CN115634693B - Preparation method of nanocomposite with hollow tube structure and application of nanocomposite in catalyzing aminoborane alcoholysis to produce hydrogen - Google Patents
Preparation method of nanocomposite with hollow tube structure and application of nanocomposite in catalyzing aminoborane alcoholysis to produce hydrogen Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 14
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 78
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 15
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 13
- 229940078494 nickel acetate Drugs 0.000 claims description 13
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical group [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 10
- 229940039790 sodium oxalate Drugs 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229940039748 oxalate Drugs 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000002131 composite material Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002071 nanotube Substances 0.000 description 5
- SJIHVGHAFMPBSY-UHFFFAOYSA-N O=[Ni].O=[Cu] Chemical compound O=[Ni].O=[Cu] SJIHVGHAFMPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
Classifications
-
- 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 application discloses a preparation method of a nanocomposite with a hollow tube structure, which relates to the technical field of nano catalytic materials; the method comprises the following steps: s1, dissolving soluble cupric salt and divalent nickel salt in water to prepare mixed salt solution A; s2, adding 2-20 mmol of oxalate into water, stirring and dissolving to form solution B; s3, slowly dropwise adding the solution B into the solution A through a separating funnel under the condition of high-speed stirring to form a solution C, and stirring for 5-15 min; s4, transferring the solution C to a reaction kettle, reacting for 2-10 hours at 120-200 ℃, filtering and washing, taking solid at the bottom of the reaction kettle, and reacting for 1-5 hours in a muffle furnace at 250-350 ℃; the application also provides an application of the nanocomposite prepared by the preparation method as a catalyst in catalyzing aminoborane alcoholysis to produce hydrogen; the scheme provided by the application is simple in preparation process operation, low in cost and easy for industrial production, and has an excellent effect in catalyzing ammonia borane to produce hydrogen.
Description
Technical Field
The application relates to the technical field of nano catalytic materials, in particular to a preparation method of a nano composite material with a hollow tube structure and application of the nano composite material in catalyzing aminoborane alcoholysis to produce hydrogen.
Background
Hydrogen is considered as the most ideal alternative to fossil energy as a clean energy source. The development of safe, efficient and stable hydrogen storage materials is one of the biggest challenges facing current research into hydrogen energy applications. Ammonia borane (NH) 3 BH 3 AB) due to its higher hydrogen storage density (146 g.L -1 The mass fraction is 19.6 percent), and the characteristics of safety, innocuity, high chemical stability and the like become an important chemical solid hydrogen storage material. The ammonia borane hydrolysis hydrogen production reaction conditions are mild, but need to be carried out in the presence of a suitable catalyst. The hydrogen production rate of the aminoborane alcoholysis can be remarkably improved by adjusting the active components, the particle size, the dispersity of the active components, the electronic structure and the like of the catalyst.
At present, ammonia borane is decomposed to produce hydrogen in three ways: thermal decomposition, hydrolysis and alcoholysis. Due to the high AB thermal decomposition temperature, and the polymer [ -B ] is accompanied in the process of thermal decomposition and hydrogen release 3 N 3 H 6 -] n NH as a gaseous byproduct 3 、B 2 H 6 And B 3 N 3 H 6 And various byproducts are generated, so that the method is difficult to be practically applied. In contrast to the pyrolysis of ammonia borane, ammonia borane can release 3 equivalents of hydrogen by hydrolysis or alcoholysis at room temperature by the introduction of a suitable catalytic system.
Ammonia borane hydrolyzes in concentrated solutions to release ammonia gas which can poison Pt-based fuel cell catalysts, while AB hydrolysates cannot be recovered due to the strong B-O bonds. Compared with the former two decomposition hydrogen production modes, the AB alcoholysis hydrogen production method has the advantages of more stability under the environmental condition and pure H production 2 No ammonia gas is released, and the decomposition byproducts are easily converted into ammonia borane. Therefore, the research of the catalytic ammonia borane alcoholysis hydrogen production system has important practical significance.
Noble metals (such as Rh, pd, ru and Pt) have been widely studied in the catalytic alcoholysis of ammonia borane to produce hydrogen; however, the precious metal cannot realize large-scale industrialized application due to the problems of storage content and cost, so that in the field of ammonia borane catalytic hydrogen production, the prepared catalyst is realized by using metal elements with more storage content and lower cost by a simple preparation method, and is one of preconditions for realizing the large-scale industrialized popularization of ammonia borane catalytic hydrogen production.
Disclosure of Invention
The technical scheme provided by the application effectively realizes the setting of the nickel-copper ratio in the raw materials, and the whole preparation process is simple to operate, environment-friendly, very good in experimental reproducibility, low in cost, easy for industrial production and excellent in effect of catalyzing ammonia borane hydrogen production.
In order to achieve the technical purpose, the application provides a preparation method of a nanocomposite with a hollow tube structure and application of the nanocomposite in catalyzing aminoborane alcoholysis to produce hydrogen, and in a first aspect, the application provides a preparation method of the nanocomposite with the hollow tube structure, which comprises the following steps:
s1, dissolving soluble cupric salt and divalent nickel salt in water to prepare mixed salt solution A;
s2, adding 2-20 mmol of oxalate into 20-100 mL of water, stirring and dissolving to form solution B;
s3, slowly dropwise adding the solution B to the solution A through a separating funnel under the condition of high-speed stirring to form a solution C, and stirring for 5-15 min;
s4, transferring the solution C to a reaction kettle, reacting for 2-10 hours at 120-200 ℃, filtering and washing, and reacting for 1-5 hours at 250-350 ℃ in a muffle furnace.
Preferably, the oxalate is sodium oxalate.
Preferably, in step S1, ni is contained 2+ /Cu 2+ Mixed salt solution a in a molar ratio of 4:1.
Preferably, the soluble cupric salt is selected from one of cupric chloride, cupric sulfate, cupric nitrate and cupric acetate.
Among them, copper acetate is further preferable.
Preferably, the soluble divalent nickel salt is selected from one of nickel chloride, nickel sulfate, nickel nitrate and nickel acetate.
Of these, nickel acetate is further preferable.
Preferably, in step S4, the reaction kettle bottom solid is reacted in a muffle furnace at 350 ℃ for 4 hours.
Preferably, in step S2, cu 2+ ：Ni 2+ ：C 2 O 4 2- The molar ratio of (2) is 1:4:10.
in a second aspect of the invention, the present application provides the use of a nanocomposite prepared by any of the above-described methods for catalyzing the alcoholysis of ammonia borane to produce hydrogen as a catalyst.
Compared with the prior art, the beneficial effect of this application lies in:
(1) The invention adopts a hydrothermal synthesis method, the oxalate is ingeniously selected as a precursor of the precipitant for generating the nickel oxide-copper oxide precipitate, and a proper calcination temperature is selected for calcining and synthesizing the composite hollow nanotube, 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, easy for industrial production and capable of producing the nickel oxide-copper oxide hollow nanotube in a large scale;
(2) The nickel oxide-copper oxide nano material prepared by the method has better performance in catalyzing aminoborane alcoholysis to produce hydrogen, and is expected to realize industrialized preparation of a catalyst for catalyzing to produce hydrogen.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is an XRD spectrum of a sample obtained in example 3;
FIG. 2 is a SEM schematic of the sample obtained in example 3;
FIG. 3 is a SEM schematic of the sample obtained in example 4;
FIG. 4 is a SEM schematic of the sample obtained in example 5;
fig. 5 is a SEM schematic of the sample obtained in example 6.
Detailed Description
The following detailed description of the present invention will provide further understanding of the objects, features and advantages of the present invention by way of example. Several embodiments of the invention are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete:
example 1
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 10mmol of sodium oxalate into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at the temperature of 250 ℃ in a muffle furnace to obtain compound powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 5mL of hydrogen gas was produced in 1 minute.
Example 2
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 10mmol of sodium oxalate into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 300 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 10mL of hydrogen gas was produced in 1 minute.
Example 3
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 10mmol of sodium oxalate into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 350 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 20mL of hydrogen gas was produced in 1 minute.
Further referring to fig. 1 and 2, the crystallization effect of the target product is better as seen in fig. 1, the hollow tube structure of the target product is seen in fig. 2, and the molding effect is good.
Example 4
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 10mmol of sodium oxalate into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 400 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 7mL of hydrogen gas was produced in 1 minute.
With further reference to FIG. 3, it can be seen that the target product eventually does not have hollow nanotubes formed, resulting in nanorod agglomerates with diameters of 300-400 nm.
Example 5
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 10mmol of hexamethylenetetramine into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 350 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 8mL of hydrogen gas was produced in 1 minute.
With further reference to fig. 4, it can be seen with reference to fig. 4 that the target product eventually has no hollow nanotubes formed, resulting in nanoplatelets.
Example 6
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 10mmol of sodium hydroxide into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 350 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 8mL of hydrogen gas was produced in 1 minute.
With further reference to fig. 5, it can be seen with reference to fig. 5 that the target product eventually has no hollow nanotubes formed, resulting in nanoparticles.
Example 7
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 2mmol of sodium oxalate into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 350 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 9mL of hydrogen gas was produced in 1 minute.
Example 8
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 5mmol of sodium oxalate into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 350 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 14mL of hydrogen gas was produced in 1 minute.
Example 9
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 15mmol of sodium oxalate into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 350 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 16mL of hydrogen gas was produced in 1 minute.
Example 10
S1, dissolving 4mmol of nickel acetate and 1mmol of copper acetate in 40mL of water, and stirring for 3 minutes to form a mixed solution A;
s2, adding 20mmol of sodium oxalate into 40mL of water, stirring and dissolving; stirring the solution B at a high speed;
s3, slowly dropwise adding the solution B into the solution A through a separating funnel to form a solution C, and continuously stirring for 5min;
s4, transferring the solution C into a 100mL reaction kettle to react for 6 hours at 170 ℃; and (3) filtering and washing the solid at the bottom of the reaction kettle, and reacting for 4 hours at 350 ℃ in a muffle furnace to obtain composite powder, namely a target product.
10mg of the composite powder prepared by the above method was put into a methanol solution containing 5mmol of sodium hydroxide and 3mmol of ammonia borane as a catalyst, and about 12mL of hydrogen gas was produced in 1 minute.
It should be noted that, without conflict, the embodiments and features of the embodiments in the present application may be combined with each other.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the present application in any way, and any simple modification, equivalent variations and modification made to the above embodiments according to the technical principles of the present application are within the scope of the technical solutions of the present application.
Claims (6)
1. The application of a nanocomposite with a hollow tube structure as a catalyst in catalyzing aminoborane alcoholysis to produce hydrogen is characterized in that: the preparation method of the nanocomposite material with the hollow tube structure comprises the following steps:
s1, dissolving soluble cupric salt and divalent nickel salt in water to prepare mixed salt solution A;
s2, adding 2-20 mmol of oxalate into water, stirring and dissolving to form solution B;
s3, slowly dropwise adding the solution B to the solution A through a separating funnel under the condition of high-speed stirring to form a solution C, and stirring for 5-15 min;
s4, transferring the solution C to a reaction kettle, reacting for 2-10 hours at 120-200 ℃, filtering and washing, taking solid at the bottom of the reaction kettle, and reacting for 1-5 hours at 250-350 ℃ in a muffle furnace;
the oxalate is sodium oxalate.
2. The use according to claim 1, characterized in that: configured to contain Ni in step S1 2+ /Cu 2+ Mixed salt solution a in a molar ratio of 4:1.
3. The use according to claim 1, characterized in that: the soluble cupric salt is selected from one of cupric chloride, cupric sulfate, cupric nitrate and cupric acetate.
4. The use according to claim 1, characterized in that: the soluble divalent nickel salt is selected from one of nickel chloride, nickel sulfate, nickel nitrate and nickel acetate.
5. The use according to claim 1, characterized in that: in step S4, the reactor bottom solid was reacted in a muffle furnace at 350℃for 4h.
6. The use according to claim 1, characterized in that: in step S2, cu 2+ ：Ni 2+ ：C 2 O 4 2- The molar ratio of (2) is 1:4:10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211214002.1A CN115634693B (en) | 2022-09-30 | 2022-09-30 | Preparation method of nanocomposite with hollow tube structure and application of nanocomposite in catalyzing aminoborane alcoholysis to produce hydrogen |
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| CN202211214002.1A CN115634693B (en) | 2022-09-30 | 2022-09-30 | Preparation method of nanocomposite with hollow tube structure and application of nanocomposite in catalyzing aminoborane alcoholysis to produce hydrogen |
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| Publication Number | Publication Date |
|---|---|
| CN115634693A CN115634693A (en) | 2023-01-24 |
| CN115634693B true CN115634693B (en) | 2024-01-26 |
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| CN105381800A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Non-noble metal oxide combustion catalyst, and preparation method and use thereof |
| CN108996557A (en) * | 2018-06-22 | 2018-12-14 | 安徽师范大学 | A kind of hollow ball structure nickel oxide/copper oxide composite nano materials and preparation method thereof |
| CN109225284A (en) * | 2017-07-11 | 2019-01-18 | 中国科学院理化技术研究所 | A kind of hydrogen storage material decomposition hydrogen release system |
| CN109663595A (en) * | 2018-12-11 | 2019-04-23 | 中科廊坊过程工程研究院 | A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage |
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| US8318126B2 (en) * | 2009-05-04 | 2012-11-27 | Wong Stanislaus S | Methods of making metal oxide nanostructures and methods of controlling morphology of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105381800A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Non-noble metal oxide combustion catalyst, and preparation method and use thereof |
| CN109225284A (en) * | 2017-07-11 | 2019-01-18 | 中国科学院理化技术研究所 | A kind of hydrogen storage material decomposition hydrogen release system |
| CN108996557A (en) * | 2018-06-22 | 2018-12-14 | 安徽师范大学 | A kind of hollow ball structure nickel oxide/copper oxide composite nano materials and preparation method thereof |
| CN109663595A (en) * | 2018-12-11 | 2019-04-23 | 中科廊坊过程工程研究院 | A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage |
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