embodiment to metal organic framework of the present invention
The preparation method of MIL-110 load ruthenium cobalt alloy nano-particle catalysts is described further, and provides its application.
Embodiment one：Carrier MIL-110 and bimetal nano loaded catalyst RuCo@MIL-110 preparation
By Al (NO3)3·9H2O, trimethyl trimesate (Me3Btc), NaOH, deionized water are 1 in molar ratio：0.5：
2.3：309 weigh, and are then mixed evenly, and being added to 50mL has in the stainless steel cauldron of polytetrafluoroethyllining lining, 210 DEG C
Reaction 3h obtains suspension.Then natural cooling, suspension is filtered, washed, is dried, obtained white solid thing.It will obtain
White solid thing be added in the 50mL reactors containing DMF (DMF) solution, 150 DEG C reaction 5h.Reaction
After end by solids in deionized water 100 DEG C backflow 12h, washing, 80 DEG C vacuum drying, obtain metal organic framework MIL-
110 white powders.
Weigh the above-mentioned MIL-110 white powders of 50mg to be added in 30mL deionized waters, ultrasonic 20min, then be added dropwise
0.025mmol rutheniums salt and 0.025mmol cobalt salt solutions, magnetic agitation 6h, obtain suspension.
By 50.0mg reducing agent NaBH4Solid dissolving is in 10mL deionized waters, by the NaBH4The aqueous solution is added dropwise
Into above-mentioned suspension, continue to stir 3h after being added dropwise.Product is filtered, washed, 80 DEG C be dried in vacuum overnight, obtain ruthenium cobalt
Bimetallic alloy manometer load-type catalyst RuCo@MIL-110.
TEM tests are carried out to prepared ruthenium cobalt dual-metal alloy nano loaded catalyst RuCo@MIL-110, as a result
As shown in Figure 1, the results showed that：The RuCo alloy nano particles of load are evenly distributed on carrier MIL-110, and average grain diameter is about
2.3nm.XPS tests, as a result as shown in Figures 2 and 3, Fig. 2 tables are carried out to catalyst RuCo@MIL-110 prepared by embodiment one
Ru 3p signal peaks in the bright catalyst be present, positioned at 462.0eV and 485.1eV；Fig. 3 shows Co 2p letters in the catalyst be present
Number peak, positioned at 781.5eV, 786.2eV, 797.5eV and 803.1eV.To sum up, Fig. 2 and Fig. 3 fully proves two kinds of elements rutheniums and cobalt
Successfully it is carried on MIL-110.
To being recycled five times in the MIL-110 (a) prepared by embodiment one and RuCo@MIL-110 (b), embodiment six
RuCo MIL-110 (c) afterwards carry out FT-IR tests, as a result as shown in Figure 4, the results showed that MIL-110 (a), RuCo MIL-
110 (b) and the RuCo@MIL-110 (c) after five times recycle infrared spectrum are basically unchanged, and illustrate that carrier MIL-110 is passed through
After overload and catalytic cycle, Stability Analysis of Structures, keep constant, still there is strong load capacity to Ru and Co.
Embodiment two：Monometallic loaded catalyst Ru@MIL-110, Co@MIL-110 preparation
Weigh the RuCl that MIL-110 and 2.5mL concentration prepared in 50mg embodiments one is 0.01mol/L3Solution, and by two
Person is added in 30mL deionized waters, and ultrasonic 10min obtains dispersed suspension.Then 50.0mg reducing agents are weighed
NaBH4Solid is simultaneously dissolved in 10mL deionized waters, by the NaBH4The aqueous solution is added dropwise in above-mentioned suspension, is added dropwise
After continue stir 3h.Products therefrom is filtered, wash, is dried in vacuum overnight, obtains Ru@MIL-110 catalyst.
Weigh the Co (NO that MIL-110 and 2.5mL concentration prepared in 50mg embodiments one is 0.01mol/L3)2Solution,
And both are added in 30mL deionized waters, ultrasonic 10min obtains dispersed suspension.Then 50.0mg reduction is weighed
Agent NaBH4Solid is simultaneously dissolved in 10mL deionized waters, by the NaBH4The aqueous solution is added dropwise in above-mentioned suspension, drop
Add and continue to stir 3h after finishing.Products therefrom is filtered, wash, is dried in vacuum overnight, obtains Co@MIL-110 catalyst.
Embodiment three：The preparation of RuCo nano-particles
Measure the RuCl that 2.5mL concentration is 0.01mol/L3Solution and the Co (NO that 2.5mL concentration is 0.01mol/L3)2Solution adds
Enter into 30mL deionized waters, dispersed mixed solution is obtained after ultrasonic 10min.Then 50.0mg reducing agents are weighed
NaBH4Solid is simultaneously dissolved in 10mL deionized waters, by the NaBH4The aqueous solution is added dropwise in above-mentioned mixed solution, drop
Add and continue to stir 3h after finishing.Products therefrom is filtered, wash, is dried in vacuum overnight, obtains RuCo nano-particle catalysts.
Example IV：Catalyst explains hydrogen experiment to the catalytic water of ammonia borine
To investigate the effect that the multiple catalysts that prepare of the present invention release ammonia borane hydrolysis hydrogen, the present inventor is by the catalyst of preparation
Hydrogen is released for being catalyzed ammonia borane hydrolysis, test process is as follows：
Experiment is carried out in two neck round-bottom flasks, and the neck connection gas-detecting device of two neck round-bottom flasks, another neck connects
Connect constant pressure funnel.5mg catalyst and 10mL deionized waters be housed in flask, uniform magnetic agitation, is equipped with constant pressure funnel
The solution that 18.5mg ammonia borine and 10mL deionized waters are formed, when the solution in funnel is added in flask, ammonia borine water
Explain that hydrogen reaction is carried out immediately, gas-detecting device produces the amount of hydrogen using buret measurement, is recorded every 30s and produces hydrogen
Volume.Whole reaction uses water-bath, and controlling reaction temperature is 25 DEG C.It is computed, ruthenium cobalt dual-metal alloy nano loads at room temperature
The TOF values that type catalyst RuCo@MIL-110 catalysis ammonia borane hydrolysis releases hydrogen are 533.2molH2×min-1(mol×Ru)-1。
It is respectively compared the carrier MIL-110 and ruthenium cobalt dual-metal alloy nano loaded catalyst of the preparation of embodiment one
RuCo@MIL-110, monometallic loaded catalyst Ru@MIL-110 and Co@MIL-110 of the preparation of embodiment two, embodiment three
The RuCo nano-particles of preparation carry out catalysis ammonia borane hydrolysis and release hydrogen experiment, as shown in Figure 5, the results showed that visible bimetallic is born
Supported catalyst RuCo@MIL-110 have highest catalytic activity.
Embodiment five：The hydrogen speed of releasing of ruthenium cobalt alloy manometer load-type catalyst is tested with activation energy under different temperatures
In order to measure the ruthenium cobalt dual-metal alloy nano loaded catalyst RuCo@MIL-110 of the invention prepared in different temperatures
Under release hydrogen speed and activation energy, hydrolysis experiment is respectively in 25,30,35 and 40 DEG C of progress, with the method for example IV
Catalysis ammonia borane hydrolysis releases hydrogen, as a result as shown in table 1.As a result show：Temperature is higher, and TOF values are bigger, and ammonia borine is released hydrogen speed and got over
It hurry up, the activation energy (Ea) that catalytic reaction is calculated according to Arrhenius formula by releasing hydrogen speed is 31.7kJ × mol-1。
The TOF values of ruthenium cobalt dual-metal alloy nano loaded catalyst catalysis ammonia borane hydrolysis under the different temperatures of table 1
| Temperature (DEG C) | 25 | 30 | 35 | 40 |
| TOF molH2×min-1(mol×Ru)-1 | 533.2 | 609.4 | 711.0 | 883.6 |
Embodiment six：The cyclical stability experiment of bimetal supported catalyst
Carrying out circulation using the ruthenium cobalt dual-metal alloy nano loaded catalyst RuCo@MIL-110 prepared by embodiment one makes
With performance test, hydrogen is released with the method catalysis ammonia borane hydrolysis of example IV.At 25 DEG C, when catalysis ammonia borane hydrolysis is complete
Afterwards, then toward the ammonia borine (18.5mg) of addition equivalent in two mouthfuls of flasks test, after 5 circulations, ruthenium cobalt dual-metal alloy is received
The relatively first activity of rice corpuscles loaded catalyst RuCo@MIL-110 still retains 79.0%, it is seen then that the catalyst has very high
Activity and stability, refer to table 2.
The ruthenium cobalt dual-metal alloy nano loaded catalyst of table 2 circulation hydrolysis ammonia borine releases hydrogen
| Catalyst cycle-index | 1 | 2 | 3 | 4 | 5 |
| Catalytic activity (%) | 100 | 94.1 | 88.2 | 83.2 | 79.0 |
To sum up, ruthenium cobalt dual-metal manometer load-type catalyst RuCo@MIL-110 of the present invention are catalyzed ammonia borine at room temperature
Hydrolysis releases hydrogen meter and reveals very high catalytic activity, and transformation frequency (TOF) is 533.2molH2×min-1(mol×Ru)-1, activation energy
(Ea) it is 31.7kJ × mol-1.The catalyst still keeps 79% activity after 5 cyclic tests, shows fabulous circulation
Stability.The average grain diameter of the ruthenium cobalt alloy particle loaded is 2.3nm, and dispersed on carrier.
Above-described embodiment elaborates to the present invention.Certainly, described above is not limitation of the present invention, the present invention
It is also not limited to above-mentioned example, person skilled change made in the essential scope of the present invention, retrofits, adds and add deduct
Less, replace, fall within protection scope of the present invention.
Claims (5)
1. a kind of ammonia borane hydrolysis releases hydrogen ruthenium cobalt dual-metal manometer load-type catalyst, it is characterised in that using ruthenium and cobalt as work
Property component, using metal organic framework MIL-110 as carrier, by ruthenium cobalt alloy nanometer particle load in obtaining ruthenium cobalt on MIL-110
Bimetal nano loaded catalyst RuCo@MIL-110.
2. a kind of ammonia borane hydrolysis according to claim 1 releases the preparation of hydrogen ruthenium cobalt dual-metal manometer load-type catalyst
Method, it is characterised in that comprise the following steps：
(1) first by Al (NO3)3·9H2O, trimethyl trimesate, NaOH, deionized water are stirring evenly and then adding into poly-
In the stainless steel cauldron of tetrafluoroethene liner, 210 DEG C of reaction 3h obtain suspension, and suspension is filtered, washed, is dried, is obtained
To white solid thing；Obtained white solid thing is added in the reactor containing DMF solution again, 150
DEG C reaction 5h；Reaction terminate after by solids in deionized water 100 DEG C backflow 12h, wash, vacuum drying, obtaining metal has
Machine skeleton MIL-110 white powders；
(2) MIL-110 white powders obtained by above-mentioned steps (1) are added in deionized water, ultrasonic disperse is uniform, and ruthenium is added dropwise
Salt and cobalt salt solution, 6h is stirred, obtains suspension；
(3) by reducing agent NaBH4The solution is added dropwise to the suspension of above-mentioned steps (2) by solid dissolving in deionized water
In, continue to stir 3h after being added dropwise, product is filtered, wash, is dried in vacuum overnight, ruthenium cobalt alloy manometer load-type is obtained and urges
Agent RuCo@MIL-110.
3. ammonia borane hydrolysis according to claim 2 releases the preparation side of hydrogen ruthenium cobalt dual-metal manometer load-type catalyst
Method, it is characterised in that Al (NO described in step (1)3)3·9H2O, trimethyl trimesate, NaOH, mole of deionized water
Than for 1：0.5：2.3：309.
4. the ammonia borane hydrolysis according to Claims 2 or 3 releases the preparation of hydrogen ruthenium cobalt dual-metal manometer load-type catalyst
Method, it is characterised in that the mol ratio of the cobalt in ruthenium and cobalt salt described in step (2) in ruthenium salt is 1:1.
5. ammonia borane hydrolysis according to claim 4 releases the preparation side of hydrogen ruthenium cobalt dual-metal manometer load-type catalyst
Method, it is characterised in that ruthenium salt described in step (2) is ruthenium trichloride, and described cobalt salt is soluble cobalt.
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