CN115739094B - Preparation method and application of copper-nickel oxide composite nanowire film - Google Patents
Preparation method and application of copper-nickel oxide composite nanowire film Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- LDSIKPHVUGHOOI-UHFFFAOYSA-N copper;oxonickel Chemical compound [Ni].[Cu]=O LDSIKPHVUGHOOI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 85
- 239000000243 solution Substances 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- 238000005187 foaming Methods 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 35
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 239000004202 carbamide Substances 0.000 claims description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 32
- 239000003054 catalyst Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 14
- 229910000365 copper sulfate Inorganic materials 0.000 description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 13
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 13
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 150000001879 copper Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- UILUIVJIQOFVPS-UHFFFAOYSA-J copper;nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Ni+2].[Cu+2] UILUIVJIQOFVPS-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
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- Catalysts (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the technical field of catalytic materials, and particularly relates to a preparation method of a copper-nickel oxide composite nanowire film and application of the copper-nickel oxide composite nanowire film in catalyzing ammonia borane hydrogen production. The process effectively realizes the setting of the nickel-copper ratio in the raw materials, the whole preparation process is simple to operate, environment-friendly, very good in experimental reproducibility, low in cost and easy for industrial production, and the copper-nickel oxide composite nanowire film prepared by the method has very high catalytic activity in the ammonia borane alcoholysis reaction.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a preparation method of a copper-nickel oxide composite nanowire film and application of the copper-nickel oxide composite nanowire film prepared by the method in catalyzing ammonia borane to produce hydrogen.
Background
Ammonia borane (Ammoniabaoriginal), which has a theoretical hydrogen content of 19.6wt%, is the chemical hydrogen storage material with the highest current hydrogen content, and when a suitable catalyst is present, ammonia borane can stably release hydrogen by alcoholysis. The nano material has extremely large specific surface area, can expose more catalytic active sites, and greatly improves the activity of the catalyst, so that the catalytic performance of the material is remarkably improved, and therefore, a plurality of nano-scale catalysts are used for ammonia borane catalytic reaction. However, during the catalytic process, the nanoparticles are associated with unavoidable agglomeration, resulting in a decrease in material stability, which greatly affects the practical application of the catalyst. To solve this problem, metal nanoparticles are often supported on certain substrates, such as metal organic frameworks, graphene, carbon nanotubes, etc., to improve the stability of the material. However, the material cost is relatively high, the preparation process is complex, and the large-scale production is difficult, and at present, no report that copper-nickel oxide can be used for producing hydrogen by ammonia borane catalytic alcoholysis is found.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a preparation method of a copper-nickel oxide composite nanowire film, which can effectively realize the proportioning of nickel and copper in raw materials, has the advantages of simple operation in the preparation process, environment friendliness, excellent experimental reproducibility, low cost, easy industrial production and large-scale production of the copper-nickel oxide composite nanowire film.
The second technical problem to be solved by the present invention is to provide a copper-nickel oxide composite nanowire film prepared by the above method, which film is composed of nanowires with a diameter of about 20 nm.
The third technical problem to be solved by the invention is to provide the application of the copper-nickel oxide composite nanowire film prepared by the method in catalyzing ammonia borane to produce hydrogen, and the copper-nickel oxide composite nanowire film prepared by the method shows very high performance in ammonia borane catalytic hydrogen production, and is expected to realize industrialized preparation of a catalyst for catalytic hydrogen production.
The invention solves the problems by the following technical proposal:
the preparation method of the copper-nickel oxide composite nanowire film comprises the following steps:
(1) Dissolving water-soluble cupric salt and nickel salt in water to prepare mixed salt solution A with cupric salt concentration of 0.075-0.3mol/L and nickel salt concentration of 0.05-0.2 mol/L;
(2) Adding urea into water, stirring and dissolving to prepare solution B with urea concentration of 0.25-2.5 mol/L;
(3) Stirring Cetyl Trimethyl Ammonium Bromide (CTAB) and dissolving in water to form a solution C with the mass fraction of 0.05-1%;
(4) The volume ratio is 1: (0.5-4): (0.5-8) solution A, solution B and solution C, firstly mixing the solutions A and B, then adding the solution C into the mixed solution, and stirring for 10-30 min;
(5) Rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the last step to the reaction kettle for reaction for 2-10 h at 120-180 ℃;
(6) And collecting the foaming nickel after the reaction, repeatedly flushing the foaming nickel by using ethanol and water, and then placing the foaming nickel into a tube furnace to calcine the foaming nickel for 1 to 6 hours at 350 to 500 ℃ in an inert gas atmosphere to obtain the copper-nickel oxide composite nanowire film.
Further, the molar ratio of the cupric salt to the nickel salt is preferably 3:2, the copper-nickel oxide composite nanowire film can obtain higher ammonia borane alcoholysis catalytic activity.
The application of the copper-nickel oxide composite nanowire film comprises the following steps of: cutting the copper-nickel oxide composite nanowire film prepared by the method, and putting the copper-nickel oxide composite nanowire film into a methanol solution containing ammonia borane and sodium hydroxide. One specific way of use is illustrated: cutting a copper-nickel oxide composite nanowire film with the length of 5 cm and the width of 3 cm prepared by the method as a catalyst for preparing hydrogen by ammonia borane alcoholysis, putting the catalyst into a methanol solution containing 3mmol ammonia borane and 10mmol sodium hydroxide, and generating 20-130 mL hydrogen in 1 minute.
The beneficial effects of the invention are as follows:
(1) The invention adopts a hydrothermal synthesis method, firstly, raw materials are mixed according to a certain proportion, urea is used as a homogeneous phase precipitator to generate hydroxide ions and metal salt to generate precipitation reaction at high temperature, nickel hydroxide-copper hydroxide precursor loaded on a foaming nickel substrate is generated, then the precursor is dehydrated in inert gas to generate a copper nickel oxide composite nanowire film by calcining, and the film is composed of nanowires with the diameter of about 20 nanometers. The preparation method effectively realizes the allocation of the nickel-copper ratio in the raw materials, has the advantages of simple operation, environment friendliness, very good experimental reproducibility, low cost and easy industrial production, and can be used for producing the copper-nickel oxide composite nanowire film in a large scale. The combination of urea, CTAB and foaming nickel plays an important role in the morphology of a synthetic sample, and the nanowire film cannot be obtained without using urea, CTAB and foaming nickel simultaneously in the synthetic process.
(2) The copper-nickel oxide composite nanomaterial prepared by the method has high performance in catalyzing the alcoholysis of ammonia borane to produce hydrogen, and is expected to realize industrialized preparation of a catalyst for catalyzing the production of hydrogen.
Drawings
Fig. 1: XRD spectrum of the sample obtained in example 1.
Fig. 2: SEM photograph of the sample obtained in example 1.
Fig. 3: SEM photograph of the sample obtained in comparative example 1.
Fig. 4: SEM photograph of the sample obtained in comparative example 2.
Detailed Description
The present invention will be further described with reference to the following detailed description and the accompanying drawings, but the present invention is not limited thereto. Reagents and apparatus for use in the present invention are commercially available from general sources unless otherwise specified.
Example 1:
3mmol of copper sulfate and 2 mmol of nickel sulfate are dissolved in 20 mL water to prepare a mixed salt solution A; adding 20 mmol of urea into 20 mL water, stirring and dissolving to form a solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 400 ℃ in a nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 130 mL hydrogen can be generated within 1 minute.
FIG. 1 is an XRD pattern of the sample obtained in example 1, and it can be seen from FIG. 1 that the CuO-NiO composite can be well supported and dispersed in the Ni matrix by the method of example 1; fig. 2 is an SEM scanning electron microscope of example 1, and it can be seen from fig. 2 that a nanowire material having a diameter of about 20nm can be prepared by the method of example 1.
Example 2: the urea dosage is reduced to 10mmol
3mmol of copper sulfate and 2 mmol of nickel sulfate are dissolved in 20 mL water to prepare a mixed salt solution A; adding 10mmol of urea into 20 mL water, stirring and dissolving to form solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 400 ℃ in a nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 107 mL hydrogen can be generated within 1 minute.
Example 3: urea usage 50mmol
3mmol of copper sulfate and 2 mmol of nickel sulfate are dissolved in 20 mL water to prepare a mixed salt solution A; adding 50mmol of urea into 20 mL water, stirring and dissolving to form solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 400 ℃ in a nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 98 mL hydrogen can be generated within 1 minute.
Example 4: the calcination temperature becomes 350 DEG C
3mmol of copper sulfate and 2 mmol of nickel sulfate are dissolved in 20 mL water to prepare a mixed salt solution A; adding 20 mmol of urea into 20 mL water, stirring and dissolving to form a solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 350 ℃ in nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 115 mL hydrogen can be generated within 1 minute.
Example 5: the calcination temperature was changed to 500 DEG C
3mmol of copper sulfate and 2 mmol of nickel sulfate are dissolved in 20 mL water to prepare a mixed salt solution A; adding 20 mmol of urea into 20 mL water, stirring and dissolving to form a solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 500 ℃ in nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 110 mL hydrogen can be generated within 1 minute.
Example 6: the ratio of copper sulfate to nickel sulfate in example 1 was changed to 4:1
Dissolving 4mmol of copper sulfate and 1 mmol of nickel sulfate in 20 mL water to prepare a mixed salt solution A; adding 20 mmol of urea into 20 mL water, stirring and dissolving to form a solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 400 ℃ in a nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 112 mL hydrogen can be generated within 1 minute.
Comparative example 1: CTAB as in example 1 was not added
3mmol of copper sulfate and 2 mmol of nickel sulfate are dissolved in 40 mL water to prepare a mixed salt solution A; adding 20 mmol of urea into 40 mL water, stirring and dissolving to form solution B; firstly, mixing the solution A and the solution B, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 400 ℃ in a nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 68 mL hydrogen can be generated within 1 minute.
Fig. 2 is an SEM image of the comparative example, and as can be seen from fig. 2, the nanowires in the obtained sample were relatively thick, with a diameter of about 50 a nm a, and the nanowires were tightly agglomerated at this time, using the method of comparative example 1.
Comparative example 2: the urea of example 1 was replaced with sodium hydroxide
3mmol of copper sulfate and 2 mmol of nickel sulfate are dissolved in 20 mL water to prepare a mixed salt solution A; adding 20 mmol of sodium hydroxide into 20 mL water, stirring and dissolving to form a solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 400 ℃ in a nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 51 mL hydrogen can be generated within 1 minute.
Fig. 3 is an SEM scanning electron microscope image of the comparative example, and as can be seen from fig. 3, a thin film composed of nanoparticles was obtained by the method of comparative example 2.
Comparative example 3: the ratio of copper sulfate to nickel sulfate in example 1 was changed to 1:4
1 mmol of copper sulfate and 4mmol of nickel sulfate are dissolved in 20 mL water to prepare a mixed salt solution A; adding 20 mmol of urea into 20 mL water, stirring and dissolving to form a solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 400 ℃ in a nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 28 mL hydrogen can be generated within 1 minute.
Comparative example 4: the ratio of copper sulfate to nickel sulfate in example 1 was changed to 2:3
2 mmol of copper sulfate and 3mmol of nickel sulfate are dissolved in 20 mL water to prepare a mixed salt solution A; adding 20 mmol of urea into 20 mL water, stirring and dissolving to form a solution B; 1 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 40 mL water with stirring to form a C solution; firstly mixing the solution A and the solution B, then adding the solution C into the mixed solution, and stirring for 10 min; rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the previous step to a 100 mL reaction kettle for reaction at 160 ℃ for 6 h; the foaming nickel after the reaction is collected, repeatedly washed by water and ethanol, and then put into a tube furnace to be calcined at 400 ℃ in a nitrogen atmosphere for 3 h. The copper-nickel oxide composite nanowire film prepared by the method is used as a catalyst for preparing hydrogen by alcoholysis of ammonia borane, a piece of foaming nickel with the length of 5 cm and the width of 3 cm is cut and put into a methanol solution containing 3mmol of ammonia borane and 10mmol of sodium hydroxide to be used as a catalyst, and 28 mL hydrogen can be generated within 1 minute.
As can be seen from a comparison of example 1 with comparative example 1, without CTAB, the nanowires in the resulting sample were relatively thick, about 50 a nm a in diameter, and the nanowires were tightly agglomerated at this time.
As can be seen from a comparison of example 1 with comparative example 2, the use of sodium hydroxide instead of urea resulted in a film consisting of nanoparticles.
As can be seen from a comparison of example 1 with comparative examples 3 to 4, a molar ratio of 3:2 and the copper-nickel oxide composite nanowire film prepared by the divalent copper salt and the divalent nickel salt has higher catalytic activity.
As can be seen from comparison of example 1 with example 6 and comparative examples 3 to 4, the molar ratio is 3:2 and the divalent copper salt and divalent nickel salt, so that the molar ratio of the divalent copper salt to the divalent nickel salt is 3:2 is a more preferable condition.
It will be understood that the above embodiments are further illustrative of the present invention and are not intended to limit the scope of the invention, and that all other modifications and variations which may be obtained without the inventive effort by those skilled in the art are within the scope of the invention.
Claims (4)
1. The application of the copper-nickel oxide composite nanowire film in catalyzing ammonia borane alcoholysis to prepare hydrogen is characterized in that the preparation method of the copper-nickel oxide composite nanowire film comprises the following steps:
(1) Dissolving water-soluble cupric salt and nickel salt in water to prepare mixed salt solution A with cupric salt concentration of 0.075-0.3mol/L and nickel salt concentration of 0.05-0.2 mol/L;
(2) Adding urea into water, stirring and dissolving to prepare solution B with urea concentration of 0.25-2.5 mol/L;
(3) Stirring and dissolving hexadecyl trimethyl ammonium bromide in water to form a solution C with the mass fraction of 0.05-1%;
(4) The volume ratio is 1: (0.5-4): (0.5-8) solution A, solution B and solution C, firstly mixing the solutions A and B, then adding the solution C into the mixed solution, and stirring for 10-30 min;
(5) Rolling the cleaned foaming nickel to be attached to the inner wall of a polytetrafluoroethylene reaction kettle, and transferring the mixed solution prepared in the last step to the reaction kettle for reaction for 2-10 h at 120-180 ℃;
(6) Collecting the foaming nickel after reaction, flushing, placing into a tube furnace, and calcining at 350-500 ℃ in an inert gas atmosphere for 1-6 h to obtain the copper-nickel oxide composite nanowire film.
2. The use of the copper-nickel oxide composite nanowire film according to claim 1 for catalyzing the alcoholysis of ammonia borane to produce hydrogen, wherein the molar ratio of the cupric salt to the cupric salt in step (1) is 3:2.
3. the use of a copper nickel oxide composite nanowire film for catalyzing the alcoholysis of ammonia borane to produce hydrogen according to claim 1, wherein the step (6) uses ethanol and water to repeatedly rinse the reacted expanded nickel.
4. The use of a copper nickel oxide composite nanowire film according to claim 1 for catalyzing the alcoholysis of ammonia borane to produce hydrogen, wherein: cutting the copper-nickel oxide composite nanowire film, and putting the copper-nickel oxide composite nanowire film into a methanol solution containing ammonia borane and sodium hydroxide.
Priority Applications (1)
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