CN110075899A - A kind of preparation method for the bimetallic catalyst that porous boron nitride is nano-fibre supported - Google Patents
A kind of preparation method for the bimetallic catalyst that porous boron nitride is nano-fibre supported Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title description 54
- 229910052582 BN Inorganic materials 0.000 title description 53
- 239000000243 solution Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229910016507 CuCo Inorganic materials 0.000 claims abstract description 17
- 239000013049 sediment Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005119 centrifugation Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 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 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
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000013528 metallic particle Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 238000009777 vacuum freeze-drying Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 8
- 229910003336 CuNi Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229910002441 CoNi Inorganic materials 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002023 wood Substances 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
-
- B01J35/394—
-
- B01J35/58—
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- C01B3/068—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 the hydrogen being generated from the water as a result of a cyclus of reactions, not covered by groups C01B3/063 or C01B3/105
-
- 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 present invention is a kind of preparation method of bimetallic catalyst that porous BN is nano-fibre supported.This method comprises the following steps: porous BN nanofiber being added in deionized water and alcohol mixed solution, BN sediment is collected；BN sediment is added in mantoquita and M mixed salt solution again, sediment is obtained and is add to deionized water, NaOH solution and NaBH is added dropwise4In mixed solution, black product is collected by centrifugation, vacuum freeze drying obtains CuCo/BNNFs compound.The present invention not only can effectively improve the dispersibility of metallic particles, but also have excellent chemical stability, can make it is compound after catalyst there is good catalytic effect and cycle performance.
Description
Technical field
Technical solution of the present invention belongs to catalytic field, specially a kind of bimetallic that porous boron nitride is nano-fibre supported
The preparation method of catalyst and its application in terms of being catalyzed ammonia borane hydrolysis hydrogen manufacturing.
Background technique
Porous boron nitride (BN) nanofiber is a kind of by being mutually communicated or closed hole constitutes the BN of network structure and receives
Rice fibrous material such as high-specific surface area and hole configurations abundant, but also has six sides not only with the characteristic of porous material
Many attracting characteristics of BN material, including high-termal conductivity, chemical inertness and high antioxidant.With porous carbon analog phase
Than the superior chemical stability of porous BN is conducive to their cycle performance, and the sp of B-N when being used as catalyst carrier2
Before hydridization facilitates the stabilisation of nano-component, thus porous BN nanofiber has wide application in terms of the catalyst carrier
Scape.
Report at present about hexagonal AlN load type metal catalyst is relatively fewer, and preparation process is relative complex, performance
Poor, catalytic rate is in 1000mL H2min-1g-1Below.Such as Liu et al. in a nitrogen atmosphere to metal ammonification boron complexes and
KBH4900 DEG C of annealings are carried out, the base metal bimetallic CoNi nano particle being wrapped in h-BN is prepared.After load
Composite material granular dispersion is more uniform, but its particle diameter is larger, causes the rate for being catalyzed ammonia borine hydrogen release lower, only
176.19mL H2min-1g-1(D.L.Fan,X.M.L,J.Feng,S.Y.Zhang,J.Bai,R.Q.Lu and J.Liu,
Int.J.Hydrogen Energy,2017,42,11312-11320).Huang etc. is born Cu nano particle using solvent-thermal method
It is loaded in h-BN nanometer sheet, prepared catalyst shows excellent cycle performance, but the metal loaded is monometallic, easy oxygen
To change and reunites, the catalytic activity shown is lower, and influence of the reaction temperature, reaction time of this method to material structure is very big,
And reaction time longer (X.Q.Qiu, X.Wu, Y.W.Wu, Q.W.Liu, C.J.Huang, Rsc.Adv., 2016,6,106211-
106217).Thus the BN load type bimetal catalyst for finding a kind of simple, short preparation period preparation method synthesizing efficient is
One meaningful work.
Summary of the invention
It is an object of the invention to it is nano-fibre supported to provide a kind of porous BN for deficiency present in current techniques
The preparation method of bimetallic catalyst.This method is using porous BN nanofiber as carrier, using immersion reduction method by transition
Ni metal and another transition metal M (Co, Ni, Fe) (magnetic base metal) are supported on porous BN nanofiber, prepared
Catalyst there is high-specific surface area, metallic particles can be evenly dispersed in porous BN nanofiber surface, and particle diameter is small
In 10nm, uniform particle diameter, and catalyst have magnetism, are easily recycled and recycle.The presence of porous BN nanofiber effectively solves
It has determined nanocatalyst reunion, the problems such as dispersion is uneven, and has enhanced the stability and dispersibility of catalyst.Metal and carrier
Between interaction combined with the synergistic effect between bimetallic, enhance metallic catalyst catalysis ammonia borane hydrolysis work
Property.
The technical scheme is that
A kind of preparation method for the bimetallic catalyst that porous BN is nano-fibre supported, includes the following steps:
(1) preparation of porous BN nanofiber: selecting melamine and boric acid for raw material, be dissolved in deionized water, dense
Degree is that every milliliter of water contains 0.01~0.04g melamine and 0.01~0.4g boric acid, and 80~90 DEG C of heating is extremely dissolved, and is kept the temperature
6~8h takes out cooled to room temperature, filters to obtain white solid；
(2) white solid that upper step obtains is redissolved in deionized water, then 90 DEG C of 3~4h of holding pass through liquid nitrogen
It is rapidly frozen hot solution, solution is made all to be transformed into white solid, and is 48~72 hours dry in vacuum freeze drier, is obtained
To White Flocculus；Finally, 1000~1200 DEG C of 3~5h of heat treatment under nitrogen atmosphere in tube furnace, it is porous for obtaining product
Hexagonal AlN nanofiber；
Wherein, 0.006~0.008g white solid is added in every 1mL deionized water；Heat treatment heating rate is 5
~20 DEG C/min；Nitrogen gas flow velocity is 50~100mL/min；
(3) preparation of porous BN nano-fibre supported bimetallic Cu-M catalyst:
The porous BN nanofiber prepared in step (2) is added in the first mixed solution, 5~30min is ultrasonically treated,
It is stirred for 10~60min, then by the way that BN sediment is collected by centrifugation；
Wherein, the first mixed solution is mixed by deionized water and ethyl alcohol, and volume ratio is deionized water: ethanol solution=
1:0.1~1；The porous BN nanofiber of 10~150mg is added in the first mixed solution of every 10-30 milliliter；
(4) BN sediment is added in mantoquita and M mixed salt solution to form the first suspension, continuously stir 10~
After 120min, supernatant is removed by centrifugation, and sediment is add to deionized water, obtains the second suspension；Later, exist
The second mixed solution is added drop-wise in the second suspension under the conditions of ice-water bath, reacts 1~3h, until bubble-free generates stopping；Centrifugation
Black product is collected, after being washed respectively with ethyl alcohol and deionized water, and dry 12 in vacuum freeze drier~for 24 hours, it obtains
CuCo/BNNFs compound；
Wherein, 10~150mg BN sediment is added in every 5mL mantoquita and M mixed salt solution；Mantoquita and M mixed salt solution
In, the molar ratio of mantoquita and M salt is 1:0.1~10, the concentration of copper ion and M ion and be 30~210mM；Every 5 milliliter first
The sediment that suspension generates is added in 5~10 ml deionized waters；Volume ratio is the second suspension: the second mixed solution=
1:1；Second mixed solution is by NaOH solution and NaBH4Solution mixes, and volume ratio is NaOH solution: NaBH4Solution=1:1
~5, the NaOH solution and NaBH4The solution concentration (mass fraction) of solution is respectively 0.5~1.0wt%.
The mantoquita is copper nitrate, copper chloride or copper sulphate；M salt is cobalt, the nitrate of nickel or iron, chlorate or sulfuric acid
Salt.
The dispersion frequency of the ultrasound is 40Hz.
Revolving speed when the described centrifuge separation is 8000~10000r/min.
The application of the porous BN nano-fibre supported bimetallic catalyst, for being catalyzed ammonia borane hydrolysis hydrogen manufacturing.
Substantive distinguishing features of the invention are as follows:
In current techniques, BN material load type metallic catalyst mostly uses solvent-thermal method and high temperature reduction method to prepare, process
Relative complex, catalytic performance is poor.The present invention, will be double using immersion reduction method on the basis of synthesizing porous BN nanofiber
Metal Supported obtains composite catalyst on its surface.Pretreatment of the porous BN nanofiber dispersion in mixed solution, metal salt
The selection of the reaction conditions such as concentration and condition of ice bath of reducing agent in the concentration and metallic particles reduction process of solution, not only
Can effectively improve the dispersibility of metallic particles, and there is excellent chemical stability, can make it is compound after catalysis
Agent has good catalytic effect and cycle performance.
The invention has the following beneficial effects:
1. the present invention prepares porous BN nanofiber by three-step synthesis method first, then uses immersion reduction method by double gold
Belong to load on the surface thereof.The length of BN nanofiber is up to 2~10 μm, and diameter is 20~120nm, and metallic particles is received in BN
Rice fiber surface is evenly dispersed, average diameter of particles 7.2nm.
2. the raw material that the present invention uses belongs to the industrial chemicals of industrialized production, cost is relatively low.It is easy to get, adopts
Synthesis technology is easy to operate, and reaction time is short, and reaction process low energy consumption, low pollution.
3. the porous nano-fibre supported bimetal type catalyst of BN prepared by the present invention has higher than general catalyst
Stability.BN nanofiber disperses bimetal nano particles effectively on its surface, avoids and reacted as carrier
Catalytic activity caused by metallic particles is reunited in journey reduces, so that the service life of catalyst extends, and institute of the present invention
Obtaining catalyst has magnetism, is easily isolated, easily facilitates recycling for catalyst.
4. catalyst synthesized by the present invention can be used for being catalyzed ammonia borane hydrolysis hydrogen manufacturing, there is preferable catalytic rate.This
It invents resulting nanocatalyst catalysis ammonia borane hydrolysis hydrogen release yield and reaches as high as 3387.1mL min-1g-1, compared to similar
Base metal is supported on hydrogen discharging rate (100~1500mL min of the catalyst on h-BN-1g-1) be higher by very much, solve BN
Problem uneven for catalysis material dispersion and that catalytic activity is not high.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectrogram of the porous BN nanofiber and CuCo/BNNFs compound that prepare in embodiment 1.
Fig. 2 is the scanning electron microscope diagram of porous BN nanofiber and CuCo/BNNFs compound in embodiment 1；Its
In, Fig. 2 a is the figure of porous BN nanofiber, and Fig. 2 b is the figure of CuCo/BNNFs compound；
Fig. 3 is the transmission electron microscope figure and high-resolution transmission electron microscopy of CuCo/BNNFs compound in embodiment 1
Mirror figure；Wherein, Fig. 3 a and Fig. 3 b is respectively the transmission electron microscope figure of CuCo/BNNFs compound, and Fig. 3 c is CuCo/BNNFs
The grain size distribution of compound, Fig. 3 d are the high resolution transmission electron microscopy of CuCo/BNNFs compound；
Fig. 4 is CuCo/BNNFs complex catalysts ammonia borane hydrolysis hydrogen release figure in embodiment 1-5.
Fig. 5 is the scanning electron microscope diagram of CuNi/BNNFs compound in embodiment 9.
Fig. 6 is CuNi/BNNFs complex catalysts ammonia borane hydrolysis hydrogen release figure in embodiment 9-13.
Specific embodiment
The present invention is further described with specific example with reference to the accompanying drawing.
Embodiment 1
It selects melamine and boric acid for raw material, is dissolved in 1000 ml deionized waters, concentration is that every milliliter of water contains
0.012g melamine and 0.018g boric acid, 90 DEG C of heating dissolve it sufficiently and keep the temperature 6h, take out cooled to room temperature, take out
Filter to obtain white solid；White solid is redissolved in deionized water, concentration is that every milliliter of water contains 0.008g white solid,
Then 90 DEG C of holding 3h are rapidly frozen hot solution by liquid nitrogen, so that solution is all transformed into white solid, and dry in vacuum refrigeration
It is 72 hours dry in dry machine (- 50 DEG C of temperature, 20Pa), obtain White Flocculus；Finally, in tube furnace 1050 under nitrogen atmosphere
DEG C heat treatment 4h, heating rate be 5 DEG C/min, gas flow rate 100mL/min, obtain porous BN nanofiber.
The porous BN nanofiber 50mg prepared is weighed, the mixed solution (body of 10mL deionized water and ethyl alcohol is dispersed in
Product is than being 9:1) in, ultrasonic treatment 5min (ultrasonic dispersion frequency is 40Hz) is stirred for 30min, then by being collected by centrifugation
BN sediment.BN sediment 45mg is added to 5mL and contains 26.5mg copper chloride (i.e. 0.155mmol) and 147mg cobalt chloride (i.e.
To form suspension in mixed solution 0.618mmol), after continuously stirring 30min, by solution centrifuge separation, (revolving speed is
8000r/min), supernatant is removed, obtained precipitating is transferred in round-bottomed flask with 5mL deionized water, is stirred evenly, in ice water
By the freshly prepd NaOH of 5mL (0.9wt%, 1mL) and NaBH under the conditions of bath4(0.9wt%, 4mL) mixed solution is added drop-wise to round bottom
In the solution of flask, 1h is reacted, until bubble-free generates, black product is collected by centrifugation, washs two respectively with ethyl alcohol and deionized water
Secondary, (- 50 DEG C of temperature, 20Pa) dryings of vacuum refrigeration obtain CuCo/BNNFs compound in 12 hours.
The diffraction maximum of the CuCo/BNNFs compound of XRD spectrum display preparation in attached drawing 1 comes from h-BN and cube Cu, Cu
The diffraction maximum of phase is clear, sharp, shows that crystallinity is good, without finding the apparent peak Co in map, illustrates that Co may be with nothing
Amorphous form exists；Attached drawing 2 is the SEM figure of porous BN nanofiber and CuCo/BNNFs compound, it can be seen that BN Nanowire
The length of dimension is up to 2~10 μm, and diameter is 20~120nm, and surface is smooth, after metal-loaded nano particle, BN nanofiber
Surface become coarse, many metal nanoparticles are evenly dispersed on the surface of BN nanofiber；It is tested by TEM (attached
Fig. 3) it will be clear that the high porosity structure of BN nanofiber, and the metal nanoparticle with relatively uniform size
It is fixed on the surface of BN nanofiber, average diameter of particles 7.2nm, HRTEM photo clearly demonstrates unordered in BNNF
BN layer, the d spacing of~0.21nm corresponds to (111) crystal face in Cu, the lattice fringe of Co is not observed, shows in metal
Co exists as amorphous phase in particle, this is consistent with XRD result.Attached drawing 4 is CuCo/BNNFs complex catalysts ammonia in embodiment 1
Borane hydrolysis passes through the hydrogen release figure of multichannel minimum gas metering device (model Rock-Solar- I) test, can by hydrogen release figure
Find out that the nano material can be used as catalyst ammonia borane hydrolysis, hydrogen-producing speed is 3387.1mL min-1g-1。
Copper chloride and cobalt chloride dosage are shown in Table 1 in embodiment 2-5, other experimental implementations and drug dosage and 1 phase of embodiment
Together.
Copper chloride and cobalt chloride dosage in 1 embodiment 2-5 of table
The resulting CuCo/BNNFs composite structure pattern of embodiment 2-5 with embodiment 1, hydrogen-producing speed is 2132.2~
2944.0mL min-1g-1。
In embodiment 6-8 BN nanofiber and metal salt mixture mixing time variation be respectively 10min, 60min,
100min, other experimental implementations and drug dosage are same as Example 1.The resulting same embodiment of CuCo/BNNFs composite structure
1。
Embodiment 9
It selects melamine and boric acid for raw material, is dissolved in 1000 ml deionized waters, concentration is that every milliliter of water contains
0.012g melamine and 0.018g boric acid, 90 DEG C of heating dissolve it sufficiently and keep the temperature 6h, take out cooled to room temperature, take out
Filter to obtain white solid；White solid is redissolved in deionized water, concentration is that every milliliter of water contains 0.008g white solid,
Then 90 DEG C of holding 3h are rapidly frozen hot solution by liquid nitrogen, so that solution is all transformed into white solid, and dry in vacuum refrigeration
It is 72 hours dry in (- 50 DEG C of temperature, 20Pa) in dry machine, obtain White Flocculus；Finally, in tube furnace under nitrogen atmosphere
1050 DEG C of heat treatment 4h, heating rate are 5 DEG C/min, gas flow rate 100mL/min, obtain porous BN nanofiber.
The porous BN nanofiber 50mg prepared is weighed, the mixed solution (body of 10mL deionized water and ethyl alcohol is dispersed in
Product is than being 4:1) in, ultrasonic treatment 5min (ultrasonic dispersion frequency is 40Hz) is stirred for 30min, then by being collected by centrifugation
BN sediment.BN sediment 45mg is added to 5mL and contains copper chloride (102.3mg, i.e. 0.598mmol) and nickel chloride
To form suspension in the mixed solution of (71.2mg, i.e. 0.299mmol), after continuously stirring 30min, solution is centrifugated
(revolving speed 8000r/min) removes supernatant, and obtained precipitating is transferred in round-bottomed flask with 5mL deionized water, and stirring is equal
It is even, by the freshly prepd NaOH of 5mL (0.9wt%, 2mL) and NaBH under the conditions of ice-water bath4(0.9wt%, 3mL) mixed solution drop
It is added in the solution of round-bottomed flask, reacts 1h, until bubble-free generates, black product is collected by centrifugation, with ethyl alcohol and deionization moisture
It does not wash twice, (- 50 DEG C of temperature, 20Pa) dryings of vacuum refrigeration obtain CuNi/BNNFs compound in 12 hours.
Attached drawing 5 is the SEM figure of the CuNi/BNNFs compound prepared in embodiment 9, it can be seen that metallic particles is supported on
BN nanofiber surface, and even particle distribution.Attached drawing 6 is CuNi/BNNFs complex catalysts ammonia borane hydrolysis in embodiment 9
Hydrogen release figure, can be seen that the nano material can be used as catalyst ammonia borane hydrolysis by hydrogen release figure, hydrogen-producing speed is
1520.7mL min-1g-1。
Copper chloride and nickel chloride dosage are shown in Table 2 in embodiment 10-13, other experimental implementations and drug dosage and embodiment 9
It is identical.
Copper chloride and nickel chloride dosage in 2 embodiment 10-13 of table
The resulting CuNi/BNNFs composite structure pattern of embodiment 10-13 with embodiment 6, hydrogen-producing speed is 1135.8~
1335.6mL min-1g-1。
In embodiment 14-16 BN nanofiber and metal salt mixture mixing time variation be respectively 10min, 60min,
100min, other experimental implementations and drug dosage are same as Example 9.The resulting same embodiment of CuNi/BNNFs composite structure
9。
As carrying out morphology analysis to sample obtained by above embodiments, we can see that: composite wood prepared by the present invention
Expect that pattern is uniform, metal nanoparticle is equably supported on the surface of BN nanofiber, and the presence of BN nanofiber is effectively dropped
The low size of metallic particles makes particle diameter in 10nm hereinafter, finally obtained nano-structured calalyst is catalyzed ammonia borine water
The performance of solution is fine, and hydrogen-producing speed is up to 3387.1mL min-1g-1。
Unaccomplished matter of the present invention is well-known technique.
Claims (5)
1. a kind of preparation method for the bimetallic catalyst that porous BN is nano-fibre supported, it is characterized in that this method includes following step
It is rapid:
(1) it the preparation of porous BN nanofiber: selects melamine and boric acid for raw material, is dissolved in deionized water, concentration is
Every milliliter of water contains 0.01~0.04g melamine and 0.01~0.4g boric acid, and 80~90 DEG C of heating is extremely dissolved, and heat preservation 6~
8h takes out cooled to room temperature, filters to obtain white solid；
(2) white solid that upper step obtains is redissolved in deionized water, 90 DEG C of 3~4h of holding, it is then quick by liquid nitrogen
Hot solution is freezed, solution is made all to be transformed into white solid, and is 48~72 hours dry in vacuum freeze drier, is obtained white
Color floccule；Finally, 1000~1200 DEG C of 3~5h of heat treatment under nitrogen atmosphere in tube furnace, obtaining product is porous six side
BN nanofiber；
Wherein, 0.006~0.008g white solid is added in every 1mL deionized water；Heat treatment heating rate is 5~20
℃/min；Nitrogen gas flow velocity is 50~100mL/min；
(3) preparation of porous BN nano-fibre supported bimetallic Cu-M catalyst:
The porous BN nanofiber prepared in step (2) is added in the first mixed solution, is ultrasonically treated 5~30min, then stir
10~60min is mixed, then by the way that BN sediment is collected by centrifugation；
Wherein, the first mixed solution is mixed by deionized water and ethyl alcohol, and volume ratio is deionized water: ethanol solution=1:
0.1~1；The porous BN nanofiber of 10~150mg is added in the first mixed solution of every 10-30 milliliter；
(4) BN sediment is added in mantoquita and M mixed salt solution to form the first suspension, continuously stirs 10~120min
Afterwards, supernatant is removed by centrifugation, and sediment is add to deionized water, obtains the second suspension；Later, in ice-water bath
Under the conditions of the second mixed solution is added drop-wise in the second suspension, react 1~3h, until bubble-free generate stopping；It is collected by centrifugation black
Color product, after being washed respectively with ethyl alcohol and deionized water, and dry 12 in vacuum freeze drier~for 24 hours, obtain CuCo/
BNNFs compound；
Wherein, 10~150mg BN sediment is added in every 5mL mantoquita and M mixed salt solution；In mantoquita and M mixed salt solution, copper
The molar ratio of salt and M salt is 1:0.1~10, the concentration of copper ion and M ion and be 30~210mM；Every 5 milliliter of first suspension
The sediment of generation is added in 5~10 ml deionized waters；Volume ratio is the second suspension: the second mixed solution=1:1；The
Two mixed solutions are by NaOH solution and NaBH4Solution mixes, and volume ratio is NaOH solution: NaBH4Solution=1:1~5, institute
State NaOH solution and NaBH4The solution concentration (mass fraction) of solution is respectively 0.5~1.0wt%.
2. the preparation method of porous BN nano-fibre supported bimetallic catalyst as described in claim 1, it is characterized in that institute
Stating mantoquita is copper nitrate, copper chloride or copper sulphate；M salt is cobalt, the nitrate of nickel or iron, chlorate or sulfate.
3. the preparation method of porous BN nano-fibre supported bimetallic catalyst as described in claim 1, it is characterized in that institute
The dispersion frequency for the ultrasound stated is 40Hz.
4. the preparation method of porous BN nano-fibre supported bimetallic catalyst as described in claim 1, it is characterized in that institute
The revolving speed when centrifuge separation stated is 8000~10000r/min.
5. the application of porous BN nano-fibre supported bimetallic catalyst as described in claim 1, it is characterized in that for urging
Change ammonia borane hydrolysis hydrogen manufacturing.
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