CN113600196B - Based on Fe 2 B-Co 2 Preparation method of B composite material sodium borohydride hydrolysis hydrogen production catalyst - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 29
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940045136 urea Drugs 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 4
- 229960002668 sodium chloride Drugs 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 238000003746 solid phase reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000004590 computer program Methods 0.000 description 6
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- 239000012085 test solution Substances 0.000 description 6
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- 230000005540 biological transmission Effects 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 229910012375 magnesium hydride Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 101800000407 Brain natriuretic peptide 32 Proteins 0.000 description 1
- 101800002247 Brain natriuretic peptide 45 Proteins 0.000 description 1
- -1 Lithium aluminum hydride Chemical compound 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 239000011232 storage material Substances 0.000 description 1
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/23—
-
- 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
-
- 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
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the field of hydrogen evolution energy, and particularly relates to a Fe-based catalyst 2 B‑Co 2 B compositeThe invention relates to a preparation method of a sodium borohydride hydrolysis hydrogen production catalyst, which adopts a solid-phase reaction method, adopts sodium chloride solid as a template, mixes cobalt chloride hexahydrate, ferric chloride hexahydrate and urea, fully and uniformly grinds the mixture, and then reacts with sodium borohydride serving as a strong reducing agent to prepare the sodium borohydride hydrolysis hydrogen production composite catalyst with excellent catalytic performance. The invention uses non-noble metal cobalt and iron which have abundant reserves and are cheaper to prepare Co 2 B‒Fe 2 The B composite material not only has higher sodium borohydride hydrogen evolution performance and excellent stability, but also provides an effective synthesis idea for preparing the efficient and stable sodium borohydride hydrogen evolution non-noble metal catalyst by the solid-phase reaction method.
Description
Technical Field
The invention belongs to the field of hydrogen evolution energy, and particularly relates to a Fe-based catalyst 2 B-Co 2 B preparing a catalyst for preparing hydrogen by hydrolyzing sodium borohydride serving as a composite material.
Background
Environmental pollution caused by the large consumption of non-renewable energy sources (such as petroleum, coal and natural gas) has forced people to accelerate the search for clean energy sources for sustainable development to replace fossil energy sources. Among the many clean energy sources, hydrogen is one of the most promising energy carriers due to its high heat of combustion (142 MJ kg-1) and environmentally friendly combustion products. And also has potential application in various energy conversion devices (hydrogen fuel cells). A common hydrogen storage material is sodium borohydride (NaBH) 4 ) Ammonia borane (NH) 3 BH 3 ) Lithium aluminum hydride (LiAlH) 4 ) And magnesium hydride (MgH2), and the like. In which NaBH is present 4 Has received much attention due to advantageous conditions of high hydrogen storage density (10.6wt.%), mild reaction conditions, high purity and convenience in collecting hydrogen. Recent studies have shown that NaBH can be regenerated using a high energy ball milling process 4 The greatest difficulty in commercial applications is solved. Because the self-decomposition speed of sodium borohydride is very slow and is difficult to meet the demand speed of people for hydrogen, an effective catalyst needs to be added to improve the hydrogen evolution reaction rate. Research proves that the noble metal catalyst has high-efficiency and stable performance on hydrogen production by sodium borohydride, and comprises catalyst RuP 3 –CoP、Ru-Fe/GO、Ru-Co/CNTs、Pt 58 Ni 33 Au 9 Pd/PD-ZIF-67, Rh/Ni BNPs and the like. Because the cost of noble metal is high and scarcity seriously affects the wide application of industrialization, the invention of a non-noble metal sodium borohydride hydrolysis hydrogen production catalyst with rich reserves, high efficiency and stability is needed.
Disclosure of Invention
The invention aims to provide a Fe-based alloy 2 B-Co 2 The preparation method of the composite material hydrolysis hydrogen production catalyst solves the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
based on Fe 2 B-Co 2 The preparation method of the B composite material sodium borohydride hydrolysis hydrogen production catalyst comprises the following steps:
step 1: weighing a certain amount of cobalt chloride hexahydrate, ferric chloride hexahydrate, sodium chloride and urea, uniformly mixing, and then grinding;
step 2: transferring the sample obtained in the step 1 into an oven, preserving heat for a plurality of hours, then taking out the sample, grinding the sample uniformly again, and finally adding a certain amount of sodium borohydride solid in a room temperature environment for mixing reaction;
and 3, step 3: fully washing the reaction product generated in the step 2 by using deionized water, collecting the obtained product, placing the collected product in a vacuum drying oven for heat preservation, and obtaining Co 2 B‒Fe 2 And B, a composite material.
Further, the Co 2 B‒Fe 2 The molar ratio of cobalt to iron in the B composite material is 1-24: 1.
further, the temperature of the oven is controlled at 60 ℃, and the heat preservation time is 4 hours; the temperature of the vacuum drying oven is 60 ℃, and the temperature is kept for 12 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. co prepared from cheap non-noble metal cobalt and iron 2 B‒Fe 2 The B composite material not only has higher sodium borohydride hydrogen evolution performance and excellent stability, but also provides the efficient and stable sodium borohydride hydrogen evolution non-noble metal catalyst by the solid-phase reaction methodAn effective synthesis thought.
2、Co 2 B‒Fe 2 The hydrogen evolution rate of the B composite material in alkaline sodium borohydride aqueous solution is up to 5315.8 mL H2 min -1 g cat -1 And under the same conditions, the composite material is superior to most of the prior non-noble metal catalyst composite materials.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of composites of example 1, example 2 and example 5 of the present invention;
FIG. 2 is (a) a scanning electron microscope picture, (b) a transmission electron microscope picture, and (c) a high-resolution transmission electron microscope picture, in example 5 of the present invention;
FIG. 3 is a graph showing the relationship between (a) the amount of hydrogen generated and time and (b) the hydrogen evolution rate in examples 1 to 6 of the present invention;
FIG. 4 is (a) the relationship between the hydrogen generation amount and the time at different test temperatures, (b) an Arrhenius plot in example 5;
FIG. 5 shows the relationship between the hydrogen generation amount and the time in different cycle tests and the hydrogen generation rate in the corresponding cycle test in example 5 of the present invention.
Detailed Description
The technical solution in the embodiment of the present invention will be described below with reference to fig. 1 to 5 of the present invention.
First, example 1
1. Preparation of Co 2 Catalyst B:
weighing 2 mmol of cobalt chloride hexahydrate, 60 mmol of sodium chloride and 60 mmol of urea, mixing, fully and uniformly grinding in a mortar, and then placing the ground sample in a blast oven at 60 ℃ for heat preservation for 4 hours. The dried sample was ground thoroughly and uniformly, and 12 mmol of sodium borohydride solid was added thereto at room temperature, followed by mixing and reacting for 1 hour. Then, fully washing a reaction product by using deionized water, collecting the obtained product, placing the collected product in a vacuum drying box at 60 ℃, and preserving heat for 12 hours to obtain a product Co 2 And (B) a catalyst.
2. And (3) testing the catalyst:
to 100 ml50 ml of 150mM NaBH was added to a three-neck round-bottom flask 4 Aqueous solution (containing 0.4 wt% NaOH), followed by placing the three-necked round bottom flask in a 25 ℃ water bath and incubating with continuous stirring for 30 minutes until the indication of the electronic balance attached to the test is unchanged. The above conditions of constant temperature and continuous stirring were maintained, 10 mg of catalyst was added to the test solution, and the generated gas was collected by a drainage method. The drained water was weighed using a scale and the scale was connected to a computer to record the mass of the instantaneous drained water. And calculating the hydrogen gas rate generated in unit time by using a computer program, thereby calculating the hydrogen evolution conversion rate.
The hydrogen evolution rate (HGR) is calculated according to the following equation:
wherein the content of the first and second substances,
is the amount of water discharged, m is the mass of catalyst and t is the total reaction time.
Second, example 2
1. Preparation of Fe 2 Catalyst B:
weighing 2 mmol of ferric chloride hexahydrate, 60 mmol of sodium chloride and 60 mmol of urea, mixing, fully and uniformly grinding in a mortar, and then placing the ground sample in a blast oven at 60 ℃ for heat preservation for 4 hours. The dried sample was ground thoroughly and uniformly, and 12 mmol of sodium borohydride solid was added thereto at room temperature, followed by mixing and reacting for 1 hour. Then using deionized water to fully wash the reaction product, collecting the obtained product, placing the product in a vacuum drying oven at 60 ℃ for heat preservation for 12 hours to obtain a product Fe 2 And B, a catalyst.
3. And (3) testing the catalyst:
to a 100 ml three-neck round-bottom flask was added 50 ml of 150mM NaBH 4 Aqueous solution (containing 0.4 wt% NaOH), followed by placing the three-necked round bottom flask in a 25 ℃ water bath and incubating with continuous stirring for 30 minutes until the indication of the electronic balance attached to the test is unchanged. Keep the above constantWith gentle continuous stirring, 10 mg of catalyst was added to the test solution and the gas produced was collected by drainage. The drained water was weighed using a scale and the scale was connected to a computer to record the mass of the instantaneous drained water. And calculating the hydrogen gas rate generated in unit time by using a computer program, thereby calculating the hydrogen evolution conversion rate.
Third, example 3
1. Preparation of Co 2 B‒Fe 2 B catalyst (Co: Fe =1: 1):
weighing 1 mmol of cobalt chloride hexahydrate, 1 mmol of ferric chloride hexahydrate, 60 mmol of sodium chloride and 60 mmol of urea, mixing, fully and uniformly grinding in a mortar, and then putting the ground sample in a forced air oven at 60 ℃ for heat preservation for 4 hours. The dried sample was ground thoroughly and uniformly, and 12 mmol of sodium borohydride solid was added thereto at room temperature, followed by mixing and reacting for 1 hour. Then using deionized water to fully wash the reaction product, collecting the obtained product, placing the collected product in a vacuum drying oven at 60 ℃ for heat preservation for 12 hours to obtain a product Co 2 B‒Fe 2 And B, a catalyst.
2. And (3) testing the catalyst:
to a 100 ml three-neck round-bottom flask was added 50 ml of 150mM NaBH 4 Aqueous solution (containing 0.4 wt% NaOH), followed by placing the three-necked round bottom flask in a 25 ℃ water bath and incubating for 30 minutes with continuous stirring until the indication of the electronic balance attached to the test is unchanged. The above conditions of constant temperature and continuous stirring were maintained, 10 mg of catalyst was added to the test solution, and the generated gas was collected by a drainage method. The drained water was weighed using a scale and the scale was connected to a computer to record the mass of the instantaneous drained water. And calculating the hydrogen gas rate generated in unit time by using a computer program, thereby calculating the hydrogen evolution conversion rate.
Fourth, example 4
1. Preparation of Co 2 B‒Fe 2 B catalyst (Co: Fe =9: 1):
weighing 1.8 mmol of cobalt chloride hexahydrate, 0.2 mmol of ferric chloride hexahydrate, 60 mmol of sodium chloride and 60 mmol of urea, mixing, and fully grinding in a mortarAfter homogenisation, the ground sample was kept in a forced air oven at 60 ℃ for 4 hours. The dried sample was ground thoroughly and uniformly, and 12 mmol of sodium borohydride solid was added thereto at room temperature, followed by mixing and reacting for 1 hour. Then using deionized water to fully wash the reaction product, collecting the obtained product, placing the collected product in a vacuum drying oven at 60 ℃ for heat preservation for 12 hours to obtain a product Co 2 B‒Fe 2 And B, a catalyst.
3. And (3) testing the catalyst:
to a 100 ml three-neck round-bottom flask was added 50 ml of 150mM NaBH 4 Aqueous solution (containing 0.4 wt% NaOH), followed by placing the three-necked round bottom flask in a 25 ℃ water bath and incubating with continuous stirring for 30 minutes until the indication of the electronic balance attached to the test is unchanged. The above conditions of constant temperature and continuous stirring were maintained, 10 mg of catalyst was added to the test solution, and the generated gas was collected by a drainage method. The drained water was weighed using a scale and the scale was connected to a computer to record the mass of the instantaneous drained water. And calculating the hydrogen gas rate generated in unit time by using a computer program, thereby calculating the hydrogen evolution conversion rate.
Fifth, example 5
1. Preparation of Co 2 B‒Fe 2 B catalyst (Co: Fe =15: 1):
weighing 1.875 mmol of cobalt chloride hexahydrate, 0.125 mmol of ferric chloride hexahydrate, 60 mmol of sodium chloride and 60 mmol of urea, mixing, fully and uniformly grinding in a mortar, and then putting the ground sample in a blast oven at 60 ℃ for heat preservation for 4 hours. The dried sample was ground thoroughly and uniformly, and 12 mmol of sodium borohydride solid was added thereto at room temperature, followed by mixing and reacting for 1 hour. Then using deionized water to fully wash the reaction product, collecting the obtained product, placing the collected product in a vacuum drying oven at 60 ℃ for heat preservation for 12 hours to obtain a product Co 2 B‒Fe 2 And B, a catalyst.
2. And (3) testing the catalyst:
to a 100 ml three-neck round-bottom flask was added 50 ml of 150mM NaBH 4 Aqueous solution (containing 0.4 wt% NaOH), then the three-neck round-bottom flask is placed in a water bath at 25 ℃ and kept for 30 minutes with continuous stirring,until the scale of the electronic balance connected with the test is unchanged. The above conditions of constant temperature and continuous stirring were maintained, 10 mg of catalyst was added to the test solution, and the generated gas was collected by a drainage method. The drained water was weighed using a scale and the scale was connected to a computer to record the mass of the instantaneous drained water. And calculating the hydrogen gas rate generated in unit time by using a computer program so as to calculate the hydrogen evolution conversion rate.
Sixth, example 6
1. Preparation of Co 2 B‒Fe 2 B catalyst (Co: Fe =24: 1):
weighing 1.92 mmol of cobalt chloride hexahydrate, 0.08 mmol of ferric chloride hexahydrate, 60 mmol of sodium chloride and 60 mmol of urea, mixing, fully and uniformly grinding in a mortar, and then putting the ground sample in a forced air oven at 60 ℃ for heat preservation for 4 hours. The dried sample was ground thoroughly and uniformly, and 12 mmol of sodium borohydride solid was added thereto at room temperature, followed by mixing and reacting for 1 hour. Then, fully washing a reaction product by using deionized water, collecting the obtained product, placing the collected product in a vacuum drying box at 60 ℃, and preserving heat for 12 hours to obtain a product Co 2 B‒Fe 2 And (B) a catalyst.
3. And (3) testing the catalyst:
to a 100 ml three-neck round-bottom flask was added 50 ml of 150mM NaBH 4 Aqueous solution (containing 0.4 wt% NaOH), followed by placing the three-necked round bottom flask in a 25 ℃ water bath and incubating with continuous stirring for 30 minutes until the indication of the electronic balance attached to the test is unchanged. The above conditions of constant temperature and continuous stirring were maintained, 10 mg of catalyst was added to the test solution, and the generated gas was collected by a drainage method. The drained water was weighed using a balance and the balance was connected to a computer for recording the mass of the instantaneous drained water. And calculating the hydrogen gas rate generated in unit time by using a computer program, thereby calculating the hydrogen evolution conversion rate.
Seventh, analysis of results
It can be seen from FIG. 1 that the composite materials of sample example 1, example 2 and example 5 respectively have Co 2 B and Fe 2 Characteristic peak of X-ray powder diffraction of B standard, showing TongThe target catalyst is successfully prepared by a solid-phase reduction method.
From fig. 2(a) it can be observed that the morphology of catalyst example 5 is uniformly dispersed nanoparticulate, which is the result of the preparation of hard templates with sodium chloride. The morphology of the catalyst of example 5 is again demonstrated by transmission electron microscopy in fig. 2(b) as nanoparticles, with the black circles representing the nanoparticles of example 2. Further, as can be seen from the high-resolution transmission electron microscope image of FIG. 2(c), in example 5, Fe was clearly present 2 B and Co 2 B lattice fringes show that Fe is successfully synthesized 2 B-Co 2 B, a composite material.
As can be seen from fig. 3 (a), the most hydrogen gas is generated in the same time in examples 1, 2, 3, 4, 5 and 6 in example 5, and the hydrogen evolution rate in examples 1, 2, 3, 4, 5 and 6 can be calculated by formula (1), and from fig. 3 (b), it can be confirmed that example 5 has the best hydrogen gas generation rate.
FIG. 4 shows that the relationship of sodium borohydride hydrogen in example 5 was studied in the temperature range of 298-318K, and from FIG. 4 (a), it can be found that the higher the temperature is, the more hydrogen is generated in the same time. The activation energy of example 5 shown in fig. 4 (b) was calculated by arrhenius' equation, and the lower activation energy was one of the reasons why the catalyst performance was excellent.
FIG. 5 shows the cycle stability obtained by repeating the cycle test, which is one of the important indicators for evaluating the catalyst performance, as shown in FIG. 5, the catalyst performance is reduced less in each cycle test, and after five cycle tests, the catalyst of example 5 still maintains higher catalytic activity, indicating that Fe 2 B-Co 2 The B composite material catalyst has excellent stability, Co 2 B‒Fe 2 The hydrogen evolution rate of the B composite material in alkaline sodium borohydride aqueous solution is up to 5315.8 mL H2 min -1 g cat -1 And under the same conditions, the composite material is superior to most of the prior non-noble metal catalyst composite materials.
The invention uses non-noble metal cobalt and iron which have abundant reserves and are cheaper to prepare Co 2 B‒Fe 2 The B composite material not only has higher sodium borohydride hydrogen evolution performance and excellent stability, but also provides an effective synthesis idea for preparing the efficient and stable sodium borohydride hydrogen evolution non-noble metal catalyst by the solid-phase reaction method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and it is to be understood that the invention is not limited thereto, but may be modified within the scope of the appended claims.
Claims (1)
1. Based on Fe 2 B-Co 2 The preparation method of the B composite material sodium borohydride hydrolysis hydrogen production catalyst is characterized by comprising the following steps:
step 1: weighing a certain amount of cobalt chloride hexahydrate, ferric chloride hexahydrate, sodium chloride and urea, uniformly mixing, and grinding;
step 2: transferring the sample obtained in the step 1 into an oven, preserving heat for a plurality of hours, then taking out the sample, grinding the sample uniformly again, and finally adding a certain amount of sodium borohydride solid in a room temperature environment for mixing reaction;
and 3, step 3: fully washing the reaction product generated in the step 2 by using deionized water, collecting the obtained product, placing the collected product in a vacuum drying oven for heat preservation, and obtaining Fe 2 B‒Co 2 B, a composite material;
said Fe 2 B‒Co 2 The molar ratio of cobalt to iron in the B composite material is 1-24: 1, controlling the temperature of the oven at 60 ℃, and keeping the temperature for 4 hours; the temperature of the vacuum drying oven is 60 ℃, and the temperature is kept for 12 hours.
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| CN1302845C (en) * | 2004-03-11 | 2007-03-07 | 上海师范大学 | Co-Fe-B amorphous alloy catalyst, its preparation method and application |
| CN101347736A (en) * | 2007-07-20 | 2009-01-21 | 中国科学院金属研究所 | Catalyst for hydrogen production by catalyzing and hydrolyzing borohydride and preparation method thereof |
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| CN111905782B (en) * | 2020-09-10 | 2022-10-28 | 广西师范大学 | Preparation method of catalyst for hydrogen production by hydrolysis based on Ru/r-CoP composite material |
| CN113171776A (en) * | 2021-04-29 | 2021-07-27 | 苏州西热节能环保技术有限公司 | Supported catalyst for preparing hydrogen by hydrolyzing sodium borohydride solution, preparation method and application |
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