CN108380238A - A kind of cobalt acid Raney nickel and preparation method thereof for sodium borohydride hydrolysis - Google Patents
A kind of cobalt acid Raney nickel and preparation method thereof for sodium borohydride hydrolysis Download PDFInfo
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- CN108380238A CN108380238A CN201810122233.7A CN201810122233A CN108380238A CN 108380238 A CN108380238 A CN 108380238A CN 201810122233 A CN201810122233 A CN 201810122233A CN 108380238 A CN108380238 A CN 108380238A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of novel preparing hydrogen by sodium borohydride hydrolysis catalyst cobalt acid nickel (NiCo2O4) and preparation method thereof, compound type catalyst is introduced into sodium borohydride hydrogen preparation field for the first time, which can be both used alone with various forms, can also load use.The present invention synthesizes cobalt acid nickel/molecular sieve catalyst by carrier, homogeneous precipitation method of molecular sieve.Specific steps include：(1) cobalt source, nickel source, urea are dissolved in deionized water and form solution A；(2) molecular sieve is added in A and forms solution B；(3) solution B is placed in 80~130 DEG C of oil baths and is stirred a few hours, suction filtration obtains solid C；(4) solid C is sintered a few hours up to target product in 300~400 DEG C.The non-precious metal catalyst that alternative field of inorganic matter prepared by the present invention uses, in sodium borohydride hydrogen production reaction, catalytic performance is good, and the recycling period is long, corrosion-resistant, and preparation process is simple and direct, and raw material availability is high.
Description
Technical field
The invention belongs to portable hydrogen technologies, and in particular to a kind of novel preparing hydrogen by sodium borohydride hydrolysis cobalt acid nickel
(NiCo2O4) catalyst and preparation method thereof.
Background technology
Sodium borohydride is a kind of ideal hydrogen storage material, and hydrogen reserves can reach 10.8wt%.To realize sodium borohydride
The release hydrogen of stability and high efficiency, searching is a kind of of low cost, simple for production, and it is its technology to recycle the excellent catalyst of performance
It is crucial.Sodium borohydride catalyzing hydrolyzation reacts：NaBH4+2H2O=NaBO2+4H2。
Research finds that noble ruthenium, palladium have good catalytic effect for sodium borohydride hydrolysis, but because of noble metal
Price and reserves problem, are difficult to extensive use in actual production.Non-precious metal catalyst is current sodium borohydride hydrolysis
Hydrogen preparation field extensively study and application metal catalyst, wherein cobalt, nickel catalytic effect make us belong to mesh.But they be all with
The form of mixtures of metal oxide and metal exists, ununified molecular formula or certain chemical form.Such as it is catalyzed
Agent with Co-Ru-Mo-B, Co-Mo-Pd-B, Ni-Co-B, Co-Ni-P-B, Co-Cr-B, Co-Mo-B, Co-W-P, Co-P etc. no
Determine the form of mixtures expression of molecular formula, and oxidation easily occurs in use, falls off.
To improve the hydrogen generation efficiency of catalyst, increases the specific surface area of catalyst, the use of carrier is currently used method
One of.Common catalyst carrier mainly has carbon nano-fiber, carbon aerogels, γ-Al2O3、TiO2, clay, graphene, foam
Metal, activated carbon, SiO2Equal porous masses.
Prepared catalyst makes great progress in terms of catalytic effect at present, but in manufacturing cost, reuses
Aspect of performance is still faced with many problems.Therefore, searching manufacturing cost is cheap, and the catalyst that the service life is longer becomes mesh
The Main way of preceding research.
Invention content
To solve the above problems, the present invention discloses a kind of new catalyst can be used for preparing hydrogen by sodium borohydride hydrolysis --- cobalt
Sour nickel；Cobalt acid nickel is that (space group is (227) Fd-3m to inverse spinel structure, and cell parameter is 8.114x 8.114x 8.114<
90.0x 90.0x 90.0>), a variety of microscopic appearances also can be obtained by controllable preparation, such as sheet, chain, spherical, cellular
Deng, it is connected in the form of ionic bond or covalent bond between element, it is tightly combined between each other.Different from noble metal used in current or
It is non-precious metal catalyst, they are a kind of mixtures of indefinite molecular formula.Cobalt acid Raney nickel is can under a kind of natural conditions
Long-standing compound has stable physical and chemical state；With the characteristics of resistance to highly basic, service life is long, high activity；Its
Preparation method has mechanical mixed calcining method, metal salt thermal decomposition method, spray heating decomposition, co-precipitation thermal decomposition method, collosol and gel
Method, low-temperature solid-phase method, electrodeposition process and method of electrostatic spinning, the present invention, will by homogeneous precipitation method by taking molecular sieve carrier as an example
Cobalt acid nickel presoma deposits over a molecular sieve, and finally obtains cobalt acid nickel/molecular sieve catalyst by Muffle furnace sintering.The present invention
Innovative uses a kind of preparing hydrogen by sodium borohydride hydrolysis catalyst of new model, starts and stop to make to be efficient, stable, quick
Hydrogen process provides new catalyst mode.
Cobalt acid nickel/molecular sieve catalyst prepared by the present invention is combined with nickel source using cobalt source, is prepared, specifically
It is achieved through the following technical solutions：
The preparation method of preparing hydrogen by sodium borohydride hydrolysis catalyst can be implemented successively as follows：
(1) using molecular sieve, cobalt source, nickel source, urea, ethyl alcohol, deionized water as raw material, load carriers is taken to be dried；
(2) cobalt source, nickel source, urea are dissolved in deionized water and form solution A；
(3) load carriers after drying are added in step (2) described solution A and form solution B；
(4) step (3) described solution B is placed in 3~5h of heating stirring in 80~130 DEG C of oil bath, waited for after reaction,
Cooled to room temperature obtains solid C through filtering drying；
(5) step (4) the solid C is placed in 300~400 DEG C of Muffle furnaces and calcines 5~7h up to target product.
This method prepare compound can be both used alone with various forms, can also support type use, load carriers can
For γ-alundum (Al2O3), molecular sieve, carbon nanotube, titanium dioxide, silica, carbon nano-fiber, carbon aerogels, clay, stone
Black alkene, foam metal, the porous materials such as activated carbon.As a preferred embodiment, molecular sieve of the present invention is Si-Al zeolite
Molecular sieve (i.e. 13X molecular sieves).
Further, cobalt source of the present invention is cobalt acetate or cobalt nitrate.
Further, nickel source of the present invention is nickel acetate or nickel nitrate.
Further, cobalt source in step (2) of the present invention, nickel source, the amount ratio of substance of urea are 2:1:10~14.
Preferred ratio is that the amount ratio of the substance of nickel source and urea is 1:10.
Further, in step (3) of the present invention, by weight, the sum of cobalt source and nickel source are the 50 of load carriers
~200%.Preferably, by weight percentage, the sum of cobalt source and nickel source are 50%, 100%, the 200% of molecular sieve.
Further, in step (4) of the present invention, after 3~5h of oil bath heating by obtained solid at 60~80 DEG C
It is dried through air dry oven；It is placed in 5~7h of calcining in Muffle furnace.
Further, the temperature of solution B oil bath of the present invention is preferably 110 DEG C；
Further, it is preferably 350 DEG C that solid C of the present invention, which is placed in the temperature calcined in Muffle furnace,；
Another aspect of the present invention is, discloses the catalyst of method as described above preparation in preparing hydrogen by sodium borohydride hydrolysis
The application of aspect；It is specifically used under the conditions of 35 DEG C in the test of sodium borohydride hydrogen production reaction in embodiment, the catalyst
It is used in sodium borohydride (sodium hydroxide of 15wt%) aqueous solution of 10wt%, shows good catalytic performance, use 9 times
Not only without any relaxation phenomenon, in addition occur hydrogen-producing speed time by time higher the phenomenon that, i.e. the result listed by embodiment 6
It has been shown that, prepared catalyst are hydrolyzed hydrogen manufacturing and reuse in test process, after using the 4th time, occur respectively
Hydrogen-producing speed once improves 5.6%, 38%, 9.4%, 19.5%, 5.9% experimental result earlier above respectively.
The method of the invention introduces preparing hydrogen by sodium borohydride hydrolysis field using inorganic compound as catalyst for the first time, changes
The current field is mainly with the present situation of noble metal or base metal type catalyst, and preparation method is easy, device structure
Simply, raw material availability is high, such as using 4g cobalt nitrates, 2g nickel nitrates, the cobalt acid nickel of 1.6g finally can be obtained, raw material availability can
Up to 96.6%；And the recycling period is long, and it is corrosion-resistant, it is that catalyst used at present is unapproachable.
Description of the drawings
Fig. 1 is the X-ray powder diffraction pattern of finished product cobalt acid Raney nickel of the present invention；
Fig. 2 is the SEM spectrum of cobalt acid nickel/molecular sieve catalyst of the present invention；Wherein：Fig. 2A is molecular sieve surface SEM pictures；
Fig. 2 B are the SEM pictures on cobalt acid nickel/molecular sieve catalyst surface；
Fig. 3 is the EDS collection of illustrative plates of cobalt acid nickel/molecular sieve catalyst of the present invention；
Fig. 4 is production hydrogen situation of 2 cobalt acid nickel of the embodiment of the present invention/molecular sieve catalyst to sodium borohydride aqueous solution；
Fig. 5 is production hydrogen situation of 3 cobalt acid nickel of the embodiment of the present invention/molecular sieve catalyst to sodium borohydride aqueous solution；
Fig. 6 is production hydrogen situation of 4 cobalt acid nickel of the embodiment of the present invention/molecular sieve catalyst to sodium borohydride aqueous solution；
Fig. 7 is production hydrogen situation of 5 cobalt acid nickel of the embodiment of the present invention/molecular sieve catalyst to sodium borohydride aqueous solution；
Fig. 8 is that 6 cobalt acid nickel of the embodiment of the present invention/molecular sieve catalyst reuses situation；
Table 1 is the EDS elemental analyses of cobalt acid nickel/molecular sieve catalyst of the present invention.
Specific implementation mode
Following non-limiting embodiments can make those skilled in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
4.0g cobalt nitrates, 2.0g nickel nitrates are weighed, stirring in 160mL water is placed it in and makes it completely dissolved, urea is added
5.0g, ultrasonic 20min；The 13X molecular sieves for weighing 6.0g are dried at 80 DEG C in air dry oven, and the solution configured is poured into
In, react 4h under conditions of 110 DEG C.Cooled to room temperature filters, drying obtains the presoma of catalyst；It will be acquired
Presoma be placed in Muffle furnace at 350 DEG C calcine 6h to get the molecular sieve carried cobalt acid Raney nickels of target product 13X.
Referring to Fig. 1, the pdf cards of the characteristic diffraction peak and cobalt acid nickel of cobalt acid nickel fit like a glove, and illustrate cobalt acid nickel by success
Prepare.
Referring to Fig. 2, the SEM of cobalt acid nickel/molecular sieve schemes, it is seen that cobalt acid nickel is covered in the table of molecular sieve in the form of sheet
Face.
Referring to Fig. 3, the EDS of cobalt acid nickel/molecular sieve schemes, it is seen that cobalt element and nickel element are evenly distributed in point on molecular sieve
Son sieve surface, green represents cobalt element distribution (in figure in place of grey), red to be represented (in place of the black splotch to gather i.e. in figure)
Nickel element is distributed；Referring to table 1, according to their weight percent and molecular weight (cobalt：58.93 nickel：58.69) theirs are understood
Molar ratio is about 2:1, with cobalt acid nickel Co2O4Theoretical atomic ratio it is suitable.
The EDS elemental analyses of 1 cobalt acid nickel/molecular sieve catalyst of the present invention of table；
Embodiment 2
4.0g cobalt nitrates, 2.0g nickel nitrates are weighed, stirring in 160mL water is placed it in and makes it completely dissolved, urea is added
5.0g, ultrasonic 20min；The 13X molecular sieves of 6.0g are weighed at 80 DEG C after air dry oven drying, pours into the solution configured
In, react 4h under conditions of 110 DEG C.Cooled to room temperature filters, drying obtains the presoma of catalyst；It will be acquired
Presoma be placed in Muffle furnace at 350 DEG C calcine 6h to get the molecular sieve carried cobalt acid Raney nickels of target product 13X.
Catalyst prepared by embodiment 2 is subjected to active testing, the results are shown in Figure 4, in 35 DEG C, the hydrogen of 5wt%
In aqueous solution of sodium oxide, the catalyst for 5wt% sodium borohydride hydrolysis hydrogen-producing speed up to 25.952L/ (min
molNiCo2O4)。
Embodiment 3
4.0g cobalt nitrates, 2.0g nickel nitrates are weighed, stirring in 160mL water is placed it in and makes it completely dissolved, urea is added
5.0g, ultrasonic 20min；The 13X molecular sieves for weighing 6.0g dry simultaneously grind into powder at 80 DEG C in air dry oven, pour into and are matched
In the solution set, 4h is reacted under conditions of 110 DEG C.Cooled to room temperature filters, drying obtains the forerunner of catalyst
Body；Obtained presoma is placed in Muffle furnace and calcines 6h at 350 DEG C to get the molecular sieve carried cobalt acid of target product 13X
Raney nickel.
Catalyst prepared by embodiment 3 is subjected to active testing, the results are shown in Figure 5, this is urged under the conditions of 35 DEG C
Agent for sodium borohydride (sodium hydroxide of 5wt%) aqueous solution of 5wt% hydrogen-producing speed up to 31.666L/ (min
molNiCo2O4)。
Embodiment 4
2.0g cobalt nitrates, 1.0g nickel nitrates are weighed, stirring in 80mL water is placed it in and makes it completely dissolved, urea is added
2.5g, ultrasonic 20min；The 13X molecular sieves for weighing 6.0g are dried at 80 DEG C in air dry oven, and the solution configured is poured into
In, react 4h under conditions of 110 DEG C.Cooled to room temperature filters, drying obtains the presoma of catalyst；It will be acquired
Presoma be placed in Muffle furnace at 350 DEG C calcine 6h to get the molecular sieve carried cobalt acid Raney nickels of target product 13X.
Catalyst prepared by embodiment 4 is subjected to active testing, the results are shown in Figure 6, this is urged under the conditions of 35 DEG C
Agent for sodium borohydride (sodium hydroxide of 15wt%) aqueous solution of 10wt% hydrogen-producing speed up to 39.047L/ (min
molNiCo2O4)。
Embodiment 5
8.0g cobalt nitrates, 4.0g nickel nitrates are weighed, stirring in 320mL water is placed it in and makes it completely dissolved, urea is added
10.0g, ultrasonic 20min；The 13X molecular sieves for weighing 6.0g are dried at 80 DEG C in air dry oven, and the solution configured is poured into
In, react 4h under conditions of 110 DEG C.Cooled to room temperature filters, drying obtains the presoma of catalyst；It will be acquired
Presoma be placed in Muffle furnace at 350 DEG C calcine 6h to get the molecular sieve carried cobalt acid Raney nickels of target product 13X.
Catalyst prepared by embodiment 5 is subjected to active testing, the results are shown in Figure 7, this is urged under the conditions of 35 DEG C
Agent for sodium borohydride (sodium hydroxide of 15wt%) aqueous solution of 10wt% hydrogen-producing speed up to 82.38L/ (min
molNiCo2O4)。
Embodiment 6
8.0g cobalt nitrates, 4.0g nickel nitrates are weighed, stirring in 320mL water is placed it in and makes it completely dissolved, urea is added
10.0g, ultrasonic 20min；The 13X molecular sieves for weighing 6.0g are dried at 80 DEG C in air dry oven, and the solution configured is poured into
In, react 4h under conditions of 110 DEG C.Cooled to room temperature filters, drying obtains the presoma of catalyst；It will be acquired
Presoma be placed in Muffle furnace at 350 DEG C calcine 6h to get the molecular sieve carried cobalt acid Raney nickels of target product 13X.
Catalyst prepared by embodiment 6 is subjected to reuse test, the results are shown in Figure 8, under the conditions of 35 DEG C
The catalyst is in sodium borohydride (sodium hydroxide of 15wt%) aqueous solution of 10wt%, after second, catalysis is imitated
Rate significantly promotes (i.e. hydrogen-producing speed increases substantially), using 9 times without any relaxation phenomenons, hydrogen-producing speed is followed successively by 82,
221、223、161、170、234、256、306、324L/(min·molNiCo2O4) or even the later stage there is the primary ratio of hydrogen-producing speed one
The phenomenon that secondary higher.
For any person skilled in the art, without departing from the scope of the technical proposal of the invention, all
Many possible changes and modifications are made to technical solution of the present invention using the technology contents of the disclosure above, or are revised as equivalent
The equivalent embodiment of variation.Therefore, every content without departing from technical solution of the present invention, according to the technical essence of the invention to
Any simple modifications, equivalents, and modifications that upper embodiment is done should all still fall within the range of technical solution of the present invention protection
It is interior.
Claims (10)
1. a kind of catalyst can be used for preparing hydrogen by sodium borohydride hydrolysis, which is characterized in that the catalyst is cobalt acid nickel.
2. the preparation method of catalyst as described in claim 1, which is characterized in that the method and step includes：
(1) cobalt source, nickel source, urea are dissolved in deionized water and form solution A；
(2) load carriers after drying are added in step (1) described solution A and form solution B；
(3) step (2) described solution B is placed in 3~5h of heating stirring in 80~130 DEG C of oil bath, waits for being formed after reaction
Precipitation, is cooled to room temperature, and solid C is obtained through filtering drying；
(4) step (3) the solid C is placed in 300~400 DEG C of Muffle furnaces and calcines 5~7h up to target product.
3. the method for preparing catalyst of preparing hydrogen by sodium borohydride hydrolysis according to claim 2, it is characterised in that：The load
Carrier is γ-alundum (Al2O3), molecular sieve, carbon nanotube, titanium dioxide, silica, activated carbon, carbon nano-fiber, carbon gas
Gel, clay, graphene, foam metal.
4. the method for preparing catalyst of preparing hydrogen by sodium borohydride hydrolysis according to claim 1, it is characterised in that：The carrier
For Si-Al zeolite molecular sieve.
5. the method for preparing catalyst of preparing hydrogen by sodium borohydride hydrolysis according to claim 2, it is characterised in that：The cobalt source
For cobalt acetate or cobalt nitrate.
6. the method for preparing catalyst of preparing hydrogen by sodium borohydride hydrolysis according to claim 2, it is characterised in that：The nickel source
For nickel acetate or nickel nitrate.
7. the method for preparing catalyst of preparing hydrogen by sodium borohydride hydrolysis according to claim 2, it is characterised in that：The step
(1) cobalt source in, nickel source, the amount ratio of substance of urea are 2:1:(10~14).
8. the method for preparing catalyst of preparing hydrogen by sodium borohydride hydrolysis according to claim 2, it is characterised in that：The step
(2) in, by weight, the sum of cobalt source and nickel source are the 50~200% of load carriers.
9. the method for preparing catalyst of preparing hydrogen by sodium borohydride hydrolysis according to claim 2, it is characterised in that：The step
(3) obtained solid C is placed in Muffle furnace through air dry oven drying at 60~80 DEG C and calcines.
10. application of the catalyst as described in claim 1 in terms of preparing hydrogen by sodium borohydride hydrolysis.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109331862A (en) * | 2018-09-30 | 2019-02-15 | 湖南理工学院 | A kind of propenal aldehyde acetal/aniline reaction prepares catalyst of quinoline and preparation method thereof |
| CN110508304A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol NiCo2O4/SiC-SiO2- Foam and preparation method |
| CN111330604A (en) * | 2020-03-16 | 2020-06-26 | 西安交通大学 | Sodium borohydride hydrolysis hydrogen production catalyst, preparation method and application thereof |
| CN113403628A (en) * | 2021-05-31 | 2021-09-17 | 华南理工大学 | Non-noble metal hydrogen evolution electrocatalyst based on structural nanocrystallization combination synergistic modification and preparation method and application thereof |
| CN114618539A (en) * | 2022-02-23 | 2022-06-14 | 燕山大学 | Sodium borohydride hydrogen production catalyst with hierarchical structure and preparation method and application thereof |
| CN114702003A (en) * | 2022-04-11 | 2022-07-05 | 安徽工业大学 | Solid-state hydrolysis hydrogen production agent and preparation method thereof |
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| CN109331862A (en) * | 2018-09-30 | 2019-02-15 | 湖南理工学院 | A kind of propenal aldehyde acetal/aniline reaction prepares catalyst of quinoline and preparation method thereof |
| CN110508304A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol NiCo2O4/SiC-SiO2- Foam and preparation method |
| CN110508304B (en) * | 2019-08-29 | 2021-09-14 | 华南农业大学 | Biological methanol catalyst NiCo for full-component conversion of biogas2O4/SiC-SiO2-Foam and preparation method |
| CN111330604A (en) * | 2020-03-16 | 2020-06-26 | 西安交通大学 | Sodium borohydride hydrolysis hydrogen production catalyst, preparation method and application thereof |
| CN113403628A (en) * | 2021-05-31 | 2021-09-17 | 华南理工大学 | Non-noble metal hydrogen evolution electrocatalyst based on structural nanocrystallization combination synergistic modification and preparation method and application thereof |
| CN113403628B (en) * | 2021-05-31 | 2022-05-24 | 华南理工大学 | Non-noble metal hydrogen evolution electrocatalyst based on structural nanocrystallization combination synergistic modification and preparation method and application thereof |
| CN114618539A (en) * | 2022-02-23 | 2022-06-14 | 燕山大学 | Sodium borohydride hydrogen production catalyst with hierarchical structure and preparation method and application thereof |
| CN114702003A (en) * | 2022-04-11 | 2022-07-05 | 安徽工业大学 | Solid-state hydrolysis hydrogen production agent and preparation method thereof |
| CN114702003B (en) * | 2022-04-11 | 2023-09-29 | 安徽工业大学 | Solid hydrolysis hydrogen production agent and preparation method thereof |
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Application publication date: 20180810 |