CN108745403A - A kind of preparation method and application of boron nitride load Ni-MoOx nanocatalysts - Google Patents
A kind of preparation method and application of boron nitride load Ni-MoOx nanocatalysts Download PDFInfo
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- CN108745403A CN108745403A CN201810599201.6A CN201810599201A CN108745403A CN 108745403 A CN108745403 A CN 108745403A CN 201810599201 A CN201810599201 A CN 201810599201A CN 108745403 A CN108745403 A CN 108745403A
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- 229910052582 BN Inorganic materials 0.000 title claims abstract description 53
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910015711 MoOx Inorganic materials 0.000 title claims abstract description 50
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- 229910000085 borane Inorganic materials 0.000 claims abstract description 34
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 229910015667 MoO4 Inorganic materials 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 208000012826 adjustment disease Diseases 0.000 claims description 3
- 238000000527 sonication Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 31
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 229910052796 boron Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 abstract 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000011684 sodium molybdate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- RAXSQXIANLNZAF-UHFFFAOYSA-N boron;hydrazine Chemical compound [B].NN RAXSQXIANLNZAF-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910015444 B(OH)3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910006078 NiCuMo Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
-
- 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
-
- 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 discloses a kind of boron nitride to load Ni-MoOxThe preparation method and application of nanocatalyst prepares the aqueous solution of hexagonal boron nitride BN, finely dispersed hexagonal boron nitride BN aqueous solutions is obtained after supersound process；By NiCl2Aqueous solution is added in the BN aqueous solutions of step 1, continues to stir to get mixed solution A；Again by Na2MoO4Aqueous solution is added in mixed solution A, and continues to stir, and obtains mixed solution B；By 20~60mg sodium borohydrides NaBH4It is added in mixed solution B, stirring 5-15min carries out reduction reaction, obtains boron nitride load Ni-MoOxNanocatalyst.The present invention loads Ni-MoO using the quick reduction method of a step to synthesize boron nitridexNanocatalyst can be completed at room temperature, have many advantages, such as that generated time is short, easy to operate；By the Ni-MoO of synthesisx/ BN catalyst still has 100% conversion ratio, 100% hydrogen selective and preferable cyclical stability and high catalytic activity for being catalyzed hydrazine borine aqueous solution 323K decomposing hydrogen-productions under the conditions of the catalyst is existing for no any additive.
Description
Technical field
The present invention relates to catalyst preparation and the sustainable development field of environment and the energy, especially a kind of boron nitride is negative
Carry Ni-MoOxThe preparation method and application of nanocatalyst.
Background technology
Hydrogen Energy causes extensive research interest as a kind of clean and efficient green energy resource, it can be extensive
Applied to fields such as power generation and fuel cells.But that there are efficiency is low, safety for traditional pressure pan and low temperature liquid hydrogen storage method
Property difference and it is of high cost the shortcomings of, therefore it is research hotspot instantly to research and develop safe and efficient hydrogen storage method.
Hydrazine borine (N2H4BH3, HB), it is at room temperature the solid of safety and stability, hydrogen content is up to 15.4wt%, therefore
It is considered as a kind of promising chemical hydrogen storage material.Complete decomposition (the N of hydrazine borine2H4BH3+3H2O→B(OH)3+N2H4+3H2)
Consist of two parts, i.e. BH3The hydrolysis of group and N2H4The selectivity of component is decomposed.For HB-3H2It is theoretical for O systems
Weight hydrogen storage content is 10.0wt%.In order to enable hydrazine borine is maximized as the efficiency of hydrogen storage material, it is necessary to avoid N2H4It is endless
It is complete to decompose (3N2H4→4NH3+N2), this is because the NH generated3It is toxic to fuel-cell catalyst.Therefore, research and development are simple, economical
Further to improve the hydrogen desorption kinetics performance and hydrogen selective of hydrazine borine it is it as hydrogen storage material with efficient catalyst
The key of material.
Be presently used for the catalyst that hydrazine borine decomposes completely be nearly all containing noble metal component, but it is of high cost, storage
The problems such as amount is few limits the large-scale practical application of noble metal-based catalysts.And in the non-precious metal catalyst of report, greatly
Partial conversion ratio all only has 50% so that the utilization rate of catalyst is relatively low.
In conclusion find a kind of simple and efficient way synthesize it is cheap, efficiently and the nanometer of good dispersion is urged
Agent is very important for reducing catalyst cost and improving hydrazine borine dehydrogenation reaction efficiency.
Invention content
The invention aims to solve the deficiencies in the prior art, a kind of boron nitride load Ni-MoO is providedxIt receives
The preparation method and application of rice catalyst.
In order to achieve the above objectives, the present invention is implemented according to following technical scheme：
A kind of boron nitride load Ni-MoOxThe preparation method of nanocatalyst, includes the following steps：
Step 1: compound concentration is the aqueous solution of the hexagonal boron nitride BN of 0.5~6mg/mL, disperseed after supersound process
Uniform hexagonal boron nitride BN aqueous solutions；
Step 2: by the NiCl of 0.01~5mL2Aqueous solution is added in the BN aqueous solutions of step 1, continue stirring 1~
After 10min, mixed solution A is obtained；
Step 3: again by the Na of 0.01~5mL2MoO4Aqueous solution is added in the mixed solution A of step 2, and continues to stir
It mixes, obtains mixed solution B；
Step 4: by 20~60mg sodium borohydrides NaBH4It is added in the mixed solution B of step 3, stirs as reducing agent
It mixes 5-15min and carries out reduction reaction, obtain boron nitride load Ni-MoOxNanocatalyst.Obtained boron nitride load Ni-MoOx
Nanocatalyst is the structure of amorphous/low-crystallinity, and Ni is metallic state, and Mo is oxidation state, and Ni-MoOxNano-particle is uniform
It is dispersed on BN carriers, particle size is about 1.1-4.1nm.
Further, sonication treatment time is 15~120min in the step 1.
Further, the NiCl in the step 22A concentration of 0.05-0.5M of solution.
Further, the Na in the step 32MoO4A concentration of 0.05-0.5M of solution, and Ni：The molar ratio of Mo is 1:
1。
Further, the NaBH in the step 44The temperature that reduction reaction is carried out with mixed solution B is room temperature.
In addition, the present invention also provides a kind of boron nitride to load Ni-MoOxThe application of nanocatalyst, for being catalyzed hydrazine boron
Alkane aqueous solution is in temperature of fuel cell<Hydrolytic hydrogen production reacts within the scope of 353K.
Further, the specific steps are：Boron nitride is loaded into Ni-MoOxNanocatalyst is distributed in water, and it is molten that NaOH is added
It is alkalinity that liquid, which adjusts pH value of solution, adds hydrazine borine aqueous solution, and adjustment reaction temperature is 323K, and wherein boron nitride loads Ni-
MoOxThe molar ratio of nanocatalyst and hydrazine borine is 0.001~0.5, and measures generated hydrogen by gas burette.
Further, the NaOH concentration is 0.5-2M, a concentration of 0.5-2M of hydrazine borine aqueous solution.
Compared with prior art, the solution have the advantages that：A kind of boron nitride of the present invention loads Ni-MoOxNanometer is urged
The method of agent loads Ni-MoO using the quick reduction method of a step to synthesize boron nitridexNanocatalyst, at room temperature can be complete
At, have many advantages, such as that generated time is short, it is easy to operate, and significantly improve Ni-MoOxDispersibilities of the NPs on BN substrates and
Reduce the particle size of metal NPs；By the Ni-MoO of synthesisx/ BN catalyst is decomposed for being catalyzed hydrazine borine aqueous solution 323K
Hydrogen manufacturing still has high catalytic activity, 100% conversion under the conditions of the catalyst is existing for no any additive
Rate, 100% hydrogen selective and preferable cyclical stability and high catalytic activity, may be implemented hydrazine boron in 5 minutes
The complete decomposition of alkane, TOF values are up to 600h-1, far above at present it has been reported that NiCuMo (conversion ratio 100%, TOF are
108h-1), Ni NPs (conversion ratio 50%, TOF 183h-1)、Ni@Rh4Ni/Al2O3(conversion ratio 95.7%, TOF 71.7h-1), Ni0.9Pt0.1/ rGO (conversion ratio 100%, TOF 240h-1) etc. catalyst, and Ni-MoOxThere is no making for noble metal in/BN
With effectively reducing the cost of catalyst.Wherein MoOxAddition effectively reduce the crystallinity of catalyst, formation has
The Ni-MoO of amorphous/low-crystallinex/ BN nanocatalysts, compared with crystalline structure, non crystalline structure has more unsaturated positions
Point and dangling bonds, therefore there is better catalytic activity.Generally speaking, this method can be as a kind of new simple functionalization
Method, come synthesize with amorphous/low-crystallinity boron nitride load Ni-MoOxCatalyst answers synthesized catalyst
For hydrazine borine, decomposing hydrogen-production reacts at a temperature of 323K, safe efficient, honest and clean to develop with extraordinary catalytic activity
The catalyst of valence provides new approach, and further promotes application of the hydrazine borine as hydrogen storage material in real life.
Description of the drawings
Fig. 1 is Ni-MoOxThe schematic diagram of/BN catalyst preparations；
The X-ray diffraction spectrogram for the catalyst that Fig. 2 is embodiment 1, prepared by comparative example 1, comparative example 2；
Fig. 3 (a) is Ni-MoO in embodiment 1xNi-MoO in/BN, comparative example 1x, in comparative example 2 Ni/BN catalyst Ni
The x-ray photoelectron spectroscopy of 2p (b) is Ni-MoO in embodiment 1xThe x-ray photoelectron spectroscopy of the Mo 3d of/BN catalyst；
Fig. 4 is Ni-MoO in embodiment 1x/ BN catalyst transmission electron microscope pictures；
Fig. 5 be embodiment 1, comparative example 1, comparative example 2 prepare catalyst be catalyzed at 323K hydrazine borine decompose when it is m-
Conditional curve.
Fig. 6 is Ni-MoO in embodiment 1x/ BN is catalyzed the cycle performance curve graph of hydrazine borine decomposition at 323K.
Specific implementation mode
With reference to specific embodiment, the invention will be further described, in the illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1
As shown in Figure 1, a kind of boron nitride loads Ni-MoOxThe preparation method of nanocatalyst, includes the following steps：
Step 1: compound concentration is the aqueous solution 15mg of the hexagonal boron nitride BN of 0.5~6mg/mL, supersound process 15~
Finely dispersed hexagonal boron nitride BN aqueous solutions are obtained after 120min；
Step 2: by the NiCl of 0.1mmol2, it is added in the BN aqueous solutions of step 1, after continuing 1~10min of stirring,
Obtain mixed solution A；
Step 3: again by the Na of 0.1mmol2MoO4It is added in the mixed solution A of step 2, and continues to stir, mixed
Close solution B；And Ni：The molar ratio of Mo is 1:1；
Step 4: by 30mg sodium borohydrides NaBH4It is dissolved in the distilled water of 1mL, step 3 is added to as reducing agent
5-15min is stirred in mixed solution B, at 25 DEG C and carries out reduction reaction, obtains boron nitride load Ni-MoOxNanocatalyst.
Boron nitride made from embodiment 1 is loaded into Ni-MoOxNanocatalyst is dried in vacuo；With reference to figure 2, x-ray powder
Diffraction (XRD) the result shows that, prepared boron nitride load Ni-MoOxNanocatalyst is the structure of amorphous/low-crystalline, and
The XRD results of sample can be clearly seen that the diffraction maximum of metal after annealing；Boron nitride made from embodiment 1 is loaded into Ni-
MoOxNanocatalyst is dried in vacuo；With reference to figure 3, x-ray photoelectron spectroscopy (XPS) the result shows that, the embodiment successfully synthesize
Boron nitride loads Ni-MoOxNanocatalyst, and Ni mainly exists with metallic state, Mo mainly exists with oxidation state；It will implement
Boron nitride made from example 1 loads Ni-MoOxNano-catalytic dilution agent drops in carbon and supports on film, dry；It is electric with reference to being transmitted in figure 4
Sub- microscope (TEM) is the results show that Ni-MoOx/ BN samples have smaller particle size (~2.6nm) and uniform dispersion
Property.
Embodiment 2
A kind of boron nitride load Ni-MoOxThe preparation method of nanocatalyst, includes the following steps：
Step 1: compound concentration is the aqueous solution 15mg of the hexagonal boron nitride BN of 0.5~6mg/mL, supersound process 15~
Finely dispersed hexagonal boron nitride BN aqueous solutions are obtained after 120min；
Step 2: by the NiCl of 0.05mmol2Aqueous solution is added in the BN aqueous solutions of step 1, continue stirring 1~
After 10min, mixed solution A is obtained；
Step 3: again by 0.05mmolNa2MoO4Aqueous solution is added in the mixed solution A of step 2, and continues to stir,
Obtain mixed solution B；And Ni：The molar ratio of Mo is 1:1；
Step 4: by 20mg sodium borohydrides NaBH4It is dissolved in the distilled water of 1mL, step 3 is added to as reducing agent
In mixed solution B, 5-15min is stirred at room temperature and carries out reduction reaction, obtain boron nitride load Ni-MoOxNanocatalyst.
Embodiment 3
A kind of boron nitride load Ni-MoOxThe preparation method of nanocatalyst, includes the following steps：
Step 1: compound concentration is the aqueous solution 15mg of the hexagonal boron nitride BN of 6mg/mL, it is ultrasonically treated 15~120min
After obtain finely dispersed hexagonal boron nitride BN aqueous solutions；
Step 2: by the NiCl of 0.5mmol2Aqueous solution is added in the BN aqueous solutions of step 1, continue stirring 1~
After 10min, mixed solution A is obtained；
Step 3: again by the Na of 0.5mmol2MoO4Aqueous solution is added in the mixed solution A of step 2, and continues to stir,
Obtain mixed solution B；And Ni：The molar ratio of Mo is 1:1；
Step 4: by 60mg sodium borohydrides NaBH4It is dissolved in the distilled water of 1mL, step 3 is added to as reducing agent
In mixed solution B, 5-15min is stirred at room temperature and carries out reduction reaction, obtain boron nitride load Ni-MoOxNanocatalyst.
Embodiment 4
A kind of boron nitride load Ni-MoOxThe application of nanocatalyst, for being catalyzed hydrazine borine aqueous solution in fuel cell
Operating temperature<Hydrolytic hydrogen production reacts within the scope of 353K, the specific steps are：Boron nitride is loaded into Ni-MoOxNanocatalyst disperses
Into water, the NaOH solution that a concentration of 0.5-2M is added adjusts pH value of solution as alkalinity, adds the hydrazine borine of a concentration of 0.5-2M
Aqueous solution, adjustment reaction temperature are 323K, and wherein boron nitride loads Ni-MoOxThe molar ratio of nanocatalyst and hydrazine borine is
0.001~0.5, and generated hydrogen is measured by gas burette.The boron nitride of the present embodiment loads Ni-MoOxNano-catalytic
Agent is catalyzed the hydrogen manufacturing amount (n of hydrazine borine aqueous solution hydrogen production processgas/nHB) with time (minute) figure as shown in figure 5, catalysis hydrazine borine
Hydrolytic hydrogen production can generate the gas of 6 equivalents in 5 minutes at a temperature of 323K, and conversion ratio reaches 100%.
Ni-MoO is loaded in boron nitridexAfter nanocatalyst catalysis hydrazine borine first round decomposition reaction terminates, equivalent
Hydrazine borine (0.5M, 2mL) solution is added to by constant pressure funnel in twoport flask, remaining operation with react before
It is identical.Same operating procedure is repeated four times under 323K bath temperatures, as shown in fig. 6, prepared boron nitride loads Ni-
MoOxNanocatalyst has good cyclical stability for catalysis hydrazine borine dehydrogenation reaction, after 5 circle of reaction, although it is anti-
It is increased slightly between seasonable, but still with 100% conversion ratio.
Comparative example 1
By the NiCl of 0.1mmol2With the Na of 0.1mmol2MoO4It is dissolved in 5mL aqueous solutions, stirs evenly；30mg's
NaBH4It is dissolved in the distilled water of 1mL, at 25 DEG C, which is added to in above-mentioned mixed solution magnetic agitation is uniform, is stirred
It mixes to complete reduction, you can Ni-MoO is madexCatalyst.As the XRD diagram piece of Fig. 2 can obtain Ni-MoOxSample also has amorphous/low
Crystalline structure.By Ni-MoOxCatalyst is distributed in water, and the NaOH of 10mmol is added, and adds the hydrazine borine of 1mmol,
And generated hydrogen is measured by gas burette.This time Ni-MoOxThe hydrogen manufacturing amount of catalyst hydrazine borine hydrogen production process
ngas/nHB) with time (minute) figure as shown in figure 5, catalysis the hydrogen manufacturing of formic acid Hydrolysis At Room Temperature hydrazine boron can be realized in 16.67 minutes
The complete decomposition of alkane.
Comparative example 2
By the NiCl of 0.1mmol2It is dissolved in the BN aqueous solutions of 15mg, stirs evenly；The NaBH of 30mg4It is dissolved in 1mL's
Distilled water, at 25 DEG C, it is uniform which is added to magnetic agitation in above-mentioned mixed solution, and stirring is to complete reduction, i.e.,
Ni/BN catalyst can be made.If the XRD diagram piece of Fig. 2 can obtain, Ni/BN samples are then crystal structure.Ni/BN catalyst is disperseed
Into water, the NaOH of 10mmol is added, adds the hydrazine borine of 1mmol, and generated hydrogen is measured by gas burette.This
Secondary Ni-MoOxThe hydrogen manufacturing amount n of catalyst hydrazine borine hydrogen production processgas/nHB) with time (minute) figure as shown in figure 5, catalysis
The hydrogen manufacturing of formic acid Hydrolysis At Room Temperature can realize the complete decomposition of hydrazine borine in 53.7 minutes.
Technical scheme of the present invention is not limited to the limitation of above-mentioned specific embodiment, every to do according to the technique and scheme of the present invention
The technology deformation gone out, each falls within protection scope of the present invention.
Claims (8)
1. a kind of boron nitride loads Ni-MoOxThe preparation method of nanocatalyst, which is characterized in that include the following steps：
Step 1: compound concentration is the aqueous solution of the hexagonal boron nitride BN of 0.5~6mg/mL, it is uniformly dispersed after supersound process
Hexagonal boron nitride BN aqueous solutions；
Step 2: by the NiCl of 0.01~5mL2Aqueous solution is added in the BN aqueous solutions of step 1, continues 1~10min of stirring
Afterwards, mixed solution A is obtained；
Step 3: again by the Na of 0.01~5mL2MoO4Aqueous solution is added in the mixed solution A of step 2, and continues to stir, and is obtained
To mixed solution B；
Step 4: by 20~60mg sodium borohydrides NaBH4It is added in the mixed solution B of step 3 as reducing agent, stirs 5-
15min carries out reduction reaction, obtains boron nitride load Ni-MoOxNanocatalyst.
2. boron nitride according to claim 1 loads Ni-MoOxThe preparation method of nanocatalyst, it is characterised in that：It is described
Sonication treatment time is 15~120min in step 1.
3. boron nitride according to claim 1 loads Ni-MoOxThe preparation method of nanocatalyst, it is characterised in that：It is described
NiCl in step 22A concentration of 0.05-0.5M of solution.
4. boron nitride according to claim 1 loads Ni-MoOxThe preparation method of nanocatalyst, it is characterised in that：It is described
Na in step 32MoO4A concentration of 0.05-0.5M of solution, and Ni：The molar ratio of Mo is 1:1.
5. boron nitride according to claim 1 loads Ni-MoOxThe preparation method of nanocatalyst, it is characterised in that：It is described
NaBH in step 44The temperature that reduction reaction is carried out with mixed solution B is room temperature.
6. a kind of boron nitride as described in claim 1 loads Ni-MoOxThe application of nanocatalyst, which is characterized in that for urging
Change hydrazine borine aqueous solution in temperature of fuel cell<Hydrolytic hydrogen production reacts within the scope of 353K.
7. boron nitride according to claim 6 loads Ni-MoOxThe application of nanocatalyst, which is characterized in that specific steps
For：Boron nitride is loaded into Ni-MoOxNanocatalyst is distributed in water, and it is alkalinity that NaOH solution, which is added, and adjusts pH value of solution, then is added
Enter hydrazine borine aqueous solution, adjustment reaction temperature is 323K, and wherein boron nitride loads Ni-MoOxNanocatalyst rubs with hydrazine borine
You measure generated hydrogen than being 0.001~0.5, and by gas burette.
8. boron nitride according to claim 7 loads Ni-MoOxThe application of nanocatalyst, it is characterised in that：The NaOH
A concentration of 0.5-2M, a concentration of 0.5-2M of hydrazine borine aqueous solution.
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