CN109225284A - A kind of hydrogen storage material decomposition hydrogen release system - Google Patents
A kind of hydrogen storage material decomposition hydrogen release system Download PDFInfo
- Publication number
- CN109225284A CN109225284A CN201710559516.3A CN201710559516A CN109225284A CN 109225284 A CN109225284 A CN 109225284A CN 201710559516 A CN201710559516 A CN 201710559516A CN 109225284 A CN109225284 A CN 109225284A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- storage material
- hydrogen storage
- metal
- release system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J23/745—Iron
-
- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
-
- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- 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
- Y02E60/32—Hydrogen storage
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of hydrogen storage materials to decompose hydrogen release system, including hydrogen storage material, catalysts and solvents；The catalyst is the mixture that two or more metallic compounds are mixed according to arbitrary proportion.The present invention provides cheap and stable catalysis hydrogen storage materials to decompose hydrogen release system, and the raw material of catalyst preparation is cheap；Catalyst property of the invention is stablized, and releases hydrogen efficiency height applied to catalysis hydrogen storage material；It is heterogeneous catalytic reaction that hydrogen system is released in catalysis of the invention, convenient for the recycling of catalyst；If catalysis of the invention is released hydrogen system and carried out in organic solvent, catalysis reaction can be carried out in 273K temperature below；Catalysis of the invention is released in hydrogen system, when the hydrogen storage material used is ammonia borine and methanol as solvent, the NH that obtains after alcoholysis4B(OCH3)4Ammonia borine can be retrieved under certain condition.
Description
Technical field
The present invention relates to hydrogen fuel cell technical fields.Hydrogen release system is decomposed more particularly, to a kind of hydrogen storage material.
Background technique
With the development of industry with the surge of population, fossil fuel is petered out to be deteriorated increasingly with environment, new cleaning energy
The exploitation and storage in source become the new focus of various countries' development.Hydrogen is used as the most clean energy, is paid much attention to by people.Due to hydrogen
The direct storage of gas faces high cost and high-risk, so highly-safe chemical hydrogen storage material is concerned in the nearly more than ten years.
At room temperature, chemical hydrogen storage material can exist with the form stable of solid perhaps liquid in heating or outer plus catalysis
Hydrogen is released under conditions of agent.Wherein, release hydrogen storage material in water, ionic liquid or organic solvent using catalyst
Hydrogen is most common method.Used catalyst has metal nanoparticle, nonmetallic compound (Ni2P、CoP、CoB、CoNiP、
Co-Ni-B), metal complex and small amounts object.
Above method and catalyst are released in hydrogen storage material achieves certain research achievement on hydrogen, but there is also following disadvantages
End: metal nanoparticle, nonmetallic compound, which are easily oxidized, not only prepares difficult and low efficiency with metal complex；Ionic liquid
Make at high cost when solvent；It releases hydrogen if being catalyzed hydrogen storage material with catalyst and being hydrolyzed and will receive the influence of temperature locating for system,
When temperature is lower than 273K, system is frozen；No matter water or ionic liquid are used, is unfavorable for producing after hydrogen storage material dehydrogenation
The recycling and reuse of object, especially ammonia borine (NH3BH3, AB).
Accordingly, it is desirable to provide a kind of stabilization, efficient, cheap, recyclable, the wide hydrogen storage material decomposition hydrogen release of use condition
System.
Summary of the invention
It is an object of the present invention to provide a kind of hydrogen storage materials to decompose hydrogen release system.
In order to achieve the above objectives, the present invention adopts the following technical solutions:
A kind of hydrogen storage material decomposition hydrogen release system, including hydrogen storage material, catalysts and solvents；The catalyst be two kinds with
The mixture that upper metallic compound is obtained according to arbitrary proportion grinding.The present invention is mixed using two or more metallic compounds
Catalyst is obtained, there is synergistic effect between various metals compound, under its mutual cooperation, synergistic effect, improves and urges
Change the efficiency for decomposing hydrogen release.
Preferably, the lapping mode includes but is not limited to hand-ground and ball mill grinding.The purpose that the present invention is ground
It is to enable between various metals compound that there is the contact of close surface, makes to generate phase interaction between the atom of various metals compound
With promoting the raising of catalytic efficiency.
Preferably, the hydrogen storage material is ammonia borine, boron hydride, hydrazine hydrate, hydrazine borine, formic acid or acetic acid.
Preferably, the hydrogen storage material, catalysts and solvents mix in any proportion.As long as three's mixing is in the present invention
Generate hydrogen.
Preferably, the catalyst is powder made of two or more metallic compounds mix, between metallic compound
Dosage is arbitrary proportion；The hybrid mode is usual manner, and preferably grinding, powder disperse ultrasound etc. in a solvent.This hair
After bright middle different metal compound grinding together, synergistic effect is generated on the contact surface；A kind of metallic compound serves as another
The carrier of kind, dispersion effect are good.
Preferably, the catalyst is the mixture that two kinds of metallic compounds are mixed according to arbitrary proportion.The technology of the present invention
Personnel have found that the mass ratio of metallic compound influences catalytic rate in the course of the research, need to be matched according to the actual situation.
For example, the catalyst is CoP and Cu in the present invention in certain embodiments3When P, CoP and Cu3The mass ratio of P is 7:3
When, obtained catalytic rate is optimal.The catalyst is Fe (OH)3With Cu (OH)2When, Fe (OH)3With Cu (OH)2Mass ratio
When for 6.5:3.5, obtained catalytic rate is optimal.
Preferably, metallic compound is metal phosphide, metal hydroxides, metal sulfide, gold in the catalyst
Belong to nitride, metal carbides, metal oxide, metal selenide, metal phosphate, metal molybdate, metal tungstates, gold
The oxyhydroxide or metal carbonate of category.The preparation method of heretofore described different metallic compounds is unrestricted.
Preferably, in the catalyst metallic compound metal be manganese, iron, cobalt, nickel, copper, molybdenum, tungsten, indium, antimony, gallium,
Tin, aluminium, zinc, cadmium or titanium.Metal in the present invention uses cheap metal, cheap, save the cost.
Preferably, the general formula of the metallic compound is MxRyOr MxPnOy, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W,
In, Sb, Ga, Sn, Al, Zn, Cd or Ti, R P, OH, S, N, C, O, Se, OOH, (MoO)n、(WO)nOr (CO)3, P represents phosphorus, O
Represent oxygen, 0 < x < 20,0 < y < 30,0 < n < 10.Further, in certain specific embodiments of the invention, for example, x's takes
Be worth range are as follows: 0 < x < 18,0 < x < 16,0 < x < 14,0 < x < 12,0 < x < 10,0 < x < 8,0 < x < 6,0 < x < 4,0 < x < 2,2 < x < 20,4 <
x<20、6<x<20、8<x<20、10<x<20、12<x<20、14<x<20、16<x<20、18<x<20、2<x<18、4<x<16、6<x<
14,8 < x < 12 etc.；The value range of y are as follows: 0 < y < 28,0 < y < 26,0 < y < 24,0 < y < 22,0 < y < 20,0 < y < 18,0 < y < 16,0 <
y<14、0<y<12、0<y<10、0<y<8、0<y<6、0<y<4、0<y<2、2<y<30、4<y<30、6<y<30、8<y<30、10<y<
30、12<y<30、14<y<30、16<y<30、18<y<30、20<y<30、22<y<30、24<y<30、26<y<30、28<y<30、2<
Y < 28,4 < y < 26,6 < y < 24,8 < y < 22,10 < y < 20,12 < y < 18,14 < y < 16 etc.；The value range of n are as follows: 0 < n < 8,0 < n <
6,0 < n < 4,0 < n < 2,2 < n < 10,4 < n < 10,6 < n < 10,8 < n < 10,2 < n < 8,4 < n < 6 etc..
Preferably, the general formula of the metal phosphide is MxPy, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga,
Sn, Al, Zn, Cd or Ti, P represent phosphorus, and the value range of x, y are as defined above；Further, the metal phosphide is specific
For Ni2P、NiP、Ni12P5、Ni5P4、Ni7P3、Ni3P、NiP2、FeP、Fe2P、FeP2、FeP4、Fe3P、CoP2、CoP4、CoP3、
CoP2、CoP、Co2P、Cu3P、Cu2P7、CuP2、MnP、MnP4、Mn5.6P3、Mn2P、WP、WP2、WP4、TiP、InP、InP3、Sn3P、
MoP、Mo4P3、MoP4、MoP2Or Mo8P5Deng.
Preferably, the general formula of the metal hydroxides is Mx(OH)y, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In,
The value range of Sb, Ga, Sn, Al, Zn, Cd or Ti, x and y are as defined above；Further, the metal hydroxides tool
Body is Fe (OH)3、Co(OH)2、Mn(OH)2、Ni(OH)2、Mn(OH)4、Ni(OH)3、Fe(OH)2、Cu(OH)2、Sn(OH)2Or Al
(OH)3Deng.
Preferably, the general formula of the metal sulfide is MxSy, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga,
Sn, Al, Zn, Cd or Ti, S are sulphur, and the value range of x, y are as defined above；Further, the metal sulfide is specially
Mo3S4、MoS2、Mo2S3、Mo7S8、Mo15S19、CoS、CoS2、Co4S3、Co9S8、Co3S4、NiS、Ni9S8、Ni3S2、Ni7S6、NiS2、
CdS、FeS、FeS2、Fe3S4、Cu7S4、Cu2S、CuS2、Cu8S5、Cu7S4Or Cu9S8Deng.
Preferably, the general formula of the metal nitride is MxNy, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga,
Sn, Al, Zn, Cd or Ti, N are nitrogen, and the value range of x, y are as defined above；Further, the metal nitride is specially
Mo3S4, for example: WN, W2N、Mo16N7、Mo2N、MoN、Mo5N6、MnN、Mn3N2、Mn4N、Mn6N2.58、Fe3N、Fe2N、FeN、Fe4N、
Co2N、CoN、Co2N0.67、Co5.47N、Ni3N、Ni4N、CuN3、Cu3N、Cu4N or InN etc..
Preferably, the general formula of the metal carbides is MxCy, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga,
Sn, Al, Zn, Cd or Ti, C are carbon, and the value range of x and y are as defined above；Further, the metal carbides are specific
For FeC, Fe3C、Fe5C2、Fe2C、Fe7C3、Mn5C2、Mn7C3、Mn15C4、MnC8、Co2C、Co3C、CoC8、Ni3C、WC、W2C、CW3Or
CuC8Deng.
Preferably, the general formula of the metal oxide is MxOy, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga,
Sn, Al, Zn, Cd or Ti, O are oxygen, and the value range of x, y are as defined above；Further, the metal oxide is specially
Mo4O11、MoO2、MoO3、Mo9O26、CoO、Co2O3、Co3O4、NiO、Ni2O3、FeO、Fe2O3、Fe3O4、CuO、Cu2O、Cu4O3、
MnO、MnO2、Mn3O4、Mn2O3、Mn5O8、WO3、WO2、W5O14、SnO2、SnO、Sn2O3、Sn3O4、TiO2、TiO、Ti3O5、Ti4O7、
Ti6O11、Ti2O3、Al2O3, CdO or CdO2Deng.
Preferably, the general formula of the metal selenide is MxSey, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb,
Ga, Sn, Al, Zn, Cd or Ti, Se are selenium, and the value range of x, y are as defined above；Further, the metal selenide tool
Body is MnSe, MnSe2、FeSe、FeSe2、Fe7Se2、Fe7Se8、Co9Se8、CoSe、CoSe2、Ni6Se5、NiSe2、Ni3Se2、
NiSe、Ni3Se4、Ni0.85Se、Cu5Se4、Cu2Se、CuSe、Cu7Se4、CuSe2、Cu3Se2、CdSe、MoSe2、Mo15Se19、
Mo3Se4、Mo9Se11Or WSe2Deng.
Preferably, the general formula of the oxyhydroxide of the metal is Mx(OOH)y, wherein M be Mn, Fe, Co, Ni, Cu, Mo,
W, the value range of In, Sb, Ga, Sn, Al, Zn, Cd or Ti, x, y are as defined above；Further, the hydroxyl of the metal
Oxide is specially FeOOH, CoOOH or NiOOH etc..
Preferably, the general formula of the metal phosphate is MxPnOy, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb,
Ga, Sn, Al, Zn, Cd or Ti, P are phosphorus, and the value range of x, y, n are as defined above.
Preferably, the general formula of the metal molybdate is Mx[(MoO)n]y, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W,
In, Sb, Ga, Sn, Al, Zn, Cd or Ti, Mo are molybdenum, and the value range of x, y, n are as defined above.
Preferably, the general formula of the metal tungstates is Mx[(WO)n]y, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In,
Sb, Ga, Sn, Al, Zn, Cd or Ti, W are tungsten, and the value range of x, y, n are as defined above.
Preferably, the general formula of the metal carbonate is Mx[(CO)3]y, wherein M be Mn, Fe, Co, Ni, Cu, Mo, W, In,
Sb, Ga, Sn, Al, Zn, Cd or Ti, C are carbon, and the value range of x, y, n are as defined above.
Preferably, the solvent is organic solvent and/or water.Solvent can be individually for water in system of the present invention, can also water and
The mixing of organic solvent any proportion, can be individually for organic solvent.Preferably, when the solvent is organic solvent, catalysis reaction
It can be carried out in 273K temperature below, widen the use scope of system.
Preferably, the organic solvent is methanol, ethyl alcohol, ethylene glycol, glycerine or propyl alcohol.Organic solvent in the present invention
It is not only that hydrogen generates offer proton, and catalysis reaction can be enabled to carry out in 273K temperature below.
Preferably, it further includes alkali that the hydrogen storage material, which decomposes hydrogen release system,.Invention technician it has been investigated that, be added
Alkali can be improved the catalytic rate of catalyst and shorten induction period.Alkali carries in the present invention are for OH-, OH-Hydrogen can be promoted to generate
Rate and shorten induction period, a part ionizes out OH to alkali in a solvent-, another part hydrolyzes, and generates OH-。
Preferably, it is NaOH, KOH, LiOH, CsOH, ammonium hydroxide, Na that the hydrogen storage material, which decomposes alkali in hydrogen release system,2CO3、
NaHCO3、K2CO3Or KHCO3。
Preferably, the concentration of the alkali in a solvent is >=0.0001mol/L；The alkali reaches saturated concentration in a solvent
Afterwards, the content that alkali can be continued growing, only theoretically without economic value.Therefore, it is highly preferred that the alkali in a solvent
Concentration be 0.0001mol/L~saturated concentration.Further, in certain specific embodiments of the invention, for example, institute
State the concentration of alkali in a solvent be 0.0001~2mol/L, 0.0001~1.5mol/L, 0.0001~1mol/L, 0.0001~
0.7mol/L, 0.0001~0.6mol/L, 0.0001~0.5mol/L, 0.0001~0.4mol/L, 0.0001~0.3mol/L,
0.0001~0.2mol/L, 0.0001~0.1mol/L, 0.1~0.7mol/L, 0.2~0.7mol/L, 0.3~0.7mol/L,
0.4~0.7mol/L, 0.5~0.7mol/L, 0.6~0.7mol/L, 0.7~2mol/L, 0.8~2mol/L, 0.9~2mol/
L, 1~2mol/L, 0.1~2mol/L, 0.2~1.5mol/L, 0.3~1mol/L, 0.4~0.9mol/L, 0.5~0.8mol/
L, 0.6~0.7mol/L etc..
How to be stablized, is efficient, is cheap, is recyclable, the hydrogen storage material decomposition hydrogen release system that use condition is wide, being this
Invent the primary technical problem overcome.In order to overcome the above technical problems, the present invention is made using stable various metals compound
It cooperates, act synergistically for catalyst, and between various metals compound, not only solve most single metal chemical combination
Object cannot be catalyzed the problem of hydrogen storage material hydrogen release, and improve catalytic rate.In addition, the solvent in the present invention is organic solvent
And/or water, widen the use scope of system.
In addition, unless otherwise specified, it is raw materials used in the present invention can be by commercially available commercially available, documented by the present invention
Any range includes that any numerical value between end value and end value and any number between end value or end value are constituted
Any subrange.
Beneficial effects of the present invention are as follows:
1) the present invention provides cheap and stable catalysis hydrogen storage materials to decompose hydrogen release system, and the raw material of catalyst preparation is just
Preferably.
2) present invention decomposes in hydrogen release system in hydrogen storage material and alkali is added, and catalytic rate and the shortening of catalyst can be improved
Induction period.
3) catalyst property of the invention is stablized, and is applied to catalysis hydrogen storage material and decomposes hydrogen releasing efficient height.
4) properties system of the invention is heterogeneous catalytic reaction, convenient for the recycling of catalyst.
If 5) catalysis of the invention is released hydrogen system and carried out in organic solvent, catalysis reaction can be in 273K temperature below
It carries out.
6) catalysis of the invention is released in hydrogen system, when the hydrogen storage material used is ammonia borine (NH3BH3, AB) and methanol make it is molten
The NH obtained when agent, after alcoholysis4B(OCH3)4Ammonia borine (NH can be retrieved under certain condition3BH3, AB), so as to
Ammonia borine is enough recycled, cost is reduced.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the CoP and Cu of the different proportion of the preparation of the embodiment of the present invention 1~43Mixed-powder diffraction (XRD) light of P
Spectrogram.
Fig. 2 shows the systems of the embodiment of the present invention 1~4 and comparative example 1~2 to release hydrogen volume at any time during catalyzed alcoholysis
Between the curve that changes.
The system that Fig. 3 shows the embodiment of the present invention 5~10 releases the song that hydrogen volume changes over time during catalyzed alcoholysis
Line.
Fig. 4 shows one of the material prepared in the embodiment of the present invention 12 Cu (OH)2Transmission electron microscope (TEM) figure.
Fig. 5 shows one of the material prepared in the embodiment of the present invention 12 Fe (OH)3Transmission electron microscope (TEM) figure.
Fig. 6 shows the Fe (OH) that the mass ratio of the preparation of the embodiment of the present invention 12 is 6.5:3.53With Cu (OH)2Powder diffraction
(XRD) spectrogram.
Fig. 7 shows the Fe (OH) that the mass ratio of the preparation of the embodiment of the present invention 12 is 6.5:3.53With Cu (OH)2Mixed-powder
Transmission electron microscope (TEM) figure.
The system that Fig. 8 shows the embodiment of the present invention 11~15 releases the song that hydrogen volume changes over time during catalyzed alcoholysis
Line.
The system that Fig. 9 shows the embodiment of the present invention 12 and embodiment 15 is released hydrogen volume during catalyzed alcoholysis and is become at any time
The curve of change.
The system that Figure 10 shows the embodiment of the present invention 16~20 releases what hydrogen volume changed over time during catalyzed alcoholysis
Curve.
Figure 11 shows what ln rate during the system catalyzed alcoholysis of the embodiment of the present invention 16~20 changed with ln [Cat]
Curve.
Figure 12 shows transmission electron microscope (TEM) figure of the catalyst recycled in the embodiment of the present invention 29.
The system that Figure 13 shows the embodiment of the present invention 21~24 releases what hydrogen volume changed over time during catalyzed alcoholysis
Curve.
Figure 14 shows what the system of the embodiment of the present invention 21~24 ln rate during catalyzed alcoholysis changed with ln [AB]
Curve.
The system that Figure 15 shows the embodiment of the present invention 25~28 releases what hydrogen volume changed over time during catalyzed alcoholysis
Curve.
Figure 16 shows the system of the embodiment of the present invention 25~28 ln rate during catalyzed alcoholysis to be changed with inverse temperature
Curve.
The system that Figure 17 shows the embodiment of the present invention 29 releases the curve that hydrogen volume changes over time during catalyzed alcoholysis.
The system that Figure 18 shows the embodiment of the present invention 56 releases the curve that hydrogen volume changes over time during catalyzed alcoholysis.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.It will be appreciated by those skilled in the art that specifically described content is illustrative and be not restrictive below, it should not be with this
It limits the scope of the invention.
It is as follows for the step of decomposing hydrogen release that hydrogen storage material of the invention decomposes hydrogen release system:
The more mouthfuls of reaction vessels equipped with magnetic stir bar are fixed in thermostat water bath, after catalyst is added, use plug
The outlet of equal closed reactors makes last remaining one outlet be connected with the eudiometer tube for filling water, it is ensured that a whole set of with rubber tube
Gas exchanges are not present in device and ambient enviroment.The solution containing hydrogen storage material is thrown by rubber stopper with syringe, record is different
When inscribe the volume that gas arranges water.The hydrogen of generation Shimadzu DC-14C gas chromatographic detection, this gas-chromatography use 0.5nm
Molecular sieve column (3m × 2mm), thermal conductivity cell detector (TCD), carrier gas is argon gas.
Examples 1 to 4 and comparative example 1~2
A kind of hydrogen storage material decomposition hydrogen release system, measures the mass ratio of metallic compound in catalyst to catalytic rate
It influences, i.e., the usage ratio of metallic compound in change System Catalyst, such as table 1, the hydrogen-producing speed of counting system.
System includes that ammonia borine, the 5mL of 50mg includes the mixed solution of sodium hydroxide and methanol, 10mg by CoP and Cu3P
According to different quality than mixed catalyst；Wherein naoh concentration is in the mixed solution of sodium hydroxide and methanol
0.6mol/L；
CoP and Cu3The preparation for the catalyst that P is mixed according to different proportion: by the CoP and Cu of different quality ratio3P exists respectively
It grinds and is mixed in platinum uniformly, be then fully ground every a sample, after being fully ground, obtain catalyst.Obtained catalyst is done
Powder diffraction, obtained result such as Fig. 1 can learn CoP and Cu from Fig. 13There is no chemical reactions between P, only merely
Physical mixed, Cu3Diffraction maximum of the P in mixed phase becomes smaller, and illustrates that crystallinity is destroyed.
1 difference CoP:Cu of table3The hydrogen-producing speed that P mass ratio obtains
| Embodiment number | CoP:Cu3P mass ratio | Hydrogen-producing speed (mL/min) |
| Comparative example 1 | 0:10 | 2.6 |
| Embodiment 1 | 3:7 | 6.8 |
| Embodiment 2 | 5:5 | 14.1 |
| Embodiment 3 | 7:3 | 21.5 |
| Embodiment 4 | 8:2 | 15.4 |
| Comparative example 2 | 10:0 | 0.3 |
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with ammonia borine, the hydrogen that record eudiometer tube was collected into different moments
Volume.Curve is made respectively to the time with each hydrogen volume, as shown in Figure 2.It can be concluded that, change CoP from result shown in Fig. 2
And Cu3The amount ratio of P, available different hydrogen-producing speed.After hydrogen-producing speed first increases as the increase of the quality of CoP is presented
Reduced rule, wherein maximum when arriving 7:3.
In addition, according to comparative example 1 and 2 it is found that producing hydrogen when the metallic compound in catalyst is single metallic compound
Rate is much smaller than the rate of mixed-metal compounds, and such as 2.6mL/min when being individually for CoP in catalyst is individually for Cu3When P
0.30mL/min, the two mix later rate and are all higher than a kind of individually rate of metallic compound as catalyst.
Embodiment 5~10
A kind of hydrogen storage material decomposes hydrogen release system, and influence of the dosage of alkali to catalytic rate in measurement system, i.e. method walk
Suddenly with embodiment 2, it the difference is that only the concentration of sodium hydroxide in change system, such as table 2, the hydrogen-producing speed of counting system.
The hydrogen-producing speed that different naoh concentrations obtain in the mixed solution of 2 sodium hydroxide of table and methanol
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with ammonia borine, the hydrogen that record eudiometer tube was collected into different moments
Volume.Curve is made respectively to the time with each hydrogen volume, as shown in Figure 3.From result shown in Fig. 3 it can be concluded that, with hydrogen
The concentration of sodium oxide molybdena increases, and the rule of first increases and then decreases is presented in the rate that hydrogen is generated in the unit time, when sodium hydroxide
When concentration is more than 0.6mol/L, rate decline, because there is the undissolvable situation of part sodium hydroxide at this time.
Embodiment 11~15 and comparative example 3~4
A kind of hydrogen storage material decomposition hydrogen release system, measures the mass ratio of metallic compound in catalyst to catalytic rate
It influences, i.e., the usage ratio of metallic compound in change System Catalyst, such as table 3, the hydrogen-producing speed of counting system.
System includes that ammonia borine, the 5mL of 50mg includes the mixed solution of sodium hydroxide and methanol, 10mg by Fe (OH)3With
Cu(OH)2According to different quality than mixed catalyst；Wherein naoh concentration in the mixed solution of sodium hydroxide and methanol
For 0.5mol/L.
Fe(OH)3With Cu (OH)2Preparation: in a round-bottomed flask, be added 250mg sodium citrate, 2.0g sodium hydroxide
Mixed liquor 1 is obtained with 80mL distilled water stirring and dissolving；1g copper nitrate (or ferric nitrate) is dissolved in 20mL distilled water to be mixed
Liquid 2；Mixed liquor 2 is slowly dropped in mixed liquor 1, after being added dropwise, is stirred at room temperature after 1h, the mixture is collected by centrifugation
In precipitating, after a large amount of distillation water washing precipitating, by it, the sufficiently dry water removal at 340K, obtains Cu (OH)2Or Fe
(OH)3, to obtained Cu (OH)2With Fe (OH)3It does transmission electron microscope (TEM), obtained result such as Fig. 4 and Fig. 5.
Fe(OH)3With Cu (OH)2According to the preparation of the catalyst of different proportion mixing: by the Fe (OH) of different quality ratio3With
Cu(OH)2It is mixed in grinding platinum respectively uniformly, is then fully ground every a sample, after being fully ground, obtains catalyst.Wherein
To Fe (OH)3With Cu (OH)2Mass ratio be 6.5:3.5 catalyst carry out powder diffraction (XRD) and transmission electron microscope (TEM), obtain
The result arrived is as shown in Figure 6 and Figure 7, can learn Cu (OH) from Fig. 6 and Fig. 72With Fe (OH)3It mixes after grinding, Cu
(OH)2Strip structure be destroyed (TEM), and the diffraction maximum in (XRD) disappears, and illustrates Cu (OH)2Crystallinity is destroyed.
3 difference Fe (OH) of table3: Cu (OH)2The hydrogen-producing speed that mass ratio obtains
| Embodiment number | Fe(OH)3: Cu (OH)2Mass ratio | Hydrogen-producing speed (ml/min) |
| Comparative example 3 | 10:0 | 0 |
| Embodiment 11 | 7:3 | 27.9 |
| Embodiment 12 | 6.5:3.5 | 37.1 |
| Embodiment 13 | 6:4 | 28.4 |
| Embodiment 14 | 5:5 | 18.0 |
| Embodiment 15 | 3:7 | 9.4 |
| Comparative example 4 | 0:10 | 1.7 |
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with ammonia borine, the hydrogen that record eudiometer tube was collected into different moments
Volume.Curve is made respectively to the time with each hydrogen volume, as shown in Figure 8.It can be concluded that, change Fe from result shown in Fig. 8
(OH)3With Cu (OH)2Mass ratio, available different hydrogen-producing speed.Hydrogen-producing speed is with Cu (OH)2The increase of quality be in
Now first increase the rule reduced afterwards, wherein maximum when arriving 6.5:3.5.
In addition, according to comparative example 3 and 4 it is found that producing hydrogen when the metallic compound in catalyst is single metallic compound
Rate is much smaller than the rate of mixed-metal compounds, is individually for Fe (OH) as worked as in catalyst3When be 0mL/min, illustrate Fe
(OH)3It cannot be catalyzed hydrogen storage material hydrogen release, be individually for Cu (OH)2When be 0.30mL/min, the two mixes later rate and is all higher than
A kind of individually rate of metallic compound as catalyst.
Embodiment 15
A kind of hydrogen storage material decomposition hydrogen release system, measures influence of the dosage to catalytic rate of sodium hydroxide, i.e. method walks
Suddenly with embodiment 12, it the difference is that only that the concentration of sodium hydroxide in system solvent is 0, the hydrogen-producing speed of counting system.It will
Hydrogen storage material decomposes hydrogen release system for decomposing hydrogen release, the volume for the hydrogen that record eudiometer tube was collected into different moments.With every
Secondary hydrogen volume makees curve to the time respectively, as shown in Figure 9.From result shown in Fig. 9, it can be concluded that, sodium hydroxide can promote
Hydrogen storage material discharges hydrogen.
Embodiment 16~20
A kind of hydrogen storage material decomposition hydrogen release system, measures influence of the dosage to catalytic rate of catalyst, i.e. method and step
With embodiment 12, the dosage of catalyst in change system the difference is that only, such as table 4, the hydrogen-producing speed of counting system.
The hydrogen-producing speed that the catalyst of 4 different quality of table obtains
| Embodiment number | Catalyst quality (mg) | Time needed for releasing hydrogen (min) | Hydrogen-producing speed (ml/min) |
| Embodiment 16 | 2.5 | 15.5 | 7.6 |
| Embodiment 17 | 5 | 5.5 | 21.3 |
| Embodiment 18 | 7.5 | 4 | 29.5 |
| Embodiment 12 | 10 | 3.2 | 36.7 |
| Embodiment 19 | 15 | 2.1 | 55.9 |
| Embodiment 20 | 20 | 1.7 | 69.8 |
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with ammonia borine, the hydrogen that record eudiometer tube was collected into different moments
Volume.Curve is made with hydrogen volume and time respectively, as shown in Figure 10.It is calculated separately by the part of every curve close to straight line
Hydrogen rate is released in the catalysis under different catalysts amount out, releases hydrogen rate to 6 catalysis and 6 catalyst particle concentration take natural logrithm
6 ln rate and 6 ln [Cat] are obtained, make that curve is as shown in figure 11, and slope of a curve is to ln [Cat] with ln rate
0.902, this shows that catalyzed alcoholysis reaction is first order reaction for catalyst.Therefore, in the system, the dosage of catalyst
Influence to catalyzed alcoholysis rate are as follows: as the dosage of catalyst increases, the alcoholysis rate of ammonia borine increases.
Embodiment 21~24
A kind of hydrogen storage material decomposition hydrogen release system, measures influence of the dosage to catalytic rate of hydrogen storage material, i.e. method walks
Suddenly with embodiment 12, it the difference is that only that the dosage of catalyst in the dosage and system of hydrogen storage material in change system is
7mg, such as table 5, the hydrogen-producing speed of counting system.
The hydrogen-producing speed that the hydrogen storage material of 5 different quality of table obtains
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with ammonia borine, records the hydrogen that each eudiometer tube is collected into different moments
The volume of gas makees curve respectively with hydrogen volume and time, as shown in figure 13.Distinguished by every curve close to the part of straight line
Hydrogen rate is released in the catalysis calculated under different AB amounts, and then 4 catalysis are released hydrogen rate and be taken respectively from right logarithm with obtaining 4 ln
Rate makees curve with 4 ln [AB] that concentration of the ln rate to 4 ammonia borines takes natural logrithm to obtain, as shown in figure 14, should
Slope of a curve is 0.515, shows that catalyzed alcoholysis reaction is 0.5 order reaction for AB.Therefore, in the system, ammonia boron
Influence of the dosage of alkane to catalyzed alcoholysis rate are as follows: as the dosage of ammonia borine increases, alcoholysis rate is slowly increased.
Embodiment 25~28
A kind of hydrogen storage material decomposition hydrogen release system, influence of the measuring temperature to catalytic rate, the i.e. same embodiment of method and step
12, it the difference is that only change temperature, such as table 6, the hydrogen-producing speed of counting system.
The hydrogen-producing speed obtained under 6 condition of different temperatures of table
| Embodiment number | Temperature (K) | Time needed for releasing hydrogen (min) | Hydrogen-producing speed (ml/min) |
| Embodiment 12 | 298 | 5.6 | 20.8 |
| Embodiment 25 | 303 | 4.05 | 29.1 |
| Embodiment 26 | 308 | 3 | 40.3 |
| Embodiment 27 | 313 | 3.42 | 34.7 |
| Embodiment 28 | 317 | 3.1 | 38.6 |
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, under condition of different temperatures, catalyst is added and is reacted
In container, the mixed solution of sodium hydroxide and methanol dissolved with ammonia borine is reinjected, records each eudiometer tube in different moments
The volume for the hydrogen being collected into wrirtes music line to the time with hydrogen volume, as shown in figure 15, with every curve close to the part of straight line
It calculates separately out the catalysis under different catalysts amount and releases hydrogen rate, be then convert into rate constant.5 rate constants are derived from so
Logarithm obtains 5 ln κ, finally according to Arrhenius formula, makees curve with inverse of the ln κ to temperature, as shown in figure 16, according to
The slope of curve, calculating the activation energy reacted in the system is about 47.6KJ/mol.In the system, reaction temperature is to catalyzing hydrolysis
The influence of rate are as follows: as the temperature rises, the alcoholysis rate of ammonia borine increases.
Embodiment 29
A kind of hydrogen storage material decomposes hydrogen release system, and catalyst recycles situation in measurement system, i.e., the described system packet
Include 50mg ammonia borine, 5mL include the mixed solution of sodium hydroxide and methanol, 10mg recycling embodiment 16-20 catalyst
Fe(OH)3With Cu (OH)2；Wherein naoh concentration is 0.5mol/L in the mixed solution of sodium hydroxide and methanol.
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, reaction vessel is added in the catalyst of recycling
In, the mixed solution of sodium hydroxide and methanol dissolved with ammonia borine is reinjected, each eudiometer tube is recorded and is collected in different moments
The volume of the hydrogen arrived.After the catalyst of recycling releases hydrogen, washing catalyst is recycled again, to put into next time
It is recycled.
Reusing above catalyst 6 times recycled, during record is reused every time respectively the volume of hydrogen with
The corresponding time.With each hydrogen volume to time composition line, as shown in figure 17, wherein a curve represents circulation primary.
From result shown in Figure 17, it can be concluded that, the catalyst of recycling still keeps high activity to catalysis ammonia borine alcoholysis.Illustrate the present invention
Catalyst can recycle, it is economic and environment-friendly.
Embodiment 30~35
A kind of hydrogen storage material decomposition hydrogen release system, measures shadow of the concentration to catalytic rate of sodium hydroxide in system solvent
It rings, changes the concentration of sodium hydroxide in system solvent, the hydrogen-producing speed of counting system.
It includes the mixed solution of sodium hydroxide and methanol, 10mg by FeP and Ni that system, which includes the hydrazine hydrate of 50mg, 5mL,2P
With the quality of 3:2 than fine catalyst that mixed grinding obtains；Wherein sodium hydroxide in the mixed solution of sodium hydroxide and methanol
Concentration be followed successively by 0,0.1mol/L, 0.3mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L.
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with hydrazine hydrate, the hydrogen that record eudiometer tube was collected into different moments
Volume, it is as a result similar with embodiment 5~10.
Embodiment 36~39 and comparative example 5~6
A kind of hydrogen storage material decomposition hydrogen release system, measures the mass ratio of metallic compound in catalyst to catalytic rate
It influences, i.e., the usage ratio of metallic compound, the hydrogen-producing speed of counting system in change System Catalyst.
System includes that ammonia borine, the 5mL of 50mg includes the mixed solution of sodium hydroxide and methanol, 10mg by Co (OH)2With
CuO is according to different quality than fine catalyst that mixed grinding obtains；Wherein hydrogen-oxygen in the mixed solution of sodium hydroxide and methanol
Change na concn is 0.6mol/L；Co(OH)2With the mass ratio of CuO be followed successively by 3:7,5:5,7:3 and 8:2 (embodiment 36~39),
0:10 and 10:0 (comparative example 5~6).
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with ammonia borine, the hydrogen that record eudiometer tube was collected into different moments
Volume, it is as a result similar with Examples 1 to 4 and comparative example 1~2.
Embodiment 40~45
A kind of hydrogen storage material decomposition hydrogen release system, measures influence of the dosage to catalytic rate of catalyst, i.e. change system
The dosage of catalyst in catalyst, the hydrogen-producing speed of counting system.
System includes that hydrazine borine, the 5mL of 50mg includes the mixed solution of sodium hydroxide and methanol, by MnC8And Cu2Se according to
The fine catalyst that 4:6 mixed grinding obtains；
Wherein naoh concentration is 0.6mol/L in the mixed solution of sodium hydroxide and methanol；
The quality of catalyst is followed successively by 2.5mg, 5mg, 7.5mg, 10mg, 15mg, 20mg.
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with hydrazine borine, the hydrogen that record eudiometer tube was collected into different moments
Volume, it is as a result similar with embodiment 16~20.
Embodiment 46~50
A kind of hydrogen storage material decomposes hydrogen release system, and influence of the dosage of lye to catalytic rate, that is, change in measurement system
The dosage of lye in system, the hydrogen-producing speed of counting system.
System includes that ammonia borine, the 5mL of 50mg includes the mixed solution of sodium borohydride and methanol, by 10mg WO3And Sn
(OH)2The fine catalyst obtained according to 3:7 mixed grinding；
Wherein in the mixed solution of sodium borohydride and methanol sodium borohydride concentration be followed successively by 0,0.1mol/L, 0.3mol/L,
0.5mol/L,0.6mol/L,0.7mol/L；
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium borohydride and methanol of the injection dissolved with ammonia borine, the hydrogen that record eudiometer tube was collected into different moments
Volume, it is as a result similar with embodiment 5~10.
Embodiment 51~54
A kind of hydrogen storage material decomposition hydrogen release system, measures influence of the dosage to catalytic rate of hydrogen storage material, i.e. change body
The dosage of hydrogen storage material in system, the hydrogen-producing speed of counting system.
It includes the mixed solution of sodium hydroxide and methanol, 7mg by Co that system, which includes ammonia borine, 5mL,3S4With Cu (CO)3According to
The quality of 1:9 is than the fine catalyst that mixed grinding obtains；Wherein sodium hydroxide is dense in the mixed solution of sodium hydroxide and methanol
Degree is 0.6mol/L；The dosage of ammonia borine is followed successively by 50mg, 60mg, 70mg, 80mg.
It is used for hydrogen storage material decomposition hydrogen release system to decompose hydrogen release, in 298K, catalyst is added in reaction vessel, then
The mixed solution of sodium hydroxide and methanol of the injection dissolved with ammonia borine, records the hydrogen that each eudiometer tube is collected into different moments
The volume of gas, resulting experimental result are similar with embodiment 21~24.
Embodiment 55
A kind of hydrogen storage material decomposition hydrogen release system, method and step the difference is that only system catalysis is anti-with embodiment 1
The temperature answered is changed to 260K, and the hydrogen-producing speed of counting system, resulting experimental result is similar to Example 1, illustrates using organic
Solvent can enable catalysis reaction carry out in 273K temperature below.
Embodiment 56
A kind of hydrogen storage material decomposition hydrogen release system, measures influence of the solvent for use to catalytic rate, i.e., method and step is the same as real
Example 12 is applied, the difference is that only solvent type in change system, such as table 7, the hydrogen-producing speed of counting system, with each hydrogen
Volume against time makees curve respectively, as shown in figure 18.
The hydrogen-producing speed that 7 different solvents type of table obtains
| Embodiment number | Solvent type | Hydrogen-producing speed (ml/min) |
| Embodiment 56 | Water | 7.6 |
| Embodiment 12 | Methanol | 37.1 |
As seen from the table, when solvent is organic solvent, obtained hydrogen-producing speed is high.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of hydrogen storage material decomposes hydrogen release system, which is characterized in that it includes hydrogen storage material that the hydrogen storage material, which decomposes hydrogen release system,
Material, catalysts and solvents；The catalyst is the mixture that two or more metallic compounds are obtained according to arbitrary proportion grinding.
2. a kind of hydrogen storage material according to claim 1 decomposes hydrogen release system, which is characterized in that metal in the catalyst
Compound be metal phosphide, metal hydroxides, metal sulfide, metal nitride, metal carbides, metal oxide,
Metal selenide, metal phosphate, metal molybdate, metal tungstates, metal oxyhydroxide or metal carbonate.
3. a kind of hydrogen storage material according to claim 1 decomposes hydrogen release system, which is characterized in that metal in the catalyst
The metal of compound is manganese, iron, cobalt, nickel, copper, molybdenum, tungsten, indium, antimony, gallium, tin, aluminium, zinc, cadmium or titanium.
4. a kind of hydrogen storage material according to claim 3 decomposes hydrogen release system, which is characterized in that the metallic compound
General formula is MxRyOr MxPnOy, wherein 0 < x < 20,0 < y < 30,0 < n < 10, M represent metal, and P represents phosphorus, and O represents oxygen, R P, OH,
S、N、C、O、Se、OOH、(MoO)n、(WO)nOr (CO)3。
5. a kind of hydrogen storage material according to claim 1 decomposes hydrogen release system, which is characterized in that the solvent is organic molten
Agent and/or water.
6. a kind of hydrogen storage material according to claim 5 decomposes hydrogen release system, which is characterized in that the organic solvent is first
Alcohol, ethyl alcohol, ethylene glycol, glycerine or propyl alcohol.
7. a kind of hydrogen storage material according to claim 1 decomposes hydrogen release system, which is characterized in that the hydrogen storage material is ammonia
Borine, boron hydride, hydrazine hydrate, hydrazine borine, formic acid or acetic acid.
8. a kind of hydrogen storage material according to claim 1 decomposes hydrogen release system, which is characterized in that the hydrogen storage material decomposes
Hydrogen release system further includes alkali.
9. a kind of hydrogen storage material according to claim 8 decomposes hydrogen release system, which is characterized in that the hydrogen storage material decomposes
Alkali is NaOH, KOH, LiOH, CsOH, ammonium hydroxide, Na in hydrogen release system2CO3、NaHCO3、K2CO3Or KHCO3。
10. a kind of hydrogen storage material according to claim 8 decomposes hydrogen release system, which is characterized in that the alkali is in a solvent
Concentration be >=0.0001mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710559516.3A CN109225284B (en) | 2017-07-11 | 2017-07-11 | Hydrogen storage material decomposition and desorption system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710559516.3A CN109225284B (en) | 2017-07-11 | 2017-07-11 | Hydrogen storage material decomposition and desorption system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109225284A true CN109225284A (en) | 2019-01-18 |
| CN109225284B CN109225284B (en) | 2022-03-04 |
Family
ID=65083734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710559516.3A Active CN109225284B (en) | 2017-07-11 | 2017-07-11 | Hydrogen storage material decomposition and desorption system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109225284B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364742A (en) * | 2019-06-25 | 2019-10-22 | 北方民族大学 | For the anode catalyst of direct borohydride fuel cell, anode material and preparation method thereof and fuel cell |
| CN110743603A (en) * | 2019-11-21 | 2020-02-04 | 江苏索普（集团）有限公司 | Cobalt-iron bimetallic nitride composite electrocatalyst and preparation method and application thereof |
| CN110835103A (en) * | 2019-11-28 | 2020-02-25 | 惠州学院 | Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen |
| CN110844881A (en) * | 2019-11-28 | 2020-02-28 | 云南电网有限责任公司电力科学研究院 | Method for dehydrogenating liquid organic hydrogen storage material by using ionic liquid |
| CN111185171A (en) * | 2020-01-18 | 2020-05-22 | 中北大学 | Preparation method of high-activity multi-response carbon-point composite variable-valence copper oxide nanoenzyme |
| CN111377480A (en) * | 2020-03-20 | 2020-07-07 | 苏州科技大学 | Application of iron (II) -doped molybdenum sulfide material in self-powered piezoelectricity-enhanced hydrogen production |
| CN111420664A (en) * | 2020-03-11 | 2020-07-17 | 惠州学院 | Preparation method of flaky cuprous oxide/cobaltous oxide nanocomposite and application of flaky cuprous oxide/cobaltous oxide nanocomposite in catalyzing ammonia borane hydrolysis hydrogen production |
| CN112079332A (en) * | 2020-09-18 | 2020-12-15 | 北京大学 | Method for preparing hydrogen by directly inducing solid ammonia borane through photo-thermal method |
| CN112663088A (en) * | 2021-01-14 | 2021-04-16 | 江西省科学院能源研究所 | Preparation method of cobalt diselenide/iron oxyhydroxide composite material with nano petal-shaped structure |
| CN113713863A (en) * | 2021-07-23 | 2021-11-30 | 山东大学 | Plasma alloy photocatalytic material, preparation method and application |
| CN114210337A (en) * | 2021-10-28 | 2022-03-22 | 惠州学院 | Nickel copper tungstate nano heterojunction particles, preparation method thereof and application of nickel copper tungstate nano heterojunction particles in catalytic hydrogen production |
| CN114272935A (en) * | 2021-11-29 | 2022-04-05 | 惠州学院 | Catalyst for catalyzing ammonia borane to produce hydrogen and preparation method thereof |
| CN114345350A (en) * | 2022-01-20 | 2022-04-15 | 河南科技大学 | Co-based bimetallic oxide catalyst and preparation method thereof |
| CN115487848A (en) * | 2022-09-29 | 2022-12-20 | 惠州学院 | Preparation method of nanowire nickel nitride-copper nitride composite material and application of nanowire nickel nitride-copper nitride composite material in catalysis of alcoholysis of ammonia borane to produce hydrogen |
| CN115634693A (en) * | 2022-09-30 | 2023-01-24 | 惠州学院 | Preparation method of nano composite material with hollow tube structure and application of nano composite material in catalysis of ammonia borane alcoholysis for hydrogen production |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001051410A1 (en) * | 2000-01-07 | 2001-07-19 | Millennium Cell, Llc | System for hydrogen generation |
| CN102906925A (en) * | 2010-03-18 | 2013-01-30 | 布莱克光电有限公司 | Electrochemical hydrogen-catalyst power system |
| CN103159171A (en) * | 2013-03-08 | 2013-06-19 | 燕山大学 | LiBH4-doped metal sulfide hydrogen-storage composite material and preparation method thereof |
| CN103515620A (en) * | 2012-06-20 | 2014-01-15 | 中国地质大学（武汉） | Electrode material, its application, direct fuel cell and electrochemical hydrogenation electrolytic tank |
| CN103864015A (en) * | 2014-03-17 | 2014-06-18 | 华北水利水电大学 | Method for releasing hydrogen by catalyzing sodium tetrahydroborate with composite catalyst |
| CN105126884A (en) * | 2015-09-22 | 2015-12-09 | 云南师范大学 | Ammonia borane or hydrazine hydrate catalytic hydrolysis hydrogen release system containing nano-metal phosphide MxPy catalyst and application of catalytic hydrolysis hydrogen release system |
| CN105645351A (en) * | 2015-12-24 | 2016-06-08 | 浙江大学 | Aluminum hydride hydrogen storage material and preparation method thereof |
| CN105958086A (en) * | 2016-05-05 | 2016-09-21 | 成都玖奇新材料科技有限公司 | Application of three-dimensional transitional metal nanoarray used as catalyst for hydrogen production from hydroboron |
-
2017
- 2017-07-11 CN CN201710559516.3A patent/CN109225284B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001051410A1 (en) * | 2000-01-07 | 2001-07-19 | Millennium Cell, Llc | System for hydrogen generation |
| CN102906925A (en) * | 2010-03-18 | 2013-01-30 | 布莱克光电有限公司 | Electrochemical hydrogen-catalyst power system |
| CN103515620A (en) * | 2012-06-20 | 2014-01-15 | 中国地质大学（武汉） | Electrode material, its application, direct fuel cell and electrochemical hydrogenation electrolytic tank |
| CN103159171A (en) * | 2013-03-08 | 2013-06-19 | 燕山大学 | LiBH4-doped metal sulfide hydrogen-storage composite material and preparation method thereof |
| CN103864015A (en) * | 2014-03-17 | 2014-06-18 | 华北水利水电大学 | Method for releasing hydrogen by catalyzing sodium tetrahydroborate with composite catalyst |
| CN105126884A (en) * | 2015-09-22 | 2015-12-09 | 云南师范大学 | Ammonia borane or hydrazine hydrate catalytic hydrolysis hydrogen release system containing nano-metal phosphide MxPy catalyst and application of catalytic hydrolysis hydrogen release system |
| CN105645351A (en) * | 2015-12-24 | 2016-06-08 | 浙江大学 | Aluminum hydride hydrogen storage material and preparation method thereof |
| CN105958086A (en) * | 2016-05-05 | 2016-09-21 | 成都玖奇新材料科技有限公司 | Application of three-dimensional transitional metal nanoarray used as catalyst for hydrogen production from hydroboron |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364742A (en) * | 2019-06-25 | 2019-10-22 | 北方民族大学 | For the anode catalyst of direct borohydride fuel cell, anode material and preparation method thereof and fuel cell |
| CN110743603B (en) * | 2019-11-21 | 2022-06-10 | 江苏索普（集团）有限公司 | Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof |
| CN110743603A (en) * | 2019-11-21 | 2020-02-04 | 江苏索普（集团）有限公司 | Cobalt-iron bimetallic nitride composite electrocatalyst and preparation method and application thereof |
| CN110835103A (en) * | 2019-11-28 | 2020-02-25 | 惠州学院 | Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen |
| CN110844881A (en) * | 2019-11-28 | 2020-02-28 | 云南电网有限责任公司电力科学研究院 | Method for dehydrogenating liquid organic hydrogen storage material by using ionic liquid |
| CN110835103B (en) * | 2019-11-28 | 2023-03-14 | 惠州学院 | Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen |
| CN111185171A (en) * | 2020-01-18 | 2020-05-22 | 中北大学 | Preparation method of high-activity multi-response carbon-point composite variable-valence copper oxide nanoenzyme |
| CN111185171B (en) * | 2020-01-18 | 2022-10-21 | 中北大学 | Preparation method of high-activity multi-response carbon-point composite variable-valence copper oxide nanoenzyme |
| CN111420664A (en) * | 2020-03-11 | 2020-07-17 | 惠州学院 | Preparation method of flaky cuprous oxide/cobaltous oxide nanocomposite and application of flaky cuprous oxide/cobaltous oxide nanocomposite in catalyzing ammonia borane hydrolysis hydrogen production |
| CN111377480A (en) * | 2020-03-20 | 2020-07-07 | 苏州科技大学 | Application of iron (II) -doped molybdenum sulfide material in self-powered piezoelectricity-enhanced hydrogen production |
| CN111377480B (en) * | 2020-03-20 | 2023-08-18 | 苏州科技大学 | Application of iron (II) -doped molybdenum sulfide material in self-powered piezoelectric enhanced hydrogen production |
| CN112079332A (en) * | 2020-09-18 | 2020-12-15 | 北京大学 | Method for preparing hydrogen by directly inducing solid ammonia borane through photo-thermal method |
| CN112663088B (en) * | 2021-01-14 | 2023-06-02 | 江西省科学院能源研究所 | Preparation method of cobalt diselenide/iron oxyhydroxide composite material with nanometer petal-shaped structure |
| CN112663088A (en) * | 2021-01-14 | 2021-04-16 | 江西省科学院能源研究所 | Preparation method of cobalt diselenide/iron oxyhydroxide composite material with nano petal-shaped structure |
| CN113713863A (en) * | 2021-07-23 | 2021-11-30 | 山东大学 | Plasma alloy photocatalytic material, preparation method and application |
| CN114210337A (en) * | 2021-10-28 | 2022-03-22 | 惠州学院 | Nickel copper tungstate nano heterojunction particles, preparation method thereof and application of nickel copper tungstate nano heterojunction particles in catalytic hydrogen production |
| CN114210337B (en) * | 2021-10-28 | 2024-02-13 | 惠州学院 | Nickel copper tungstate nano heterojunction particles, preparation method thereof and application of nickel copper tungstate nano heterojunction particles in catalytic hydrogen production |
| CN114272935A (en) * | 2021-11-29 | 2022-04-05 | 惠州学院 | Catalyst for catalyzing ammonia borane to produce hydrogen and preparation method thereof |
| CN114345350A (en) * | 2022-01-20 | 2022-04-15 | 河南科技大学 | Co-based bimetallic oxide catalyst and preparation method thereof |
| CN114345350B (en) * | 2022-01-20 | 2023-10-27 | 河南科技大学 | Co-based bimetallic oxide catalyst and preparation method thereof |
| CN115487848A (en) * | 2022-09-29 | 2022-12-20 | 惠州学院 | Preparation method of nanowire nickel nitride-copper nitride composite material and application of nanowire nickel nitride-copper nitride composite material in catalysis of alcoholysis of ammonia borane to produce hydrogen |
| CN115487848B (en) * | 2022-09-29 | 2023-11-24 | 惠州学院 | Preparation method of nanowire nickel nitride-copper nitride composite material and application of nanowire nickel nitride-copper nitride composite material in catalyzing aminoborane alcoholysis to produce hydrogen |
| CN115634693A (en) * | 2022-09-30 | 2023-01-24 | 惠州学院 | Preparation method of nano composite material with hollow tube structure and application of nano composite material in catalysis of ammonia borane alcoholysis for hydrogen production |
| CN115634693B (en) * | 2022-09-30 | 2024-01-26 | 惠州学院 | Preparation method of nanocomposite with hollow tube structure and application of nanocomposite in catalyzing aminoborane alcoholysis to produce hydrogen |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109225284B (en) | 2022-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109225284A (en) | A kind of hydrogen storage material decomposition hydrogen release system | |
| Zhang et al. | Vacancies boosting strategy enabling enhanced oxygen evolution activity in a library of novel amorphous selenite electrocatalysts | |
| CN104220168B (en) | Prepare the method for the core-shell particles being supported on carrier and the thus obtained core-shell particles being supported on carrier | |
| CN102489314B (en) | Graphene-loaded double-metal nano particles for methanol and ethanol fuel cells, and preparation method for graphene-loaded double-metal nano particles | |
| CN104681823B (en) | A kind of nitrogen-doped graphene and Co3O4 hollow nano-sphere composites and its preparation method and application | |
| CN102744067B (en) | Hollow magnetic nano-grade composite catalytic material and preparation method thereof | |
| CN104966842B (en) | A kind of water oxidation reaction catalyst and preparation method thereof based on porous carbon materials | |
| Cai et al. | PdTex/C nanocatalysts with high catalytic activity for ethanol electro-oxidation in alkaline medium | |
| Hu et al. | Facet-evolution growth of Mn3O4@ CoxMn3-xO4 electrocatalysts on Ni foam towards efficient oxygen evolution reaction | |
| CN103657649B (en) | A kind of prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst | |
| WO2006086457A2 (en) | Palladium-cobalt particles as oxygen-reduction electrocatalysts | |
| CN105016399B (en) | Nano thin sheet assembled nickel-iron hydroxide multistage microspheres and preparation method thereof | |
| An et al. | Recent Advances in Dual‐Atom Site Catalysts for Efficient Oxygen and Carbon Dioxide Electrocatalysis | |
| Busser et al. | Photodeposition of Copper and Chromia on Gallium Oxide: The Role of Co‐Catalysts in Photocatalytic Water Splitting | |
| CN106848335B (en) | A kind of CuMn2O4The preparation method of/CNT composite electrocatalyst | |
| Hoseini et al. | High CO tolerance of Pt/Fe/Fe 2 O 3 nanohybrid thin film suitable for methanol oxidation in alkaline medium | |
| Jin et al. | Electrocatalytic activity of PdNi/C catalysts for allyl alcohol oxidation in alkaline solution | |
| CN110280288A (en) | The preparation method of bifunctional catalyst is precipitated in a kind of nitrogen co-doped carbon material hydrogen reduction of novel transition metal -/oxygen | |
| Mao et al. | Surface Palladium rich CuxPdy/carbon catalysts for methanol and ethanol oxidation in alkaline media | |
| Tu et al. | Cobalt oxyhydroxide and carbon dots modified by platinum as superior electrocatalyst for methanol oxidation | |
| Wang et al. | Mo remarkably enhances catalytic activity of Cu@ MoCo core-shell nanoparticles for hydrolytic dehydrogenation of ammonia borane | |
| Li et al. | A highly active porous Pt–PbOx/C catalyst toward alcohol electro-oxidation in alkaline electrolyte | |
| Zhou et al. | Oriented and robust anchoring of Fe via anodic interfacial coordination assembly on ultrathin Co hydroxides for efficient water oxidation | |
| CN104230634B (en) | Hydrogenation of acetophenone prepares the method for ethylbenzene | |
| Kumar et al. | A stable and active three-dimensional carbon based trimetallic electrocatalyst for efficient overall wastewater splitting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |